- JCF Berlin

Transcription

- JCF Berlin

1 5 th
JCF-Frü h j ah rssym posi u m
M a rc h 6 t h - 9 t h , 2 0 1 3
B e rl i n
S p o n s o rs
Imprint
JungChemikerForum Berlin
2013
LATEX realization by courtesy of the JCF Erlangen-Nürnberg
We are grateful to Hans-Jörg Drescher for his help with the LATEX code.
Contents
Greetings
1
Program
7
Information
15
Plenary Lectures
23
Prof. Hashmi (Thursday 9:30 - 10:30)
24
Dr. Loth (Thursday 14:50 - 15:50)
26
Dr. habil. Becker (Friday 9:10 - 10:10)
28
Prof. Schreiner (Friday 14:50 - 15:50)
30
Prof. Roth (Saturday 11:30 - 12:30)
32
Oral Presentations
35
Session 1 (Thursday 10:50 - 12:00)
36
39
42
Session 4 (Friday 10:30 - 12:00)
46
50
53
Posters
Poster Session 1 (Thursday 17:40 - 20:10)
Poster Session 2 (Saturday 9:00 - 11:30)
57
58
188
Index
315
Sudoku
329
Greetings
1
Liebe Jungchemikerinnen und Jungchemiker,
in diesem Jahr treffen Sie sich zu Ihrem Forum in Berlin, einer Stadt, die dank ihrer
zahlreichen Hochschulen und weiterer Forschungseinrichtungen in besonderer Weise
dazu geeignet ist, sich über Wissenschaft auszutauschen. Sie ist zugleich aber auch
besonderes Symbol für Deutschland, für Vereinigung von Ost und West und für internationale Sichtbarkeit. Das sind wichtige Charakteristika, wenn Sie miteinander
reden wollen über unsere Wissenschaft, die Chemie - ihre Inhalte, ihre Bedeutung
und ihre Relevanz für die Zukunft unserer Gesellschaft!
Bereits im letzten Jahr schrieb ich Ihnen, wie wichtig und gut ich es finde, dass
Sie mit der aufwändigen Organisation und Durchführung der jährlich stattfindenden
Konferenz des Jungchemikerforums das persönliche Treffen und das Gespräch über
elektronische Kommunikationswege setzen. Täglich erlebe ich in meinem Beruf als
Professorin an einer Universität, dass Ideen und Einsichten, gedankliche Fortschritte
und neue wissenschaftliche Ergebnisse durch persönliche, barrierelose Gespräche und
Diskussionen geboren werden oder zur Reife gelangen. Nur so ersetzen wir in meiner
Überzeugung Routine und Mittelmass durch Inspiration und Exzellenz. Sie wissen es
alle: Eine Gruppe von Menschen ist mehr als die Summe einzelner Personen.
In diesem Sinne wünsche ich Ihnen auch für 2013, dass sie in Berlin die Faszination von Wissenschaft und menschlicher Begegnung spüren, in überdurchschnittlichen,
anspruchsvollen und kurzweiligen Vorträgen, an Postern, in Diskussionsrunden und
bei geselligen Treffen.
Prof. Dr. Barbara Albert
(Präsidentin der Gesellschaft Deutscher Chemiker e.V.)
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Dear “Jungchemiker“,
it provides me with great pleasure to welcome all of you to the 15th JCF Spring
Symposium here at Berlin’s Humboldt-Universität. Based on the great tradition of
this unique event, I am absolutely convinced that you will enjoy the next few days
with lots of exciting new chemistry, inspiring discussions, and joyful moments.
Right from the beginning, I wish to thank all of the people, who were involved in the
excellent organization. After all it is an event for young chemists by young chemists
and you did a marvelous job.
I am particularly grateful that this event has developed in such a success story as it
brings together the people, who actually DO the science. While academic supervisors
are concerned with arguably too much management, administration, and politics, it is
mostly doctoral students such as YOU, who are carrying out experiments on a daily
basis thereby paving the way to new scientific discoveries. The JCF Spring Symposia
are a great platform to meet and get to know the person behind a specific type of
research. After all, science is being carried out by individuals and it’s communication
among them that makes science a unique social endeavor as well.
In this spirit, I wish you a great and successful symposium – enjoy the chemistry in
all dimensions!
Prof. Stefan Hecht, Ph.D.
(Dean of the Faculty of Mathematics and Natural Sciences I of the Humboldt-Universität
zu Berlin)
3
Dear Participants,
it is my great pleasure to welcome you to this conference on behalf of the whole
organizing team! We are the Berlin division of the Young Chemists Forum. Our
members are either studying chemistry or doing their PhD work here in the capital
of Germany.
Berlin has got three universities with chemistry studying courses as well as a few other
colleges that pursue related topics. The local Young Chemists Forum meets once a
month to exchange experiences, share ideas and also organize events.
In the past two years, we have respectively hosted a one-day scientific symposium on
the natural science campus of the Humboldt-Universität. This year, we have worked
hard in order to incorporate our experiences into this year’s Frühjahrssymposium to
make it truly enjoyable for all of you. But a symposium like this would not be feasible
without a long list of supporters. We are extremely grateful for the big number of
institutes, companies and organizations that helped us in various ways to make this
conference happen. We are also very thankful for all the helpers that lend us a hand
and serve your coffee.
Once again, welcome to Berlin and enjoy the conference!
Christin Büchner
(Chair of the Young Chemists Forum Berlin)
4
Dear participants of the 15th Frühjahrssymposium,
I am very pleased to welcome you on behalf of the JungChemikerForum to the Frühjahrssymposium at the Humboldt-Universität zu Berlin this year.
The continuous rising number of participants shows the obvious success of the Frühjahrssymposium and the increasing need for communication between young scientists.
But especially the great number of the international students allows an interesting
and wide-ranging exchange of knowledge. In consideration of present scientific challenges, like increasing lack of raw materials, growing and ageing world population
and related food supply and medical care, the motivated young scientists all over the
world can contribute to solutions of problems of our everyday life by meeting and
exchanging at a conference like the Frühjahrssymposium.
The planning and carrying out of such a big event would not be possible without
a great team. For that reason I want to thank on behalf of all participants of the
Frühjahrssymposium the organization team and the assistants for the great job. Furthermore I want to express my gratitude to all the companies for the financial support.
I wish all participants a pleasant time in Berlin, fruitful discussions, creative ideas
and many new friends.
Anna Hofmann
(Chair of the Young Chemists Forum of the German Chemical Society)
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6
Program
7
Wednesday (March 6th )
12:00 – 20:00
Registration
Unter den Linden 6 - Foyer
12:00 – 19:00
Strukturwettbewerb - Organized by JCF Jena
Dorothenstr. 24 - Room 1.406
16:00 – 20:00
JCF Sprechertreffen
Dorothenstr. 24 - Room 1.103
16:00 – 19:00
City Tour
Unter den Linden 6
16:00 – 17:00
Boat Trip
Unter den Linden 6
20:00 – 23:00
Welcome Reception - Sponsored by Lanxess
Dorothenstr. 24 - Foyer
8
Thursday (March 7th )
8:50 – 9:30
Opening Ceremony
Unter den Linden 6 - Kinosaal
Christin Büchner
Chair of the 15th JCF Frühjahrssymposium
Prof. Dr. Peter Frensch
Vice President for Research of the Humboldt-Universität zu Berlin
Prof. Dr. Stefan Hecht
Dean of the Faculty of Mathematics and Natural Sciences I
Prof. Dr. Eckhard Ottow
Vice President of the German Chemical Society (GDCh)
Anna Hofmann
Chair of the Young Chemists Forum (JCF)
9:30 – 10:30
Plenary Lecture
Prof. Dr. S. Hashmi - Ruprecht-Karls-Universität Heidelberg
"Gold Catalysis 2.0"
10:50 – 12:00
Session 1
Anne-Kathrin Baum - Universität Hamburg
"Sugar Complexes and the Asymmetric Transfer Hydrogenation"
Laith Almazahreh - Friedrich-Schiller-Universität Jena
"Novel [FeFe] Hydrogenase Models with (SCH2 )2 P=O Linker"
Burkhard Butschke - The Weizmann Institute of Science, Rehovot
"From ’Rollover’ Cyclometalation towards the Catalytic
Dehydrogenation of Alkanes"
12:00 – 12:20
Conference Photo
Unter den Linden 6
9
13:30 – 14:30
Session 2
Björn Raimer - Technische Universität Braunschweig
"New Insights into the Chemistry of Photoaffinity Labeling with
Diazirines"
Chiara Palumbo - Sapienza University of Rome
"Asymmetric synthesis of Natural-product-inspired Spiro
epoxyoxindoles via Hydrogen-Bond Organocatalysis"
Guillaume Povie - Universität Bern
"Polar Effects in Hydrogen Atom Transfers from Catechols
to Alkyl Radicals"
14:50 – 15:50
Plenary Lecture
Dr. S. Loth - Center for Free-Electron Laser Science, Hamburg
"Atom-by-atom assembly of stable nanomagnets"
16:10 – 17:40
Session 3
Maria Wuithschick - Humboldt-Universität zu Berlin
"Understanding the Growth Mechanism: Key to Size Control
of Colloidal Nanoparticles"
Lydia Liebscher - Technische Universität Dresden
"PbS-mesocrystals - Coherence between atomistic arrangement
and internal nanocrystal superstructure ordering"
Jonathan De Roo - Ghent University
"Synthesis of BaZrO3 , Ta2 O5 and HfO2 nanoparticles as artificial
pinning centers in High Temperature Superconductors"
Krzysztof Sozanski - Polish Academy of Sciences, Warsaw
"Viscosity at the Nanoscale"
17:40 – 20:10
Poster Session 1 and Champagne Reception
Unter den Linden 6 - Senatssaal
10
Friday (March 8th )
9:10 – 10:10
Plenary Lecture
Dr. habil. J. S. Becker - Forschungszentrum Jülich
"Mass Spectrometry Imaging (MSI) of Elements in Biological Tissue"
10:30 – 12:00
Session 4
Gerrit Hermann - BOKU Wien
"Studying arsenic in cancer cells by elemental speciation analysis"
Inga Pfeffer - University of Oxford
"2-Oxoglutarate Oxygenases as Therapeutic Targets"
Fernando Gomollon-Bel - Universidad de Zaragoza
"Design and synthesis of fungical transglycosidase inhibitors"
Aleksandra Kubica - Jagiellonian University, Krakow
"2 H NMR spectroscopy in application to selected amino-acids"
13:30 – 14:30
Session 5
P. Skupin-Mrugalska - Poznan University of Medical Sciences
"Synthesis and development of the novel phthalocyanine derivatives
possessing 2-(morpholin-4-yl)ethyloxy groups of potential applications
in photodynamic therapy"
Sören Gehne - University of Potsdam
"Novel drug carrier systems - Spectroscopic characterization
of cell-penetrating peptide analogous"
Torsten Rossow - Freie Universität Berlin
"Controlled Synthesis of Cell-Laden Degradable Microgels by
Radical-Free and Supramolecular Gelation in Droplet Microfluidics"
14:50 – 15:50
Plenary Lecture
Prof. Dr. P. R. Schreiner - Justus-Liebig Universität Giessen
"Tunneling Control of Chemical Reactions"
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16:10 – 17:40
Session 6
Ismael Gracia - Universidad de Zaragoza
"Liquid Crystal and Electro-Optic Block Codendrimers:
Synthesis and Characterization"
Nicolas Dietl - Technische Universität Berlin
"Great Insights from a Small System: Structure and reactivity
of [VPO4 ]+ in comparison with [V2 O4 ]+ "
Gregor Koch - Technische Universität Berlin
"Comparison of different Cu particles supported on SBA-15 as
methanol steam reforming catalysts"
Maria Fritz - Lomonosov Moscow State University
"New Trifluoromethyl Derivatives of 5 IPR Isomers the
Fullerene C84 "
19:00 – 21:30
Conference Dinner
Unter den Linden 6 - Zeltmensa
22:00
Conference Party
Revaler Straße 99 - Cassiopeia
12
Saturday (March 9th )
9:00 – 11:30
Poster Session 2 and "Frühschoppen"
Unter den Linden 6 - Senatssaal
11:30 – 12:30
Closing Lecture
Prof. Dr. K. Roth - Freie Universität Berlin
"’Berliner Currywurst’ - Some like it hot"
12:30 – 13:30
Closing Ceremony
14:00 – 17:00
Paper Chase
Unter den Linden 6
14:20 – 17:30
Memorial Hohenschönhausen
Unter den Linden 6
17:00 – 18:30
Berlin Underworld
Badstraße/Böttgerstraße
13
14
Information
15
Poster Sessions
There will be two poster sessions. To find out in which session your poster is, go to
the index of this book and look up your name. Go to the page which is indicated
there. Beneath your abstract you’ll find the session you are in. The poster number
right next to the session you’ll need to find your poster wall.
If your poster is part of the first session: You may put up your poster during Thursday
afternoon. Since the room is used for a different event during Friday, please remove
your poster directly after the poster session. Posters that remain after the end of the
poster session will be removed.
If your poster is part of the second session: You may put up your poster on Saturday
morning right before your poster session. Please remove your poster before the start
of the social activities. Posters that remain after 2 pm will be removed.
Poster Prize
The prizes for the best posters will be awarded by all participants. All posters with
highlighting talks will be awarded in their separate category. Each participant can
cast TWO votes for EACH poster session. Both on Thursday and on Saturday each
participant can vote for one highlighted poster and one other poster.
For the Thursday session, please drop your ballot into the box (located in foyer of
poster session) by the end of the Thursday session. For the Saturday session, please
drop your ballot into the box (located in foyer of poster session) by the end of the
Saturday session.
All prizes for best posters and best talks will be handed over in the Closing Ceremony
on Saturday morning.
Information regarding Social Activities
At the registration desk you will receive vouchers for the social events that you booked.
Please have your vouchers ready for the respective social events.
On Wednesday
City Tour:
Meet at the Humboldt-Universität main building near the registration desk at 15:50.
Tour will take approximately 3 hours.
Boat Trip:
Meet at the Humboldt-Universität main building near the registration desk at 15:40.
On Saturday
Paper Chase:
Meet near the info desk on Saturday at 14:00. Tour will take approximately 3 hours.
Underworld Tours:
Tour in English: Meet near the info desk on Saturday at 16:15 or come directly to the
Bad- / corner Böttgerstraße, 13357 Berlin at 17:00. Tour in German: Meet near the
info desk on Saturday at 17:15 or come directly to the Bad- / corner Böttgerstraße,
13357 Berlin at 18:00. Tours will take approximately 1.5 hours.
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Memorial Hohenschönhausen:
Meet near the info desk on Saturday at 14:20 or come directly to the Genslerstr. 13
A, 13055 Berlin at 15:30. Tour will take approximately 2 hours.
Lunch Options
Around the main building of the Humboldt-Universität you will find various lunch
options. In the yard of the main building, the student canteen of the HumboldtUniversität is located in the large white tent. If you want to have your lunch there,
please come to the conference desk and buy a meal voucher worth 9 e (per day), as the
canteen discourages payment with cash. Around the university, you can find various
restaurants. The closer you get to either S-Bahnhof Friedrichstraße or S-Bahnhof
Alexanderplatz, the larger will be the selection of inexpensive food alternatives.
Public Transport
During the conference (Wednesday to Saturday) every participant may use the public
transport in the zones A, B, C (Berlin, Potsdam and surroundings) for free. You
need your conference nametag and an ID card or passport. All information (routes,
timetables etc.) on public transport may be found here: www.bvg.de
WLAN Access
If your home institute takes part in the eduroam project, you may use the WLAN
infrastructure of the Humboldt-Universität by just logging in with your account from
your home university. If you are not sure what eduroam is, please visit www.eduroam.org
and ask your local IT administrator for it.
In case you can not use eduroam you may ask for a guest account at the registration
desk. Unfortunatly this has several disadvantages: The connection is much slower and
less stable and you have to accept the IT regulations of the Humboldt-Universität.
Thus, please consider to use eduroam!
Science Location Berlin
With its large number of scientific institutions, Berlin provides excellent opportunities
for researchers from all over the world. Berlin is home to four universities (Freie Universität, Humboldt-Universität, Technische Unversität and Universität der Künste),
several universities of the applied sciences and 70 non-university research institutions.
The Charité hospital is the largest medicine faculty in Europe. It is a perfect example
of how basic and applied research are in symbiosis here in Berlin. You find unique
research facilities like the synchrotron radiation source BESSY, the research reactor
BER-II (both parts of the Helmholtz-Zentrum Berlin for Materials and Energy) and
the free electron laser in the Fritz-Haber-Institute of the Max-Planck-Society. As
an example for other research institutions the Max Delbrück Center for Molecular
Medicine, three additional Max-Planck-Institutes or the Federal Institute for Materials Research and Testing should be mentioned.
In so-called clusters of excellence, funded by the German government, different institutes collaborate on larger topics that are relevant from a social and economic
17
standpoint. UniCat is one of these clusters in Berlin. It deals with unifying different
concepts in heterogeneous, homogeneous and biological catalysis.
Berlin was one of the first cities to host a "long night of the sciences". In this annual
event, research institutes open their doors to the public to give people insights into
the projects they research and the methods they use. Last year over 34,000 people
came to the 73 participating academic institutions.
Berlin at a Glance
If you have a bit more time in Berlin, there is a large number of different places to go
and things to see. A few of our recommendations:
Museumsinsel
It is the name for the northern part of an island in the center of Berlin, with five
internationally significant museums. Last year this museum complex was visted by
2,75 million people. It consists of the Altes Museum (antique collection), the Neues
Museum (Prehistorical, Egyptian and Early History collections), the Alte Nationalgallerie (collection of Neoclassical, Romantic, Biedermeier, Impressionist and early
Modernist artwork), the Bode-Museum (collection of sculptures, Byzantine art, and
coins and medals) and the Pergamonmuseum (antiquity collection, the Middle East
Museum, and the Museum of Islamic art).
Naturkundemuseum
It is the largest museum of natural history in Germany with 30 million zoological,
paleontological, mineralogical, and geological objects. The mineral collection includes
75 % of all minerals in the world. Two spectacular exhibits are the largest mounted
dinosaur in the world which is 23 m long and 12 m high and an exemplar of the
earliest known bird, Archaeopteryx.
Deutsches Technikmuseum Berlin
This museum exhibits a large collection of historical technical exhibition pieces, it
is focused on the waterways and rail transport in / to Berlin and in Germany, the
beer, jewelry production and energy. Also a reproduction of the Z1, the first freely
programmable computer in the world, is shown.
Old Airport Tempelhof
Built in the 1920ies, this was the first airport in Berlin. The Nazis added a monumental airport building, the US Army used it as their air base after WWII. During
the Berlin blockade in 1948/49, the airport was a major hub for the historic airlift
that provided supplies for two million citizens. The airport was closed in 2008 and
the area converted into a recreational territory. A huge plane stretches in the middle
of the city, allowing running, skating, biking, kiting, areas for barbecues, lacrosse,
baseball, urban gardening and many more activities. You can visit for free daily from
6 AM to 7 PM. Just get off the S-Bahn at station Tempelhof and walk for 5 minutes.
Views Above the City
On Alexanderplatz, you find one of Berlins landmarks: the 356 metres high TV tower.
The visitors platform provides spectacular views in all directions. Just opposite to
the TV Tower, also on Alexanderplatz, you can visit the 37th floor of the Park Inn
Hotel and view the city centre. On Potsdamer Platz, you can use the fastest elevator
in Europe to get to a platform with a view over all the important landmarks of Berlin.
TV tower: 12 e pp http://www.tv-turm.de Park Inn: 3 e pp Just walk in and take
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the elevator to the top (only open in good weather) Panorama (Potsdamer Platz):
5.50 e p.P. http://www.panoramapunkt.de
Not a lot of time? Hop on public bus line 100!
Operating from S Alexanderplatz to S Zoologischer Garten, this bus line takes you
past a big number of the important sites in Berlin. There is Alexanderplatz, home to
the Rotes Rathaus, the town hall of Berlin and the most famous landmark of Berlin,
the TV tower which is the tallest structure in Germany. St. Marys Church is one of
the oldest churches in Berlin, the exact age is unknown. The Nikolaiviertel is the reconstructed historical heart of the city with the oldest church in Berlin Nikolaikirche,
build between 1220 and 1230. The Staatsoper Berlin unfortunately is under reconstruction at the moment, but you can try to get a glance across Bebelplatz at the very
beautiful Alte Bibliothek. On the other site of the street you can find the main building of Humboldt-Universität. The Brandenburger Tor is a building that is attached
to a lot of German history. When the copper statue of the victory goddess was first
put on top, the citizens complained that the lady was wearing too revealing clothes,
so the copper robe was added. Marking the border between Warsaw Pact and NATO,
it was a symbol of the cold war. From 1990, it became a symbol for the reunification
of Germany. The Reichstag building accommodates the German Parliament, called
the Bundestag. After the abdication of the Kaiser in 1918, the first German republic
was proclaimed to the public from one of the Reichstags balconies. The Haus der
Kulturen der Welt (Berliners call it the pregnant oyster because of its shape) was a
gift from the United States of America and is the national centre for contemporary
non-European art. Schloss Bellevue is the official residence of the German president.
Due to many reconstruction periods and the representative rooms taking up a lot of
space, there is only one German president who has actually lived in the castle (Roman
Herzog). At the Großer Stern intersection, in the center of the Großer Tiergarten,
the Siegessäule watches over the west part of Berlin. It was built after a series of wars
that lead to the unification of the many small states to the Kaiserreich. In the late
90s, the Siegessäule was the focal point for the annual Loveparade, one of the largest
Techno festivals at that time. Behind the park lies the Potsdamer Platz, an example
for the ’new Berlin’ and the urban renewal after the cold war. On the place stands
a replica of the first traffic light in Berlin from the year 1924. The Breitscheidplatz
lies at one end of the most prestigious shopping street of the city, the Kurfürstendamm. Its most striking building is the Kaiser-Wilhelm-Gedächtnis-Kirche, which
was heavily damaged in World War II, and is kept in its state as a war memorial.
The remarkably large church bells, which were made out of cannon balls captured in
the German-French war (1871) were repurposed for weaponry in 1943. The Zoologischer Garten is a zoo that also consists of a very large aquarium where marine animals
as well as reptiles, amphibians and insects can be found.
Personal Recommodation of the Organizers
District Friedrichshain:
In the triangle between S Warschauer Straße, S Ostkreuz and U Samariterstraße you
will find a large selection of bars, restaurants and pubs. Just start at one corner and
find something you like.
Near the conference venue:
Along the Oranienburger Straße you will find many international bars and restaurants. Start at S Oranienburger Straße and walk through the Oranienburger Straße
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or the small byroads. Or take a small walk starting at the conference hall along the
Friedrichstraße.
Burger Restaurant Rosenburger – Brunnenstr. 196, 10119 Berlin-Prenzl. Berg
At U Rosenthaler Platz, in Brunnenstr. 196, you get served some of the nicest burgers
in Berlin. You can choose from a range of toppings and organic meat patties are
available as well. Homemade curly fries are my personal favourite.
Que Pasa – Skalitzer Str. 107, 10997 Berlin-Kreuzberg or Oranienburger Str. 27,
10117 Berlin-Mitte Here you can eat mexican food or drink tasty cocktails. My
personal favourite is Chilli con Carne. If you are with a bigger group, you should try
this bar, as they have a bit more space.
Hops & Barley – Wühlischstr. 22/23, 10245 Berlin-Friedrichshain This pub has
its own brewery and serves several homebrewed beers and cider.
Aspendos – Hauptstraße 11, 10827 Berlin-Schöneberg This little restaurant has
Turkish specialities (including the Berlin default fast food - the Döner) in great quality.
Varadero – Vorbergstraße 11, 10823 Berlin This Cuban restaurant serves great
typical food. The music and overall atmosphere are perfect, and they make good
cocktails.
Paules Metal Eck – Krossener Straße 15, 10245 Berlin-Friedrichshain For friends
of metal musik, Paules Metal Eck can be recommended.
Vapiano – Mittelstraße 51, 10117 Berlin This self service restaurant offers you delicious low budget mediterranean food.
Villa Rixdorf – Richardplatz, 12055 Berlin There you can eat good traditional fare
in a characteristic german atmosphere.
Important Telephone Numbers
Police
Ambulance & Fire Department
Taxi (english speaking)
Poison hotline
Emergency dental service (information)
National enquiries
International enquiries
BVG (public transport) customer services
Central (public) lost property office
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110
112
(+49) 30 20 20 21 22 0
(+49) 30 19 2 40
(+49) 30 89 00 43 33
(+49) 11 8 33
(+49) 11 8 34
(+49) 30 19 4 49
(+49) 30 902 77 31 01
Map of the Conference Venue – Unter den Linden 6
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Plenary Lectures
23
Prof. Dr. A. Stephen K. Hashmi
Professor for Chemistry
Organisch-Chemisches Institut
Ruprecht-Karls-Universität Heidelberg
Im Neuenheimer Feld 270
69120 Heidelberg
Germany
[email protected]
www.hashmi.de
Curriculum Vitae
2007 –
Chair for Organic Chemistry at the Institute of Organic Chemistry of the
Ruprecht-Karls-University Heidelberg, Germany
2001 – 2007 Appointed to professor for Organic Chemistry at the Institute of Organic
Chemistry of Stuttgart University, Germany
1999 – 2000 Temporary professorship for organic chemistry at the Department of
Chemistryof Philipps-University Marburg, Germany
1998
End of the Habilitation with the initiation-lecture as Privatdozent at the
Institute of Organic Chemistry of Johann Wolfgang Goethe-Universität
Frankfurt, Germany
1995
Move with Prof. Dr. J. Mulzer to the Institute of Organic Chemistry of
Johann Wolfgang Goethe-University Frankfurt, Germany
1993
Beginning of the Habilitation in the group of Prof. Dr. J. Mulzer at the
Institute of Organic Chemistry of Free University Berlin, Germany
1991 – 1993 Postdoctoral studies in the group of Prof. B. M. Trost at Stanford University, California, USA
1983 – 1991 Chemistry studies at Ludwig-Maximilians-University Munich, Germany;
Diploma thesis in the group of Prof. Dr. G. Szeimies; Doctoral thesis in
the group of Prof. Dr. G. Szeimies
Awards
2010
Hector Research Award
2007
Prize awarded by the students for the best lecture 2007 in Chemistry at
Ruprecht-Karls-University Heidelberg
2002
ORCHEM Prize for natural sciences of the German Chemical Society
2001
Karl-Ziegler Memorial Fellowship
1999
Heisenberg Fellowship of the Deutsche Forschungsgemeinschaft
1998
Dr. Otto Röhm Memorial Fellowship
1995
Habilitanden-fellowship of the Deutsche Forschungsgemeinschaft
1993
Justus von Liebig Fellowship of the Fonds der Chemischen Industrie for
the Habilitation
1991
Postdoctoral fellowship of the Deutsche Forschungsgemeinschaft
24
Thursday 9:30 - 10:30
Plenary: Prof. Hashmi
Gold Catalysis 2.0
Stephen Hashmi
The first decade of homogeneous gold catalysis has been dominated by simple nucleophilic addition reactions.[1] The field has experienced an exponential growth during
that time. Within the last 12 months new results indicate very interesting new options, which are based on entirley new reactivity patterns and complex catalytic
cycles.[2]
[1]
a) A. S. K. Hashmi, G. J. Hutchings, Angew. Chem. 2006, 118, 8064-8105; Angew. Chem.
Int. Ed. 2006, 45, 7896-7936; b) M. Rudolph, A. S. K. Hashmi, Chem. Soc. Rev. 2012, 41,
2448-2462.
[2]
a) R. Döpp, C. Lothschütz, T. Wurm, M. Pernpointner, S. Keller, F. Rominger, A. S. K. Hashmi,
Organometallics 2011, 30, 5894-5903; b) A. S. K. Hashmi, I. Braun, P. Nösel, J. Schädlich, M.
Wieteck, M. Rudolph, F. Rominger, Angew. Chem. 2012, 124, 4532-4536; Angew. Chem. Int.
Ed. 2012, 51, 4456-4460; c) A. S. K. Hashmi, M. Wieteck, I. Braun, M. Rudolph, F. Rominger,
Angew. Chem. 2012, 124, 10785-10789; Angew. Chem. Int. Ed. 2012, 51, 10633-10637.
Plenary: Prof. Hashmi
Thursday 9:30 - 10:30
25
Dr. Sebastian Loth
Group Leader
Max Planck Research Department for Structural Dynamics
Center for Free-Electron Laser Science
Notkestrasse 85
22607 Hamburg
Germany
[email protected]
www.fastatoms.de
Curriculum Vitae
2011 –
Max-Planck Research Group - Dynamics of Nanoelectronic Systems –
Group Leader hosted at the Center for Free-Electron Laser Science, Hamburg, Germany and the Max-Planck Institute for Solid State Research,
Stuttgart, Germany
2008 – 2011 IBM Almaden Research Center, San Jose CA, USA – Postdoctoral Researcher exploration of atomically assembled nanostructures for novel
schemes in data-storage and quantum information processing
2007
Ph.D. degree in Physics, IV. Physikalisches Institut (Semiconductor
Physics) studies of nanoscale phenomena in operating semiconductor elements using low-temperature scanning tunnelling microscopy, GeorgAugust-University of Göttingen, Germany
2004
Diploma degree in Physics, Georg-August-University of Göttingen, Germany
2001 – 2002 General Manager – Olesno Konstrukcje + Montaz Sp. z o. o., Zabrze,
Poland administration and time scheduling for assembly of industrial
wood processing plants
2001
Intermediate diploma, University of Bielefeld, Germany
Awards
2008 – 2010 Feodor-Lynen research scholarship of the Alexander von Humboldt foundation
2007
Dissertation award of the Berliner-Ungewitter foundation
2005 – 2007 Doctorate scholarship of the German National Academic Foundation
26
Thursday 14:50 - 15:50
Plenary: Dr. Loth
Atom-by-atom assembly of stable nanomagnets
Sebastian Loth
The scanning tunneling microscope has changed our view of the nanoworld. Atoms are
no longer intangible objects. They can be imaged individually and even manipulated
into structures that do not exist naturally.
We focus on magnetic nanostructures and test how classical concepts of magnetism
emerge from the quantum mechanical behavior of individual atoms. We use a lowtemperature scanning tunneling microscope (STM) and assemble the nanostructures
from different transition metal elements. Inelastic tunneling spectroscopy serves as
a highly sensitive tool to achieve chemical identification of the atoms and to resolve
their magnetic properties.
With this technique we can quantify magnetic exchange interaction and follow the
evolution of magnetic states as we build the nanostructure one atom at a time. This
makes it possible to optimize arrangements of atoms that either enhance or reduce
magnetic stability. We identified a new route to create stable magnetic states using antiferromagnetic spin-spin interaction enabling a model demonstration of dense
magnetic memory with only 12 atoms per bit.[1]
[1]
Sebastian Loth, Susanne Baumann, Christopher P. Lutz, D. M. Eigler, Andreas J. Heinrich,
Science 2012, 335, 196.
Plenary: Dr. Loth
Thursday 14:50 - 15:50
27
Dr. habil. J. Sabine Becker
Leader of trace and ultratrace analysis
Forschungszentrum Jülich
Analytik (ZEA-3)
Wilhelm-Johnen-Str.
52428 Jülich
Germany
[email protected]
www.brainmet.de
Curriculum Vitae
2009 –
Head of BrainMet
1997 – 2003 Deputy head of the Central Division of Analytical Chemistry
1992 –
Head of mass spectrometry, Central Division of Analytical Chemistry,
Forschungszentrum Jülich
1988
Habilitation on "Ultrasensitive Mass Spectrometric Techniques", University Leipzig
1974 – 1991 Central Institute for Isotope and Radiation Research, Leipzig
1974
Promotion in Quantum Chemistry, University Leipzig
1967 – 1974 Studies of Chemistry, University Leipzig
Awards
2012
Winter Conference Award on Plasma Spectrochemistry sponsored by
Thermo Fisher Scientific, Tucson, Arizona
2010
IUPAC Fellow (International Union of Pure and Applied Chemistry)
2009
DGMS-Award "Massenspektrometrie in den Biowissenschaften" (Mass
Spectrometry in the Bioscience)
2001 – 2012 Different Guest Professorships at Universities and Research Centres
including Bulgaria, Rumania, France, Czech Republic, Israel, China,
Poland, Brazil, Thailand, Canada, Taiwan and the USA
1999 – 2004 Guest professor: Nuclear Research Centre, Atomic Energy Authority,
Cairo
28
Friday 9:10 - 10:10
Plenary: Dr. habil. Becker
Mass Spectrometry Imaging (MSI) of Elements in Biological
Tissue
J. Sabine Becker
The application of mass spectrometry with soft ionization techniques (ESI, electrospray ionization, and MALDI, matrix-assisted laser desorption ionization) in the life
sciences for the detection and identification of biomolecules is already well established.
The application of elemental mass spectrometry using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the determination of metals, metalloids and non-metals biological tissue is rather new and there is some hesitation in
accepting this analytical method, although it offers many advantages. Elemental and
biomolecular mass spectrometric methods are highly complementary. LA-ICP-MS, as
a solid state mass spectrometric technique, allows the direct determination of trace
elements in biological and environmental samples and is applied for microlocal and
imaging technique of elements with spatial resolution in the µm range.[1-5] Based
on the established routine BrainMet technique (BrainMet - Bioimaging of Metals in
Brain and Metallomics) in quantitative elemental imaging using LA-ICP-MS with a
spatial resolution between 200 to ∼ 10 µm, we developed the combination of a laser
microdissection apparatus to ICP-MS (LMD-ICP-MS) to imaging of metals at higher
spatial resolution (10 to < 1 µm) and develop a method combining elemental imaging
by LA/LMD-ICP-MS with molecular imaging by MALDI-MS.
Fig. 1: Mass spectrum of a line scan (top left) and images of selected metals and
non-metals measured by LA-ICP-MS in routine mode.[4]
On the basis of selected examples, it will be shown that the combination of different elemental and biomolecular mass spectrometric techniques can solve analytical problems in
the life sciences. Future developments and trends will be discussed concerning instrumental developments of new mass spectrometric techniques providing improvement of spatial
resolution and high sensitivity with lower detection limits for different application areas in
life sciences.
[1]
J. S. Becker, Inorganic Mass Spectrometry: Principles and Application, J. Wiley and Sons:
Chichester, 2007, 520 pages.
[2]
J. S. Becker et al., Mass Spectrom. Rev. 2010, 29, 156.
[3]
J. S. Becker, N. Jakubowski, Chem. Soc. Rev. 2009, 38 (7),1969-1983.
[4]
J. S. Becker, Int. J. Mass Spectrom. 2010, 289, 65-75.
[5]
J. S. Becker et al., Int. J. Mass Spectrom. 2011, 307, 3-15.
Plenary: Dr. habil. Becker
Friday 9:10 - 10:10
29
Prof. Dr. Peter R. Schreiner
Profssor for Organic Chemistry
Institute of Organic Chemistry
Justus-Liebig Universität Giessen
Heinrich-Buff-Ring 58
35392 Giessen
Germany
[email protected]
www.chemie.uni-giessen.de/schreiner
Curriculum Vitae
2002 –
Full professor of Organic Chemistry, Justus-Liebig-University Giessen
1999 – 2002 Associate Professor of Organic Chemistry, Univ. of Georgia, Athens, USA
1996 – 1999 Habilitand, Georg-August-Universität Göttingen
1995 – 1996 Project Coordinator, The Encyclopedia of Computational Chemistry
1995
Ph.D. (Computational Chem., Prof. H. F. Schaefer III), UGA, Athens,
USA
1994
Dr. rer.nat. (Organic Chem., Prof. P. v. R. Schleyer), Univ. Erlangen
1992
Dipl.Chem. (Organic Chem., Prof. P. v. R. Schleyer), Univ. Erlangen
1991
M.Sc. (Organic Chem., Prof. R. K. Hill), UGA, Athens, USA
Awards
2012
Schulich Visiting Professorship, Technion-Israel Institute of Technology
2010
P. v. R. Schleyer Lectureship Award (University of Georgia, USA)
2010
Lifetime Honorary Member, Israel Chemical Society
2009
Török Lectureship Award (Eötvös University, Budapest, Hungary)
2009
Chair, Gordon Research Conference on Physical-Organic Chemistry Molecular Design and Synthesis (New Hampshire, USA)
2003
Dirac Medal of the World Association of Theoretical and Computational
Chemists
2000
Research Innovation Award of the Research Corporation
2000
Chemical Research Publicity Award , The University of Georgia
1999
Chair, Gordon Research Conference on Physical-Organic Chemistry Molecular Design and Synthesis (New Hampshire, USA)
1999
Dirac Medal of the World Association of Theoretical and Computational
Chemists
1999
Research Innovation Award of the Research Corporation
1997 – 1999 Chemical Research Publicity Award , The University of Georgia
1996
Robert C. Anderson Memorial Award
1995
Martin-Reynolds-Smith-Award, American Chemical Society (ACS)
1993
Karl-Giehrl-Prize, Best Promotion 1994, University of Erlangen-Nürnberg
30
Friday 14:50 - 15:50
Plenary: Prof. Schreiner
Tunneling Control of Chemical Reactions[1,2]
David Ley, Dennis Gerbig, Hans Peter Reisenauer, Jan Philipp Wagner, Peter R.
Schreiner*
Chemical reactivity is traditionally understood[3,4] in terms of kinetic versus thermodynamic control,[5,6] wherein the driving force is the lowest activation barrier among
the possible reaction paths or the lowest free energy of the final products, respectively. Here we expose quantum mechanical tunneling as a third driving force that
can overwrite traditional kinetic control and govern reactivity based on nonclassical
penetration of the potential energy barriers connecting the reactants and products.
These findings are exemplified with the first experimental isolation and full spectroscopic and theoretical characterization of the elusive hydroxycarbenes (R-C-OH,
1)[7-10] that undergo facile [1,2]hydrogen tunneling to the corresponding aldehydes
under barriers of nearly 30.0 kcal mol−1 with half-lives of around 1-2 h even at
experimental temperatures as low as 10 K, despite of the presence of paths with substantially lower barriers (e.g., CH-tunneling in 1b to 3 or rearrangement of 1c to 4).
We will demonstrate that this is a general phenomenon,[11-13] as exemplified by other
OH-tunneling examples such as the rotational isomerization of monomeric benzoic
acid.[14] Such tunneling processes do not merely represent corrections to the reaction
rate, they are the reaction rate, i.e., the completely control the reaction outcome.[1]
[1]
P. R. Schreiner, H. P. Reisenauer, D. Ley, D. Gerbig, C.-H. Wu, W. D. Allen, Science 2011,
332, 1300.
[2]
D. Ley, D. Gerbig, P. R. Schreiner, Org. Biomol. Chem. 2012, 19, 3769.
[3]
H. Eyring, J. Chem. Phys. 1935, 3, 107.
[4]
M. G. Evans, M. Polanyi, Trans. Faraday Soc. 1935, 31, 875.
[5]
R. B. Woodward, H. Baer, J. Am. Chem. Soc. 1944, 66, 645.
[6]
A. G. Catchpole, E. D. Hughes, C. K. Ingold, J. Chem. Soc. 1944, 11, 8.
[7]
D. Gerbig, H. P. Reisenauer, C.-H. Wu, D. Ley, W. D. Allen, P. R. Schreiner, J. Am. Chem.
Soc. 2010, 132, 7273.
[8]
D. Gerbig, D. Ley, H. P. Reisenauer, P. R. Schreiner, Beilstein J. Org. Chem. 2010, 6, 1061.
[9]
P. R. Schreiner, H. P. Reisenauer, F. C. Pickard IV, A. C. Simmonett, W. D. Allen, E. Mátyus,
A. G. Császár, Nature 2008, 453, 906.
[10]
P. R. Schreiner, H. P. Reisenauer, Angew. Chem. Int. Ed. 2008, 47, 7071.
[11]
D. Gerbig, D. Ley, P. R. Schreiner, Org. Lett. 2011, 13, 3526.
[12]
D. Ley, D. Gerbig, J. P. Wagner, H. P. Reisenauer, P. R. Schreiner, J. Am. Chem. Soc.
2011, 133, 13614.
[13]
D. Ley, D. Gerbig, P. R. Schreiner, Chem. Sci. 2013, 2, in press.
[14]
S. Amiri, H. P. Reisenauer, P. R. Schreiner, J. Am. Chem. Soc. 2010, 132, 15902.
Plenary: Prof. Schreiner
Friday 14:50 - 15:50
31
Prof. Dr. Klaus Roth
Professor Emeritus
Institute of Chemistry and Biochemistry
Freie Universität Berlin
Takustr. 3
14195 Berlin
Germany
[email protected]
www.klausroth.de
2000 –
Professor at the Institute of Chemistry, Freie Universität Berlin
1991 – 2000 Director of Dahlem Conferences, Freie Universität Berlin
1990
Supernumerary professor, Freie Universität Berlin
1986 – 1988 Visiting Professor, University of California San Francisco
1981
Habilitation, Freie Universität Berlin
1979 – 1980 Postdoctoral research, Institute for Medical Research in Mill Hill, London
1973
Promotion, Freie Universität Berlin
1964 – 1969 Studies of Chemistry, Freie Universität Berlin
Awards
2008
Author award of the Gesellschaft Deutscher Chemiker for the book
"Chemische Delikatessen"
1986 – 1988 Max-Kade-Fellowship for a research stay as a Visiting Associate Professor
in the group of M.W. Weiner, Department of Radiology, University of
California, San Francisco
1979 – 1980 DFG-fellowship for a research stay in the group of J. Feeney, Institute for
Medical Research, London
32
Saturday 11:30 - 12:30
Plenary: Prof. Roth
“Berliner Currywurst” - Some like it hot
Klaus Roth
A typical local specialty in Berlin is the “Currywurst”, a fried sausage covered with a
sauce based mainly on tomato ketchup and a mixture of more or less hot spices. It’s
not a gourmet but fast food, and with an additional helping of French fries it contains
a four-digit number of kilocalories and keeps your stomach busy for a couple of hours.
When you order a “Currywurst”, the person behind the counter may ask you how hot
the sausage should be. You should answer quickly and exactly, because if you hesitate
too long, people in the queue behind you will start to get nervous. In that critical
moment solid chemical knowledge can be of great help.
Indeed the biochemistry of Bell Pepper and Chili has many surprises to offer. The
brilliant red color is based on the “paprika ketones”, compounds that only capsicum
can synthesize. The extraordinary pungency, which many humans all over the world
enjoy so much, is due to capsaicin and dihydrocapsaicin, which are also compounds
that only capsicum can produce. With all that knowledge about capsicums’s unique
and outstanding chemical achievements, you can order your “Currywurst”, more precisely, qualified, and relaxed, which can make a “Currywurst”, a delicious experience
you shouldn’t miss. This is just another proof that chemistry not only can be exciting
but also taste good.
Guten Appetit!
Plenary: Prof. Roth
Saturday 11:30 - 12:30
33
34
Oral Presentations
35
Sugar Complexes and the Asymmetric Transfer
Hydrogenation
Anne-Kathrin Baum, Jürgen Heck
Institut für Anorganische und Angewandte Chemie –
Fachbereich Chemie, Universität Hamburg – Martin-Luther-King-Platz 6 –
20146 Hamburg – GER
[email protected]
The use of carbohydrates as ligands offers the chance of transferring the natural
chirality from the ligand not only to the complex but, using the derived complex in
asymmetric reactions, also to a prochiral substrate.
Various carbohydrate ligands have been synthesised and applied in organometal complexes in our group.[1] Glucopyranosidato and allopyranosidato ligands with their
oxygen donor atoms were applied in zirconium and titanium complexes presenting different structural motifs and a possible application in the hydroamination reaction.[2-5]
The successful change of donor atoms from oxygen to nitrogen by synthesis of a diaminoglucoside ligand afforded the opportunity for synthesis of group 6 sugar carbonyl
complexes.[6]
To enable the use of sugar ligands in late transition metal complexes a N,O-motif was
chosen for coordination. Three ligand precursors, aminoglucopyranoside 1, aminoallopyranoside 2 and aminomannopyranoside 3, have been prepared and their coordination chemistry on ruthenium complexes of the type [Ru(η 6 − arene)Cl2 ]2 is being
investigated.[7] The first promising results applying the derived complexes in the
Asymmetric Transfer Hydrogenation have been achieved and are subject to further
studies.[7]
Just recently, the molecular structure of dichlorido(η 6 -p-cymene)(methyl-2amino-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside-κN 2 )ruthenium(II) 4 could be
determined.[7]
Molecular Structure and Structural Formula of Complex 4
[1]
[2]
[3]
[4]
[5]
[6]
[7]
36
S. Tschersich, M. Böge, D. Schwidom, J. Heck, Rev. Inorg. Chem. 2011, 31(1), 27-55.
L. Jessen, E. T. K. Haupt, J. Heck, Chem. Eur. J. 2001, 7, 3791-3797.
D. Küntzer, L. Jessen, J. Heck, Chem. Commun. 2005, 5653-5655.
D. Küntzer, S. Tschersich, J. Heck, Z. Anorg. Allg. Chem. 2007, 633, 43-45.
D. Schwidom, D. Zeysing, M. Schmidt, J. Heck, Eur. J. Inorg. Chem. 2009, 5295-5298.
C. Fowelin, A.Matyja, M. Schmidt, J.Heck, Z. Anorg. Allg. Chem. 2007, 633, 2395-2399.
A.-K. H. Baum, J. Heck manuscript in preparation.
Thursday 11:00 - 11:20
Talk 01
Novel [FeFe] Hydrogenase Models with (SCH2 )2 P=O Linker
Laith Almazahreh ∗ , Wolfgang Weigand∗ , Ulf Peter Apfel† , Wolfgang Imhof∗ ,
Helmar Görls∗ , Manfred Rudolph∗ , Mohammed El-khateeb‡
∗
Institut für Anorganische und Analytische Chemie – Friedrich-Schiller-Universität –
Humboldtstraße 8 – Jena – GER
†
Department of Chemistry – Massachussetts Institute of Technology –
77 Massachusetts Avenue – Cambridge – USA
‡
Chemistry Department – Jordan University of Science and Technology – 22110 Irbid –
JOR
[email protected]
[FeFe] Hydrogenases are enzymes that have high efficiency to catalyze reduction of
protons to form dihydrogen, which in microorganisms occur at potentials of -0.1 to
-0.55 V.[1] These high catalytic efficiency and low energy features were the impetus to
scientists for paving the way to macroscale hydrogen production, based on designing
of inexpensive electrocatalyst that resembles the structure of the [FeFe] active site
[Figure a].[2] Protonation of the Fe-Fe core to form terminal or bridging hydride, as
well as the nitrogen atom of the cofactor (SCH2 )2 NH is considered as a fundamental
step in the function of the active site to catalyze the production of hydrogen.[3] The
biological function of the azathiolate cofactor, (SCH2 )2 NH, is proposed to relay protons to and from the diiron core via agostic [Figure b] or hydrido-proton interaction
[Figure c].[4-6] In our research we introduce the synthesis of novel [FeFe] hydrogenase
models, namely [Fe2 (CO)5 X][(µ-SCH2 )2 (Ph)P=O] (X = CO, PPh3 , P(OEt)3 ) [Figure d] to investigate the influence of the P=O functionality and the ligand X toward
the electrochemical and the electrocatalytic properties of the [Fe2 S2 ] cluster in the
presence of the weak acid, acetic acid, and moderately strong acids, trifluoro acetic
acid and pyridinium cation. Herein we report a catalytic mechanism for reduction of
protons where the P=O function as protonation site and hence can be involved in proton relay. This protonation of the P=O functionality was proved by monitoring the
reaction of the complexes with HBF4 ·Et2 O by IR and 31 P NMR spectroscopic methods. High level DFT calculations of the protonation by HBF4 ·Et2 O or pyridinium
acid have been carried out considering the P=O functionality and the dithiolato sulfur
atoms as potential sites for protonation.
[1]
P. M. Vignais, B. Billoud, J. Meyer, JFEMS Microbiol. Rev. 2001, J25, 455.
C. Topf, U. Monkowius, G. Knör, J. Inorganic Chemistry Communications 2012, J21, 147.
M. G. I. Galinato, M. W. Whaley, D. Roberts, P. Wang, N. Lehnert, JEur. J. Inorg. Chem.
2011, 1147.
[4]
Y. Nicolet, A. L. de Lacey, X. Vernede, V. M. Fernandez, C. E. Hatchikian, J. C. FontecillaCamps, J. Am. Chem. Soc. 2001, J123, 1596.
[5]
Y. Nicolet, B. J. Lemon, J. C. Fontecilla-Camps, J. W. Peters, JTrends Biochem. Sci. 2000,
J25, 138.
[6]
Y. Nicolet, C. Cavazza, J. C. Fontecilla-Camps, J. Inorg. Biochem. 2002, J91, 1.
[2]
[3]
Talk 02
Thursday 11:20 - 11:40
37
From “Rollover” Cyclometalation towards the Catalytic
Dehydrogenation of Alkanes
∗
Burkhard Butschke ∗ , Helmut Schwarz†
Department of Organic Chemistry – The Weizmann Institute of Science – P.O.Box 26 –
Rehovot – ISR
†
Institut für Chemie – Technische Universität Berlin – Straße des 17. Juni 135 –
Berlin – GER
[email protected]
“Rollover” cyclometalation, which constitutes a special case of the well-known cyclometalation reaction, requires decomplexation and rotation of the ligand as key steps
prior to metal mediated C–H bond activation (1 → 2 + HX in Figure 1).[1] While
“rollover”-cyclometalated complexes are well known for a long time, their reactivity
has hardly been studied. In mass-spectrometric experiments, however, which constitute a powerful tool to probe chemical reactions in a highly idealized environment,
this particular kind of cyclometalated species exhibits a rich chemistry.[2] “Rollover”cyclometalated [Pt(bipy - H)]+ (2) (bipy = 2,2’-bipyridine) is conveniently produced
by electrospray ionization (ESI) of methanolic solutions of dimeric [Pt(CH3 )2 (µ(CH3 )2 S)]2 and 2,2’-bipyridine. In ion/molecule reactions of this complex with ethane,
the liberation of neutral ethene is observed concomitant with the formation of the
platinum-hydride complex [Pt(H)(bipy)]+ (2 + C2 H6 → 3 + C2 H4 , Figure 1). The
latter species might, based on DFT results, undergo ejection of H2 via “rollover” cyclometalation to regenerate [Pt(bipy – H)]+ (2) as demonstrated earlier for the corresponding methyl and chloro complexes [Pt(X)(bipy)]+ (1, X = CH3 , Cl).[3] This
sequence of processes might be regarded as a catalytic cycle for the oxidative dehydrogenation of ethane by “rollover”-cyclometalated [Pt(bipy - H)]+ (2) as summarized
in Figure 1. When the classically cyclometalated platinum complexes [Pt(L - H)]+
(L = 2-phenylpyridine, 7,8-benzoquinoline) are subjected to reactions with ethane,
similar processes occur as encountered for [Pt(bipy - H)]+ (2), while the relative rates
are drastically reduced when compared with the “rollover”-cyclometalated analogue.
This observation is interpreted in terms of a pathway that proceeds directly at the
cyclometalated platinum complexes instead of taking the route via retro-“rollover” cyclometalation. This process, however, which generates [Pt(L - H)(H2 )(C2 H4 )]+ as an
intermediate, is more energy demanding, which explains the decreased relative rates.
Figure 1: Illustration of the gas-phase generation of "rollover"-cyclometalated [Pt(bipy –
H)]+ (2) and its potential use for the catalytic dehydrogenation of ethane.
[1]
B. Butschke, H. Schwarz, Chem. Sci. 2012, 3, 308-326.
a) B. Butschke, M. Schlangen, D. Schröder, H. Schwarz, Chem. Eur. J. 2008, 14, 1105011060; b) B. Butschke, M. Schlangen, D. Schröder, H. Schwarz, Int. J. Mass Spectrom. 2009,
283, 3-8; c) B. Butschke, S. Ghassemi Tabrizi, H. Schwarz, Chem. Eur. J. 2010, 16, 3962-3969;
d) B. Butschke, S. Ghassemi Tabrizi, H. Schwarz, Int. J. Mass Spectrom. 2010, 291, 125-132;
e) B. Butschke, H. Schwarz, Int. J. Mass Spectrom. 2011, 306, 108-113; f) B. Butschke, H.
Schwarz, Chem. Eur. J. 2012, 18, 14055-14062.
[3]
B. Butschke, H. Schwarz, Organometallics 2010, 29, 6002-6011.
[2]
38
Thursday 11:40 - 12:00
Talk 03
New Insights into the Chemistry of Photoaffinity Labeling
with Diazirines
Björn Raimer , Thomas Lindel
Chemistry – TU Braunschweig – Hagenring 30 – Braunschweig – GER
[email protected]
3-Aryl-3-trifluoromethyl-3H -diazirines (TFD) developed by Brunner et al.[1] have
been used as covalent linkers in photoaffinity labelling (PAL), which aims at the
identification an analysis of biological targets. Although a growing number of natural products and other biologically active molecules have been functionalized with a
diazirine moiety, relatively little has been improved regarding the chemoselectivity of
diazirines.[2]
Based on extensive quantum mechanical calculations searching for suitable carbenes
with a singlet ground state, we investigated experimentally the selectivity of a 3-(pmethoxyphenyl)-3-trifluoromethyl-3H -diazirine towards phenolic motifs. By deuteration experiments, we were able to show for the first time that electron rich positions
are alkylated via a carbene-protonation mechanism, which becomes dominant if the
ground state of the carbene is singlet.[3]
We are currently working on the design of sterically hindered diazirines which should
ideally undergo only one chemoselective reaction with structural motifs present in
proteins and nucleic acids. This would clearly facilitate the interpretation of mass
spectra of covalent ligand-protein adducts formed by PAL and the investigation of
binding modes.
1
[1]
J. Brunner, H. Senn, F. M. Richards, J. Biol. Chem. 1980, 255, 3313-3318.
Reviews: a) A. Blencowe, W. Hayes, Soft Matter 2005, 1, 178-205; b) L. Dubinsky, B. P.
Krom, M. M. Meijler, Bioorg. Med. Chem. 2012, 20, 554-570.
[3]
B. Raimer, T. Lindel, 2012, submitted.
[2]
Talk 04
Thursday 13:30 - 13:50
39
Asymmetric synthesis of Natural-product-inspired Spiro
epoxyoxindoles via Hydrogen-Bond Organocatalysis
Chiara Palumbo ∗ , Tecla Gasperi† , Andrea Mazziotta∗ , Martina Miceli∗ ,
Maria Antonietta Loreto∗ , Augusto Gambacorta†
∗
Department of Chemistry – Sapienza University of Rome – Piazzale Aldo Moro 5 –
Rome – ITA
†
Department of Sciences – University of Studies Roma Tre – Via della Vasca Navale 79 –
Rome – ITA
[email protected]
The spirooxindolic core is among the most valuable building blocks, as it is featured
in several natural products which are endowed of biological interesting properties. For
instance convolutamidines, are proved to be anti-leukaemia agents.[1] Furthermore,
epoxides bearing a phosphonate moiety, like phosphonomycine, display a quite good
antiviral and antibiotic activities.[2]
Over the last decades organocatalysis has proved to be an excellent asymmetric activation mode, which can also be used to get new, challenging reactions and to mold
highly complex scaffolds.[3] Hydrogen-bond interactions have recently had a breakthrough in this field and, whereas covalent organocatalysis has broadly been explored,
non covalent catalysis still represents a novelty for organic chemists.[4] For instance
interesting and very efficient examples of this activation mode have recently been
reported by the use of thioureas, or confined Brønsted acids, that have proved to be
very efficient and selective in many kinds of synthetic transformations.[5]
Our research group has reported about the epoxidation of new 3-alkylidenoxindoles
bearing a phosphonate group, because of the previously highlighted expected
properties.[6] Moreover we have recently proved how prolinol derivatives could act
as H-bonding catalysts towards this kind of reaction.[7]
Herein we report the last results of a H-bonding catalysed, enantioselective, nucleophilic epoxidation of 3-alkylidenoxindoles; this reaction, catalysed by prolinol in a
fast, mild way, gave us quite good results in terms of enantioselectivities (up to 93%
ee), substrate scope (more than 30 spiro epoxyoxindoles), and yields (up to 98% Y).
We hypothesised a reaction mechanism which involve a H-bond network between the
catalyst/oxidant system and the olefin. We checked, as well, the effect on reactivity and selectivity of different substituents on the nitrogen atom, on the aromatic
ring, and on the exocyclic double bond, such as phosphonates which could result in
antiviral activity.[2]
[1]
S. Peddibhothla, CBC 2009, 5, 20.
M. Jackson, et al., Science 1969, 166, 122.
[3]
D. W. C. MacMillan, Nature 2008 455, 304.
[4]
E. N. Jacobsen, et al., ACIE, 2006, 45, 1520.
[5]
P. R. a) Schreiner, et al., CSR 2009, 38, 1187; b) List, B. et al., Nature, 2012, 483, 315; c)
Lattanzi, A. CC 2009, 1452.
[6]
T. Gasperi, et al., EJOC 2011, 385.
[7]
T. Gasperi, et al., OL 2011, 13, 6248.
[2]
40
Thursday 13:50 - 14:10
Talk 05
Polar Effects in Hydrogen Atom Transfers from Catechols to
Alkyl Radicals
Guillaume Povie, Giorgio Villa, Davide Pozzi, Leigh Ford, Philippe Renaud
Department für Chemie und Biochemie – Universität Bern – Freiestrasse 3 – Bern – CH
[email protected]
In combination with organoboranes, 4-tert-butylcatechol can be used as an efficient
hydrogen atom donor in radical chain reactions.[1] This surprising behavior of a class
of compounds generally seen as chain breaking anti-oxydants allowed the development
of a broad scope method for the reduction of organoboranes.[2] Extending this concept to the reduction of alkyl iodides, the hydrogen atom transfer step was found to
be particularly sensitive to the polarity of the attacking radical. While alkyl substituted radicals are efficiently reduced, electron poor radicals slowly react with catechol
derivatives giving them sufficient lifetime to undergo addition reactions. This peculiar
feature could be used to trigger inter and intramolecular processes such as the contrathermodynamic 3-exo-trig cyclisation shown here. The Arrhenius parameters for
the hydrogen atom transfer to different alkyl radicals could be determined using substituted 5-hexenyl radical clocks. The variations of the activation energies in function
of the exothermicity of the reaction and of the polar effects affecting the transition
state are discussed.
Catechol/triethylborane mediated 3-exo-trig radical cyclisation
[1]
G. Povie, G. Villa, L. Ford, D. Pozzi, C. H. Schiesser, P. Renaud, Chem. Commun. 2010,
803-805.
[2]
G. Villa, G. Povie, P. Renaud, J. Am. Chem. Soc. 2011, 133, 5913-5920
Talk 06
Thursday 14:10 - 14:30
41
Understanding the Growth Mechanism: Key to Size Control
of Colloidal Nanoparticles
Maria Wuithschick , Klaus Rademann, Jörg Polte
Institut für Chemie – Humboldt-Universität zu Berlin – Brook-Taylor-Str. 2 –
12489 Berlin – GER
[email protected]
Metal nanoparticles have attracted much attention due to their specific catalytic,
optical and magnetic properties. These properties can be adjusted by altering size,
composition, crystal structure and morphology.[1] Thus, size control provides one
effective key to an accurate adjustment of the colloidal properties but is often challenging. The common approach to size control is a simple parameter variation via trial
and error. The actual particle growth mechanisms and in particular the parameter
influences on the growth process remain a black box.[2]
This contribution presents an approach to size control which is based on a profound
mechanistic understanding. It comprises three steps: (A) the investigation of the
principle growth mechanism for one set of parameters, (B) the investigation of parameter influences on the growth mechanism which leads to the identification of size
determining parameters and (C) the well-directed development of synthetic recipes.
This approach is exemplified for a silver nanoparticle synthesis, namely the reduction
of AgClO4 with an excess of NaBH4 in water.
Recently, we deduced the principle growth mechanism from time-resolved in-situ
SAXS investigations (see figure 1).[3] It comprises (1) the rapid reduction of the ionic
silver, (2) the coalescence of these preliminary formed clusters, (3) an intermediate
phase of stability and (4) a second coalescence which is the result of the complete
conversion of residual BH4- to B(OH)4-. The final particle mean radius ranges from
4 to 9 nm and is poorly reproducible. In the next step of the approach, the influences
of reaction parameters on the growth mechanisms were elucidated.[4] It was found
that the reproducibility can be improved by controlled aging of the reducing agent
solution. In addition, the decisive size determining parameters could be identified.
As a result, synthetic procedures for silver colloids were developed which allow a size
control in a wide range without additional steric stabilization.
Figure 1: Principle nanoparticle growth mechanism for the reduction of silver perchlorate
with sodium borohydride
[1]
Y. Sun, Y. Xia, Science 2002, 298, 2176-2179.
Xia, Y. et al., Angewandte Chemie International Edition 2009, 48, 60-103.
[3]
J. Polte, et al., ACS Nano 2012, 6, 5791-5802.
[4]
M. Wuithschick, et al., submitted.
[2]
42
Thursday 16:20 - 16:40
Talk 07
PbS-mesocrystals - Coherence between atomistic
arrangement and internal nanocrystal superstructure
ordering
Lydia Liebscher ∗ , Igor A. Baburin∗ , Wilder Carrillo-Cabrera∗ , Elena Rosseeva† ,
Paul Simon† , Stephen G. Hickey∗ , Alexander Eychmüller∗
∗
Physikalische Chemie – TU Dresden – Bergstraße 66b – Dresden – GER
†
MPI for Chemical Physics of Solids – Max Planck Institute – Nöthnitzer Straße 40 –
Dresden – GER
[email protected]
Self aggregation and organization of nanoparticulate building blocks to form mesocrystals (Quantum dot solids) with special shapes and tunable properties is promising for
many applications because such 2D and 3D arrangements combine the size-dependent
properties of the individual nanoparticles (NPs) with new features that are derived
from the unique collective properties inherent within arrays of ordered particles. At
the present time mesocrystals are of increasing interest because these structures have
further promising applications as light emitting devices, photodetectors and solar
cells.[1]
In this work we investigate the internal ordering of PbS mesocrystals at the atomistic scale with respect to the superlattice formed through the self assembly of the
NPs.[2] The hierarchical structures were synthesized using a gentle diffusion technique
employing spherical lead chalcogenide NPs as building blocks.
The PbS mesocrystals were characterized by SEM. In order to shed some light on the
inner ordering of the PbS mesocrystals FIB cuts have been performed and subjected to
detailed TEM investigations. The results of the HR-TEM studies show that a distinct
structural relationship between the crystallographic orientation of the PbS (galena)
core of the NPs and their ordering within the fcc superstructure of the mesocrystals
exists. Additionally, careful examinations of the HR-TEM images along the different
projections of the individual nanocrystals have revealed that the appearance of the
individual NPs is closely related to that of truncated octahedra. These findings are
further supported by means of atomistic simulations undertaken on the NP assemblies
as well as of the constitution of the monomeric building blocks.
[1]
S. M. Rupich, E. V. Shevchenko, M. I. Bodnarchuk, B. Lee, D. V Talapin, Journal of the
American Chemical Society 2010, 132, 289-296.
[2]
P. Simon, E. Rosseeva, I. a Baburin, L. Liebscher, S. G. Hickey, R. Cardoso-Gil, A. Eychmüller,
R. Kniep, W. Carrillo-Cabrera, Angewandte Chemie (International ed. in English) 2012, 51,
10776-10781.
Talk 08
Thursday 16:40 - 17:00
43
Synthesis of BaZrO3 , Ta2 O5 and HfO2 nanoparticles as
artificial pinning centers in High Temperature
Superconductors
Jonathan De Roo ∗ , Katrien De Keukeleere∗ , Jonas Feys∗ , Petra Lommens∗ ,
Zeger Hens∗ , Isabel Van Driessche∗
†
Department of Inorganic and Physical Chemistry – Ghent University –
Krijgslaan 281, building S3 – Ghent – BEL
[email protected]
The development of Y Ba2 Cu3 O7−δ (YBCO) high-temperature superconductors has
reached the level of high performance applications such as magnets, generators and
transformers. These materials will contribute to a sustainable future by providing
major energy savings. However, the critical current density (Jc ) remains too low
for optimal application in high magnetic fields. Moreover, the dependence of Jc
on the orientation of the magnetic field poses problems for practical application.[1]
These problems can be circumvented by the introduction of various structural and
morphological defects (artificial pinning centers).
Recently, BaZrO3 and Y2 O3 nanostructures have proven some effectiveness via insitu approaches.[1] However, our innovative research focuses on the ex-situ addition
of nanosized BaZrO3 , T a2 O5 and HfO 2 of which the latter have never been used as
artificial pinning centers up to date. This ex-situ approach provides more control over
the size and morphology of the nanostructures and hence their pinning properties.
We explored solvothermal, microwave and hot-injection synthesis methods for the
creation of these nanostructures. We try to restrain the use of organics in those
synthesis routes and use as much as possible environmental-friendly, even water-based
precursors. The synthesized nanoparticles were incorporated in YBCO precursor
solutions. In order to do this we needed to carefully assess the surface chemistry of
the different types of nanoparticles, and study the influence of ligand exchange on the
stability of the nanoparticle/YBCO precursor mixtures. In the end, these mixtures
will be used as inks in order to deposit ex-situ pinned YBCO on selected substrates
through ink-jet printing.
TEM picture of solvothermally prepared Hf O2 nanoparticles. Inset (upper left): High
Resolution TEM picture of an isolated particle. Inset (upper right): TEM diffraction
pattern of the Hf O2 nanoparticles.
[1]
44
X. Obradors et al., Comprehensive Nanoscience and technology 2011, 1, 303-349.
Thursday 17:00 - 17:20
Talk 09
Viscosity at the Nanoscale
Krzysztof Sozanski, Tomasz Kalwarczyk, Robert Holyst
Department of Soft Condensed Matter –
Institute of Physical Chemistry of the Polish Academy of Sciences – Kasprzaka 44/52 –
Warsaw – POL
[email protected]
One of the main factors influencing the kinetics of biochemical processes in living cells
is the mobility of proteins and other macromolecules. It is mostly determined by the
diffusion coefficient of a given molecule in the cytoplasm. However, in an environment
as crowded as the cytoplasm, accurate description of the diffusion rates becomes much
more complicated than in simple liquids. It has been frequently observed that small
proteins present diffusion coefficients much greater (even by orders of magnitude)
than predicted by the classical Stokes-Einstein equation.
The experiment-based explanation we suggest utilizes the notion of the so-called
nanoviscosity.[1] This parameter includes both the properties of the complex liquid
as well as the length scale of the object whose mobility is investigated. Thus, two
objects differing is size may effectively experience different viscosity of the very same
environment.[2]
The scaling we propose may be merged with the reaction rate theory to produce a
simple yet universal and extremely functional physical description of diffusion processes in complex liquids. Most of the experimental work was performed by means
of fluorescence correlation spectroscopy (FCS) – a fairly new and little known technique of great potential. To provide a straightforward framework of parameters, we
focused on polymer model systems. However, the results are not only a contribution
to the development of polymer theory. A new perspective is opened for modeling the
transport processes and predicting the mobility of any nano-scaled objects in crowded
environment.
[1]
R. Hołyst, A. Bielejewska, J. Szymański, A. Wilk, A. Patkowski, J. Gapiński, A. Żywociński,
T. Kalwarczyk, E. Kalwarczyk, M. Tabaka, N. Ziębacz, S. A. Wieczorek, Physical Chemistry
Chemical Physics 2009, 11 (40), 9025-9032.
[2]
T. Kalwarczyk, N. Ziębacz, A. Bielejewska, E. Zaboklicka, K. Koynov, J. Szymański, A. Wilk,
A. Patkowski, J. Gapiński, H.-J. Butt, R. Hołyst, Nano Letters 2011, 11, 2157.
Talk 10
Thursday 17:20 - 17:40
45
Studying arsenic in cancer cells by elemental speciation
analysis
Gerrit Hermann ∗ , Petra Heffeter† , Walter Berger† , Stephan Hann∗ ,
Gunda Koellensperger∗
∗
Division of Analytical Chemistry –
University of Natural Resources and Life Sciences – BOKU Vienna – Muthgasse 18 –
Vienna – AUT
†
Institute of Cancer Research – Medical University of Vienna – Borschkegasse 8a –
Vienna – AUT
[email protected]
More than 2000 years Arsenic trioxide (ATO) was used as a remedy by mankind.
Since the 30ies of the 20th century the importance of the compound as drug declined
as more effective medication was available for diseases like syphilis and its side effects
were put more into focus. At the end of the 20th century more evidence emerged for
new application of ATO as a cancer therapeutic. Recently ATO was approved by the
FDA for the use in the treatment of relapsed/refractory acute promyelotic leukemia
(APL). Since the introduction of ATO in chemotherapy, we keep learning about the
cytostatic activity of the drug. Still the knowledge on the intracellular chemistry of
ATO with regard to the activity profile of the drug is however fragmentary. The
debate continues if ATO can be applied for other blood and solid cancers.[1,2] The
contoversity about scientific results in this case and the etablished concepts of mode
of action for ATO was motivation for this work.
The intracellular metabolism of ATO concerning the binding dynamics between cytosolic compounds with special emphasis on the interaction with glutathione and the
formation of its oxidized form was extensively studied. Sensitive versus resistance
cancer cell models as well as cell lines derived from different types of cancer were
subject due to this investigation.
[1]
J. Zhu, Z. Chen, V. Lallemand-Breitenbach, H. De Thé, “How acute promyclocytic leukaemia
revived arsenic”, Nature Reviews Cancer 2002, 2 (9), 705-713.
[2]
H. De Thé, Z. Chen, “Acute promyelocytic leukaemia: Novel insights into the mechanisms of
cure”, Nature Reviews Cancer 2010, 10 (11), 775-783.
46
Friday 10:40 - 11:00
Talk 11
2-Oxoglutarate Oxygenases as Therapeutic Targets
Inga Pfeffer , Michael McDonough, Martin Münzel, Ben G. Davis,
Christopher J. Schofield
Chemistry Research Laboratory – University of Oxford – 12 Mansfield Road – Oxford –
UK
[email protected]
2-Oxoglutarate oxygenases[1] are non-haeme Fe(II)-dependent oxygenases that require
2-oxoglutarate (2OG) and oxygen as cosubstrates. They catalyse a wide range of
oxidative reactions on unactivated C-H bonds and are involved in all steps of gene
expression. 2OG oxygenases are ‘druggable‘ targets; both inhibition and activation
of different 2OG oxygenases can be of therapeutic interest. However, selectivity vs.
other ‘key‘ 2OG oxygenases will be important.
Human aspartyl/asparaginyl-β-hydroxylase (AspH)[2] is a 2OG oxygenase and catalyses hydroxylation of a specific aspartate or asparagine residue in epidermal growth
factor-like (EGF-like) domains. The physiological role of hydroxylations catalysed by
AspH is not yet fully determined. AspH is strongly expressed in various cancers,[3]
and mice knockouts show increased incidence of tumour growth. The role of AspH
for cancer needs to be further investigated but it is already being used as a biomarker
for cancerous tissue in histopathological studies.
Crystallographic studies revealed a common structural feature of 2OG oxyenases: The
catalytic domain contains a double-stranded helix core fold (‘jelly roll’) which supports a highly but not universally conserved Fe(II)-binding motif in form of a triad
of two histidines and one carboxylate, either Asp or less frequently Glu (HXD/E· · ·H
triad motif). AspH lacks the HXD/E· · ·H triad Fe(II)-binding motif. Instead, it has
a His-Xxx-Gly· · ·His motif, the Asp or Glu residue is not present. AspH therefore
differs from other 2OG oxygenases and contains two Fe(II)-binding residues only. Its
unique active site geometry makes AspH an attractive potential drug target. Here we
demonstrate that the hydroxylase domain of the protein alone has no substrate hydroxylation activity but another domain, the tetratricopeptide repeat (TPR) domain,
is required for substrate recognition. We present new crystal structures for a multidomain construct of AspH including enzyme-substrate-complexes with a peptide from
the natural substrate coagulation factor X and designed cyclic peptides which provide
valuable insight for further mechanistic studies and selective inhibitor design.
AspH in complex with a substrate peptide from factor X.
[1]
R. Chowdhury et al., Chem. Soc. Rev. 2008, 37 (7), 1308-1319.
B. A. McMullen, et al., Biochem. Biophys. Res. Comm. 1983, 115 (1), 8-14.
[3]
H. Yang, et al., Oncology Reports 2010, 24 (5), 1257-1264.
[2]
Talk 12
Friday 11:00 - 11:20
47
Design and synthesis of fungical transglycosidase inhibitors
Fernando Gomollon-Bel ∗ , Eduardo Marca∗ , Ramon Hurtado-Guerrero† , Ignacio Delso∗ ,
Tomás Tejero∗ , Pedro Merino∗
∗
Departamento de Síntesis y Estructura de Biomoléculas –
Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) –
Universidad de Zaragoza - CSIC - C/ Pedro Cerbuna 12 – Zaragoza – ESP
†
BIFI – Instituto de Biocomputación y Física de Sistemas Complejos –
Universidad de Zaragoza - C/ Mariano Esquillor s/n – Zaragoza – ESP
[email protected]
Transglycosydases are a group of key enzymes in preserving the structure of the
cell-wall in most fungi. Therefore, the study of their active site and preparation of
inhibitors could lead to the obtention of powerful fungicides which could be active
against infectious organisms such as Aspergillus fumigatus or Candida albicans.
We were able to study the x-ray crystalline structure of Gas2[1] , a membrane bound
enzyme from Saccharomices cerevisae, a fungus that is usually studied in Biochemistry because of its genetical and structural analogies to pathogens like A. fumigatus
and C. albicans. Knowing the active site and the optimal substrate for the enzyme,
molecular docking studies were carried out to design the target molecules to be synthesized.
We have optimized a purification method[2] of β(1,3)-oligosaccharides from commercially available glucans (Figure 1, A) and we have studied the synthesis of cyclic six
membered nitrones that can be functionalized[3] with hydrophobic substituents (R)
(Figure 1, B) which will be able to fit in a lipophilic cavity close to Gas2 active site.
Nowadays, new docking, molecular dynamics and inhibition studies are being carried
out to determine the activity as fungicides of the prepared compounds.
Figure 1 - Saccharomyces cerevisae Gas2 transglycosidase and synthetic goals
Acknowledgments: F. G.-B. thanks the Spanish Council for Scientific Research (CSIC) for a
JAE-Predoctoral grant. R. H.-G. thanks the ARAID Foundation for a permanent position.
[1]
R. Hurtado-Guerrero, A. W. Schüttelkopf, I. Mouyna, A. F. M. Ibrahim, S. Shepherd, T.
Fontaine, J.-P. Latgé, D. M. F. van Aalten, J. Biol. Chem. 2009, 284, 8461-8469.
[2]
V. Moreau, J.-L. Viladot, E. Samain, A. Planas, H. Driguez, Bioorg. Med. Chem. 1996, 4,
1849-1855.
[3]
a) P. Merino, S. Franco, F. Merchán, T. Tejero, Synlett. 2000, 442-454; b) I. Delso, T. Tejero,
A. Goti, P. Merino, J. Org. Chem. 2011, 76, 4139-4143.
48
Friday 11:20 - 11:40
Talk 13
2
H NMR spectroscopy in application to selected amino-acids
Aleksandra Kubica ∗ , Danuta Kruk† , Artur Birczyński‡
Faculty of Physics, Astronomy and Applied Computer Science –
Jagiellonian University – Reymonta 4 – Krakow – POL
†
Faculty of Mathematics and Computer Science – University of Warmia and Mazury –
Sloneczna 54 – Olsztyn – POL
‡
Institute of Nuclear Physics – Polish Academy of Science – Radzikowskiego 152 –
Krakow – POL
∗
[email protected]
2H
Nuclear Magnetic Resonance (NMR) is one of the key methods providing information on mechanisms of molecular dynamics.[1] 2 H NMR spectral shapes as well
as spin relaxation are dominated by strong quadrupolar interaction.[1] Combining
these great advantages of 2 H NMR with selective substitution of 1 H by 2 H one gets
powerful tool for studying dynamics of biomolecules. Generally 2 H spectral shapes
analysis of 2 H NMR is based on perturbation theory. For biological systems the description of time scale outside of the perturbation regime is needed. Unswerving to
this need in this work a theory of 2 H lineshape based on Stochastic Liouville Equation
is presented.[2] . This treatment is an adaptation of “Swedish slow motion theory” [3,4]
applied in Electron Spin Resonance (ESR). The presented theory of 2 H lineshapes is
valid for arbitrary motional conditions and allow for considering various mechanisms
of motion, for instance simple (Brownian), free - or jump rotational dynamics. The
free diffusion model assumes that the molecule reorients freely for a given time and
then jumps to a new orientation and then reorients again. In the case of jump diffusion it is assumed that the molecule has a fixed average direction around which it
reorients for a given time and then jumps to a new direction. These models are described by two times: τ - life time of single orientation and τR - rotational correlation
time. Illustrative simulations of 2 H lineshapes for the simple, jump- and free diffusion
models are shown in the Fig.1. The theory has been applied to analyze 2 H lineshapes
of amino acids (lizyne, glicyne, alanine) and proteins[5] (concanavaline and leucine69 from chicken villin - spectra were taken from [6] ) for the purpose of extracting
information on the dynamical mechanisms of the selectively deuterated parts of the
molecules. One can conclude from this attempt that the models capture the essential
features of the dynamical processes and allow for a consistent interpretation of the
2 H NMR spectral shapes.
Left: 2 H NMR spectra, B0 =0.1T for quadrupolar coupling constant aq =220kHz and
different models of diffusion. Right: 2 H NMR spectra for leucine-69 and simulations.
[1]
D. Kruk, Theory of Evolution and Relaxation of Multi-Spin Systems (Arima, Bury St Edmunds,
2007).
[2]
D.Kruk et al., J.Chem. Phys. 2011, 135, 224511.
[3]
T. Nilsson, J. Kowalewski, J. Magn. Reson. 2000, 146, 345.
[4]
D. Kruk et al., J. chem. Phys. 2011, 135, 224511.
[5]
D. Kruk et al., J. chem. Phys. 2012, 136, 244509.
[6]
Vugmeyster et al., J. Am. Chem. Soc. 2009, 131, 13652.
Talk 14
Friday 11:40 - 12:00
49
Synthesis and development of the novel phthalocyanine
derivatives possessing 2-(morpholin-4-yl)ethyloxy groups of
potential applications in photodynamic therapy
P. Skupin-Mrugalska ∗ , L. Sobotta∗ , W. Szczolko† , K. Konopka , E. Tykarska† ,
M. Wierzchowski† , J. Dlugaszewska‡ , M. Kucinska‡ , M. Murias‡ , N. Duzgunes ,
T. Goslinski† , J. Mielcarek∗
∗
Department of Inorganic and Analytical Chemistry –
Poznan University of Medical Sciences – Grunwaldzka 6 – Poznan – POL
†
Department of Chemical Technology of Drugs –
‡
Department of Toxicology – Poznan University of Medical Sciences – Dojazd 30 –
Poznan – POL
Department of Biomedical Sciences – University of the Pacific – 2155 Webster Street –
San Francisco – USA
[email protected]
Phthalocyanines (Pcs) are macrocyclic compounds which possess many applications.
In biomedical field, Pcs have been investigated as potential photosensitizers (PSs)
for photodynamic therapy (PDT). PDT is a medical modality which exploits oxygen,
visible light and PS to treat various diseases including cancer, age-related macular
degeneration, psoriasis, keratosis, etc.[1] Chemical modifications of existing PSs, designing novel molecules and pharmaceutical formulations are ongoing approaches aiming to improve PSs properties. As most Pcs are highly insoluble in water, they have
been mainly modified either by chemical reactions leading to more soluble derivatives
or by incorporation into vehicles like liposomes.[2] Herein, novel Pcs endowed with
2-(morpholin-4-yl)ethyloxy substituents were synthesized (1-4). Moreover, alkylation
reaction of 1 led to water soluble Pc (4). Novel macrocycles were characterized using
NMR techniques and crystallography. Their purity was assessed by HPLC method. In
addition, absorption, emission and aggregation properties of the novel Pcs were studied. Singlet oxygen quantum yield of compounds 1-4 was measured both in DMSO
and in DMF. Cytotoxic activity of these compounds was investigated using panel of
cancer cell lines. The Pc 3 was found the most active compound which showed light
but not dark cytotoxicity. Pcs 1-3 were then incorporated into liposomes following
hydration procedure, and extruded to achieve a uniform size distribution. Liposomes
were characterized by dynamic light-scattering method. Finally, the biological activity against human squamous cell carcinoma of novel Pcs, both non-incorporated and
incorporated into liposomes, was studied.
Studies supported by the National Science Centre - Grant No. N401 067238 and funds from University of the Pacific, A.A. Dugoni School of Dentistry. P. Skupin-Mrugalska, W.Szczolko -scholarship
holders “Scholarship support for Ph.D. students specializing in majors strategic for Wielkopolska’s
development”, Sub-measure 8.2.2 Human Capital Operational Programme, co-financed by EU under the ESF.
[1]
S. Yano, S. Hirohara, M. Obata, Y. Hagiya, S. Ogura, A. Ikeda, H. Kataoka, M. Tanaka, T.
Joh, J. Photochem. Photobiol. 2011, C 12, 46.
[2]
Y.N. Konan, R. Gurny, E. Allemann, J. Photochem. Photobiol. 2002, B 66, 89.
50
Friday 13:30 - 13:50
Talk 15
Novel drug carrier systems - Spectroscopic characterization
of cell-penetrating peptide analogous
Sören Gehne ∗ , Karl Sydow† , Margitta Dathe† , Michael U. Kumke∗
Physical Chemistry – University of Potsdam – Karl-Liebknecht-Str. 24-25 – Potsdam –
GER
†
Peptide Lipid Interaction/Peptide Transport –
Leibniz Institute for Molecular Pharmacology – Robert-Roessle-Str. 10 – Berlin – GER
∗
[email protected]
The specific transport of pharmaceutical ingredients to the point of need is a very hot
topic in life sciences. Among the molecular transport systems investigated colloidal
vehicles (e.g. micelles) are of special interest because they are able to transport also
only poorly soluble or rapidly degradable molecules.[1]
We report on the lipopeptide (LP) P2A2, which consists of a cell-penetrating peptide
part A2 (derived from apoliprotein E) and of two palmitoyl chains P2.[2,3] The unique
combination of cell-penetrating and micelle-forming properties paves the road for the
development of a novel class of powerful drug carrier systems (DCS). Knowledge on
the physico-chemical properties as well as the interaction of the DCS with the target
(e.g. cells, cell membranes) is indispensible for the design of novel highly effective
tailor-made DCS. Fundamental properties such as the critical micelle concentration
(cmc), the aggregation number (Nagg ) as well as the exchange rates of drugs between
DCS and environment are needed, which – in some cases – are only accessible with
sensitive spectroscopic methods.
For the spectroscopic investigation A2 and P2A2 were labeled with 5(6)-Carboxyfluorescein (FAM) and used as fluorescent probe. By using different spectroscopic
methods (e.g. fluorescence anisotropy, fluorescence correlation spectroscopy) the
FAM-labeled biomolecules were characterized regarding their aggregation behavior
(cmc, Nagg ). To study the influence of the chemical composition of the peptide part
on the micelle formation, P2A2 analogous with modified peptide sequences were investigated.
P2A2 turned out to be a very strong detergent with an outstanding low cmc in the
micromolar(!) range. For a powerful drug delivery system also the targeted delivery to specific cells[4] or the exchange kinetics of the pharmaceutical agents is highly
important. Therefore, the exchange kinetics of P2A2 micelles were investigated in
biomimetic systems using fluorescent probes as drug analogous.
P2A2-micelle (yellow - palmitoyl chains).
[1]
V. P. Torchilin, Pharm Res 2007, 24, 1-16.
S. Keller et al., Angew. Chem. Int. Ed. 2005, 44, 5252-5255.
[3]
E. Leupold et al., Biochimica et Biophysica Acta 2009, 1788, 442-449.
[4]
I. Sauer et al., Biochimica et Biophysica Acta 2006, 1758, 552-561.
[2]
Talk 16
Friday 13:50 - 14:10
51
Controlled Synthesis of Cell-Laden Degradable Microgels by
Radical-Free and Supramolecular Gelation in Droplet
Microfluidics
Torsten Rossow , Sebastian Seiffert
Organische Chemie – Freie Universität Berlin – Takustraße 3 – Berlin – GER
[email protected]
Hydrogels with micrometer-scale dimensions (microgels) are useful scaffolds for cell
encapsulation, because they mimic the natural extracellular matrix with the possibility to tailor it.[1] We fabricate microgel particles that contain living cells with
exquisite control through droplet-based microfluidics, as shown in Figure 1. The microgel gelation is achieved via the bio-orthogonal thiol-ene click reaction of dithiolated
polyethyleneglycol (PEG) macrocrosslinkers and acrylated hyperbranched polyglycerol (hPG) building blocks and does not require any initiator.[2] This approach yields
high cell viabilities of about 90%.
To perform efficient cell analysis, fast and stimuli-responsive microgel degradation
must be achievable to release encapsulated cells on demand. For this purpose, reversibly crosslinked supramolecular polymer gels are an interesting class of materials. We follow this approach and prepare supramolecularly crosslinked cell-laden
microgels that consist of bipyridine-terminated PEG, crosslinked by complexation of
non-harmful metal salts such as iron(II)-sulfate. To study the influence of the microgel elasticity on mammalian-cell viabilities, we use bpy-PEG-bpy precursors with
different molecular weights and at different concentrations. That way, the microgel
properties can be optimized to obtaining cell viabilities of up to 96%. These microgels are stable enough to use them as in-vitro 3D-cell culturing systems, but they are
labile enough to release the cells on demand. This can be achieved by simple dilution
on a timescale of hours or by the addition of decomplexing agents on a timescale of
minutes, with no effect on the viability of the encapsulated and released cells.
Figure 1. Formation of cell-laden microgel particles through the use of droplet-based
microfluidic particle templating and bio-orthogonal crosslinking of thiol-terminated polyethyleneglycol (PEG) and ene-terminated hyperbranched polyglycerol (hPG) precursor
polymers.
[1]
D. Velasco, E. Tumarkin, E. Kumacheva, Small 2012, 8, 1633-1642.
T. Rossow, J. A. Heyman, A. J. Ehrlicher, A. Langhoff, D. A. Weitz, R. Haag, S. Seiffert, J.
Am. Chem. Soc. 2012, 134, 4983-4989.
[2]
52
Friday 14:10 - 14:30
Talk 17
Liquid Crystal and Electro-Optic Block Codendrimers:
Synthesis and Characterization
Ismael Gracia ∗ , Beatriz Feringán∗ , Joaquín Barberá∗ , Ana Omenat∗ , Jose Luis Serrano†
∗
Dpto. Química Orgánica –
Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza - CSIC –
C/ Pedro Cerbuna 12 – Zaragoza – ESP
†
Dpto. Química Orgánica –
Instituto de Nanociencia de Aragón, Universidad de Zaragoza - CSIC –
C/ Pedro Cerbuna 12 – Zaragoza – ESP
[email protected]
Dendrimers are polymeric materials that have attracted a lot of attention, in many
fields, all over the last decade. One of the main properties of dendrimers is that
it is possible to achieve a high degree of control over their functionalization, both
in the backbone and in the periphery. In our group, we have experience in the
study of the structure-properties relationship of liquid crystal dendrimers, or the socalled dendromesogens.[1] In this work, different bifunctional materials have been
synthesized based on block codendrimers. The objective is to obtain ordered and
light emitting materials based on highly controllable dendritic structures.
For the dendrimer backbone, we have used the first and second generation of bis-MPA
dendrons.[2] From this starting material and by means of an orthogonal synthetic
procedure, we obtain compounds with two or four peripheral hydroxyl groups for the
first and second generations, respectively. Since our first goal was to prepare a liquid
crystal material, we have introduced four mesogenic groups, which should favour the
mesophase formation, and a variable amount of chromophores on the other side of the
molecule, in order to study the relationship between the mesogenic and the emissive
properties of the codendrimer. Afterwards, we have introduced some modifications
in the structure to favour the formation of room temperature stable smectic and
columnar phases that would benefit the ordered fluorescence emission.
WAXD patterns show that dendrons and codendrimers with one terminal chain
present type A and C smectic mesophases, whereas those with three terminal chains
show columnar mesomorphism in some cases. Even though smectic phases are quite
stable in the materials under study, the columnar mesomorphism is not always reached
maybe due to the destabilization caused by the photoactive species. Calculations
based on WAXD patterns allow us to propose molecular models for the mesophases.
UV-vis absorption and fluorescence emission experiments show strong signals with
maxima at 264 -268 nm and 351 nm, respectively, while when emission was measured
from multi-domain oriented films maximum emission was found at 370 nm. Optical properties of these codendrimers show that the introduction of one, two or four
carbazole units does not affect the emission quantum yield.
Fig. 1. Schematic representation of the codendrimers synthesized
[1]
[2]
M. Marcos, R. Martín-Rapún, A. Omenat, J. L. Serrano, Chem. Soc. Rev. 2007, 36, 1889.
H. Ihre, A. Hult, J. M. Fréchet, I. Gitsov, Macromolecules 1998, 31, 4061.
Talk 18
Friday 16:20 - 16:40
53
Great Insights from a Small System: Structure and
reactivity of [V P O4 ]+ in comparison with [V2 O4 ]+ .
∗
Nicolas Dietl ∗ , Maria Schlangen∗ , Knut Asmis† , Helmut Schwarz∗
Institut für Chemie – Technische Universität Berlin – Straße des 17. Juni 135 – Berlin –
GER
†
Institut für Molekülphysik – Fritz-Haber-Institut der Max-Planck-Gesellschaft –
Faradayweg 4-6 – Berlin – GER
[email protected]
The selective oxidation of hydrocarbons still constitutes one of the major challenges in
contemporary chemistry to solve global problems, such as the environmentally benign
and economically feasible conversion of natural gas into value-added products.[1] Today, there exist numerous effective homogeneous and heterogeneous catalysts which
cover a broad spectrum of oxidation reactivity; however, it is not exaggerated to
note the lack of substantiated knowledge about the intrinsic properties of many of
the catalysts which, after all, control the selectivity of the various oxidation processes. A well-known example for such a poorly understood catalytic process represents the chemical transformation of n-butane to maleic anhydride by the so-called
VPO-catalysts; this highly complex and selective reaction involves the abstraction of
eight hydrogen atoms from, as well as the transfer of three oxygen atoms to C4 H10 .
One approach in the elucidation of mechanistic aspects at a molecular level employs
reactivity studies which are conducted under near single-collision conditions in a mass
spectrometer in conjunction with computational studies.[2]
Our recent results report on the electrospray-ionization (ESI) generation of the small,
mixed-oxo cluster [V P O4 ]+ , its electronic structure in the gas phase as well as its
reactivity towards small hydrocarbons, thus permitting a comparison to the long-time
known and extensively investigated vanadium-oxide cation [V2 O4 ]+ .[3] As described
in previous studies, the latter exhibits no reactivity towards small hydrocarbons, such
as CH4 , C2 H6 , C3 H8 , C4 H1 0, and C2 H4 , while the substitution of one vanadium
atom by a phosphorous atom yields the reactive [V P O4 ]+ ion which brings about
oxidative dehydrogenation from saturated hydrocarbons, i.e. propane and butane, as
well as oxygen-atom transfer to unsaturated hydrocarbons, i.e. ethene, at thermal
conditions. Further, the structure of [V P O4 ]+ was characterized in the gas phase
by advanced IR photodissociation spectroscopy, and a comparison is made to the
also structurally characterized gaseous [V2 O4 ]+ system, including structure-reactivity
relationships. Finally, reaction mechanisms are elucidated by DFT calculations; the
results underline the key role of phosphorous in terms of C-H bond activation of
hydrocarbons by mixed VPO-clusters.
[1]
J. R. Webb, T. Bolaño, T. B. Gunnoe, ChemSusChem 2011, 4, 37.
H. Schwarz, Angew. Chem. Int. Ed. 2011, 50, 10096.
[3]
a) R. C. Bell, K. A. Zemski, K. P. Kerns, H. T. Deng, A. W. Castleman, J. Phys. Chem. A
1998, 102, 1733; b) K. R. Asmis, J. Sauer, Mass Spectrom. Rev. 2007, 26, 542.
[2]
54
Friday 16:40 - 17:00
Talk 19
Comparison of different Cu particles supported on SBA-15
as methanol steam reforming catalysts
Gregor Koch, Thorsten Ressler
Institut für Anorganische und Analytische Chemie – Technische Universität –
Straße des 17. Juni 135, 10623 Berlin – Berlin – GER
[email protected]
Intensive research has shown the importance of Cu containing catalysts for methanol
steam reforming (MSR) as H2 source.[1] For subsequent fuel cell application CO
formation due to side reactions like water gas shift needs to be avoided. Therefore,
the correlation between catalyst structure and activity has to be understood. From
investigations of Cu/ZnO/Al2 O3 catalyst, Cu was found to be the active phase, while
ZnO and Al2 O3 were suggested as both functional and structural promoters.[2] To
further reveal the effect of structural changes of the active Cu phase (e.g. micro strain)
on MSR activity, suitable model systems have to be investigated. Therefore, binary
Cu-ZnO catalysts, for instance, have been studied in detail[3] . Here, Cu particles were
deposited on nanostructured silica to reveal correlations between the structure of Cu
particles and their catalytic activity. This approach shall allow distinguishing these
effects from any further promoting effect of ZnO.
Cu catalysts were prepared by incipient wetness. Therefore, SBA-15 was treated with
Cu citrate solution. Subsequent decomposition in air resulted in the oxidic precursor.
XAS at the Cu K edge showed that CuO is the major copper phase in the oxidic
precursor of all catalysts. During reduction in 5 % H2 , formation of an intermediate
phase before generation of Cu particles was observed with in situ XAS measurements.
After reduction, partially oxidized metallic Cu was found. The average oxidation state
was shifted from ± 0 up to + 0.4. In situ diffraction patterns illustrated enlarged Cu
particles with increasing Cu loading on silica support. XAS measurement of the Cu
K edge also indicated that higher loading of Cu resulted in bigger Cu particles after
reduction (Fig. 1). However, these Cu catalysts showed a good catalytic activity
with high selectivity to CO2 . Correlation between structure of the Cu phase and the
performance of the catalysts will be discussed.
Fig.1 Comparison of the FT(χ(k )*k 3 ) of three Cu/SBA-15 catalysts with different
loadings after reduction.
[1]
S. Sá, H. Silva, L. Brandão, J. M. Soua, A. Mendes, Appl. Catal., B Environmental 2010,
99, 43.
[2]
M. Behrens, F. Studt, I. Kasatkin, S. Kühl, M. Hävecker, F. Abild-Pederson, S. Zander, F.
Girgsdies, P. Kurr, B. L. Kniep, M. Tovar, R. W. Fischer, J. K. Nørskov, R. Schlögl, Science
2012, 366, 893.
[3]
P. Kurr, I. Kasatkin, F. Girgsidies, A. Trunschke, R. Schlögl, T. Ressler, Appl. Catal. A
2008, 348, 153.
Talk 20
Friday 17:00 - 17:20
55
New Trifluoromethyl Derivatives of 5 IPR Isomers the
Fullerene C84
Maria Fritz ∗ , Kaichin Chang† , Natalia A. Romanova∗ , Sergey I. Troyanov∗ ,
Nadezhda B. Tamm∗
∗
Chemical Department – Lomonosov Moscow State University – Leninskie Gori/1-3 –
Moscow – RUS
†
Institute of Chemistry – Humboldt University Berlin – Brook-Taylor Straße/2 –
Berlin – GER
[email protected]
The C84 fullerene corresponds to the higher fullerenes of more than 70 carbon atoms.
As is widely known, the number of possible isomers rapidly grows with the number
of carbon atoms, the isomers which obey the Isolated Pentagon Rule (IPR)[1] being
the most stable. There are 24 possible IPR-isomers of C84 fullerene. Unambiguous
structural determination of the fullerene molecules requires an X-ray study of pristine
isomers or their derivatives. In this regard, the derivatized molecules frequently prove
advantageous as the attached moieties suppress rotational disorder thereby enabling
reliable determination of both cage connectivity and addition patterns.
Here we report synthesis, separation, and structural characterization by means of
single crystal X-ray diffraction new trifluoromethyl derivatives of 5 IPR isomers the
fullerene C84 . Mixtures of higher fullerenes were reacted with CF3 I in a sealed
ampoule at 420◦ C and 550◦ C. The C2m (CF3 )2n reaction products were dissolved in
hexane or toluene and subjected to multistep HPLC separation (Lomonosov Moscow
State University, Moscow, Russia). Single crystals grown from isolated fractions were
studied by X-ray diffraction with the use of synchrotron radiation (BESSY, Free
University, Berlin, Germany). Structural relationship accompanied with theoretical
investigation (DFT/PRIRODA) allowed determining the main addition rules and
revealing the sequential addition pathways.
[1]
56
P. W. Fowler, D. E. Manolopoulos, An Atlas of Fullerenes, Dover Publications, 2006, 392.
Friday 17:20 - 17:40
Talk 21
Posters
Nanoporous anodic titanium oxide (ATO) layers as surface
for microbial and cell growth
Magdalena Jarosz ∗ , Katarzyna Malec† , Justyna Sygula-Cholewinska‡ ,
Tomasz Sawoszczuk‡ , Iwona Wybranska† , Grzegorz Sulka∗ , Marian Jaskula∗
∗
Department of Physical Chemistry & Electrochemistry – Jagiellonian University –
Ingardena 3/30-060 – Krakow – POL
†
Department of Clinical Biochemistry – Collegium Medicum, Jagiellonian University –
Kopernika 15a/31-501 – Krakow – POL
‡
Department of Microbiology, Faculty of Commodity Science –
Cracow University of Economics – Rakowicka 27/31-510 – Krakow – POL
[email protected]
The most commonly considered materials for bone-implants are titanium and its
alloys due to their good biocompatibility, high strength to weight ratio.[1] Titaniumbased materials are widely used in medicine and dentistry, for orthopedic, dental and
other implants, as well as in medical devices (e.g. screws and plates). Unfortunately,
there are some drawbacks and limitations to the use of titanium implants, e.g. their
inertness and long-term osseointegration via the natural oxide (TiO2 ) existing on
their surface. Therefore, titanium with nanoporous materials on its surface becomes
a novel solution for bone implant technology.[2]
Anodic titanium oxide (ATO) films on Ti foils were prepared via a three-step anodization in glycol ethylene based solutions containing NH4 F (0.38 wt.%) and H2 O
(1.79 wt.%) under a constant voltage of 40 V. The duration of first and second anodizing step was 3h. The duration of the third step was 10 min. Titanium foils
(99.5 % purity) were used as both working and counter electrodes. The anodization was performed in two-electrode cells at a constant temperature of 20◦ C. After
anodization, some samples were annealed at the temperature of 400 or 1000◦ C in
order to achieve different polymorphic structures of TiO2 (anatase and rutile). Other
samples were modified with silver nanoparticles. Such prepared samples were used
for the cell growth and microbial examinations. Adipocyte derived stem cells obtained from abdominal liposuction were seeded onto TiO2 surfaces. Cell viability,
proliferation and phenotype were assessed by the measurement of redox reactions in
the cells, cellular DNA, tritiated thymidine ([3H]-TdR) incorporation and alkaline
phosphatase (ALP) production. Staphylococcus aureus bacteria were used for examination of antimicrobial character of nanoporous TiO2 on Ti. The evaluations of
the inhibition of microorganism growth and biofilm formation on various nanoporous
TiO2 surfaces were performed. Nanoporous TiO2 surfaces were placed either on the
surface of Mueller-Hinton agar which was inoculated with microorganisms before or
stroked perpendicularly into the inoculated selected broth. In both techniques a zone
of inhibition on broths was measured. For biofilm formation tests, nanoporous TiO2
surfaces were placed in liquid broths with suspension of microorganisms. The occurrence of biofilm on plates was investigated with a microscopic and UV radiation
methods.
[1]
[2]
58
K.M. Buettner, A.M. Valentine, Chem. Rev. 2012, 112, 1863-1881.
M. Stigter, J. Bezemer, K. de Groot, P. Layrolle, J. Control. Release 2004, 99, 127-137
Thursday 17:40 - 20:10
Poster 001
Superparamagnetic Iron Oxide Nanoparticles Coated with
Chitosan - Physicochemical Characterization
Agnieszka Szpak , Szczepan Zapotoczny, Maria Nowakowska
Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Kraków – POL
[email protected]
Superparamagnetic Iron Oxide Nanoparticles (SPIONs) have attracted attention due
to their great magnetic properties, biodegradablility and nontoxicity, what is crucial
for biomedical applications, especially as tools in advanced diagnostic and therapy
(contrast enhancement for magnetic resonance imaging, drug delivery, detoxification,
hyperthermia treatment, cell separation, detoxification of biological fluids). [1,2]
Here we present results of our studies on fabrication and physicochemical characterization of stable suspensions of SPIONs. Nanoparticles are covered with ultrathin
layer of polymer preventing aggregation process.
For investigating SPIONs properties we used a wide range of methods such as Dynamic Light Scattering (size and charge), Transmission Electron Microscopy (size),
Vibrating Sample Magnetometer (magnetization of suspension) and High Resolution
Electron Microscope for (crystallographic structure) among others. The possibility of
using SPIONs towards biological applications will be investigated in the next step.
Acknowledgements: This work was supported by the European Union from the resources of the European Regional Development Found under the Innovative Economy
Programme (grant coordinated by JCET-UJ, No POIG.01.01.02-00-060/09)
[1]
A.K. Gupta, M. Gupta, Biomaterials 2005, 26, 3995-4021.
S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L. Vander Elst, R.N. Muller, Chemical
Reviews 2008, 108, 2064-2110.
[2]
Poster 002
Thursday 17:40 - 20:10
59
Synthesis of Substituted Pyridinyl Iminothiazolidinone
Compounds via One-Pot Method
Fatma Tülay Tugcu
Department of Chemistry – Yildiz Technical University, Faculty of Science – İstanbul –
TUR
[email protected]
Because of their reaction capabilities both as N-nucleophiles and as S-nucleophiles,
thioureas are successfully used in the synthesis of biologically active compounds. As a
result of comprehensive researches made in recent years, new thiourea compounds having anticancer, antitumor, antiviral, anti-HIV, antimalarial and other various pharmacological activities have been synthesized.[1]
On the other hand, antimicrobial, antituberculosis and antibacterial activities of
iminothiazolidinone compounds have been observed in their biological and pharmacological activity studies.[2] In addition, existence of anti-inflammatory[3] and antifungal[4] effects of these compounds are also mentioned.
Therefore, in this study, some new substituted pyridinyl iminothiazolidinone derivatives which are considered that may possess biological activity have been obtained via
one-pot multicomponent method by using thiophene-2-carboxaldehyde, chloroacetic
acid and several hetaryl-thioureas; and the structures of all these synthesized compounds have been clarified with spectral data:[5]
Thanks for Yıldız Technical University Scientific Research Projects Coordination’s support in this study.Project No: 2010-01-02-GEP01.
[1]
W. Liu, J. Zhou, T. Zhang, H. Zhu, H. Qian, H. Zhang, W. Huang, R. Gust, Bioorganic and
Medicinal Chemistry Letters 2012, 22, 2701-2704.
[2]
Ş. G. Küçükgüzel, S. Rollas, H. Erdeniz, M. Kiraz, A. C. Ekinci, A. Vidin, European Journal
of Medicinal Chemistry 2000, 35, 761-771.
[3]
R. Ottana, R. Maccari, M.L. Barreca, G. Bruno, A. Rotondo, A. Rossi, G. Chiricosta, R. Di
Paola, L. Sautebin, M. G. Vigorita, Bioorganic and Medicinal Chemisty 2005, 13, 4243-4252.
[4]
H. Liu, Z. Li, T. Anthonsen, Molecules 2000, 5, 1055-1061.
[5]
S. Kasmi-Mir, A. Djafri, L. Paquin J., Hamelin, M. Rahmouni, Molecules 2006, 11, 597-602.
60
Thursday 17:40 - 20:10
Poster 003
Nanoscaled phosphors based on metal (II) and gadolinium
mixed borates doped with dysprosium (III) ions
Andrii Shyichuk , Stefan Lis
Faculty of Chemistry – Adam Mickiewicz University – Umultowska 89b – Poznań – POL
[email protected]
Summary
Mixed borate-based nanophosphors of general formula MeMe’2 Gd2 (BO3 )4 , where:
Me, Me’ = Ca, Sr, Ba, were obtained by the sol-gel Pechini method. According to
Scherrer XRD analysis, the size of particles was about 50 nm. The dope of Dy3+
resulted in white emission. The phosphors can be excited by 350 nm near-ultraviolet
light. The emission color can be tuned between yellowish-white, bluish-white and almost pure white, what was confirmed with CIE chromaticity diagrams. The materials
can find potential applications in luminescent tubes and light emitting diodes.
Structure
The composition of the materials was kept as MeMe’2 Gd2−x Dyx (BO3 )4 , where Me,
Me’ = Ca, Sr, Ba. The details of the synthesis procedure are described in our paper
[1]. The materials were studied by means of powder X-ray diffraction (XRD), spectrofluorimetry in the visible range and luminescence lifetime measurements. In the
case of Me = Me’ the XRD patterns of the studied compounds matched the related
entries of JCPDS database. However, in the case of different Me and Me’ the peaks in
XRD patterns were located between the peaks of appropriate references. The width
of peaks was much smaller than the shifts. It means, that new structures containing
both Me and Me’ were formed and no mixture of two phases was present. Sherrer
XRD analysis [2] showed particles size of about 50 nm.
Photoluminescence
The excitation spectra of the samples contained maxima in the spectral range of 330400 nm, corresponding to 4f-4f transitions from the ground state of 6 H15/2 to 4 F7/2 ,
6F
4
4
4
4
4
3+ . The emission was
9/2 , G21/2 , H15/2 , K15/2 , P3/2 , P7/2 levels of Dy
represented by two main bands at 486 and 577 nm corresponding to transitions from
4F
3+ level to 6 H
6
9/2 Dy
15/2 and H13/2 levels, respectively. The decay times varied
within the range of 2-2.5 ms and the luminescence decay curves were monoexponential.
The color of emission (characterized by CIE 1931 color coordinates) linearly changed
in the series of Ba3 Gd2 (BO3 )4 , Ba2 SrGd2 (BO3 )4 , BaSr2 Gd2 (BO3 )4 , Sr3 Gd2 (BO3 )4 ,
CaSr2 Gd2 (BO3 )4 , Ca2 SrGd2 (BO3 )4 , Ca3 Gd2 (BO3 )4 from yellowish-white to bluishwhite being very close to pure white (D65 standard source) in all cases. Additional
excitation bands arising from transitions from the ground state of 8 S7/2 to 6 I15/2 and
6P
3+ were present in spectra of Gd-based compounds. Those bands
7/2 level of Gd
were located at 272.8 and 310 nm, respectively. No emission from Gd3+ was observed.
It means that efficient energy transfer occurred from Gd3+ to the Dy3+ dope ions.
[1]
A.A. Shyichuk, S. Lis, J. Rare Earth 2011, 29 (12), 1161.
A. Patterson, Phys. Rev. 1939, 10, 56.
[3]
C. Kodaira, H.F. Brito, O.L. Malta, O.A. Serra, J. Lumin. 2003, 101, 11.
[4]
H. Mataki, Rare earth-metal nanocluster doped organic/inorganic optical nanocomposites
(thesis), Waseda University, Tokyo 2007.
[2]
Poster 004
Thursday 17:40 - 20:10
61
A versatile approach for coating oxidic surfaces with a range
of nanoparticulate materials.
Jan Poppe, Stefanie Gabriel, Lydia Liebscher, Stephen G. Hickey, Alexander Eychmüller
Physical Chemistry and Electrochemistry – TU Dresden – Bergstraße 66b – Dresden –
GER
[email protected]
A versatile and effective method by which a wide range of nanoparticulate materials
can be attached to a variety of oxidic surfaces is presented. After synthesizing the
nanocrystals (PbS, CdSe, CdSe@CdS core shell, Au) via standard hot injection routes,
the stabilizing ligands are exchanged to 3-mercatopropyl-trimethoxysilane (MPTMS).
The ligand exchange is monitored using FTIR-spectroscopy and transmission electron
microscopy (TEM). The modified nanocrystals were then applied to different oxidic
substrates, yielding homogeneous and dense particle films. The effectiveness of this
coating procedure is then compared with the commonly employed deposition methods
by means of electrochemical measurements and scanning electron microscopy imaging
and found to be vastly superior in its particle deposition efficiency. The applicability
of this methodology is further verified by depositing a layer of PbS nanoparticles onto
a silica sphere colloidal crystals to modify its optical properties.
SEM image of PbS nanoparticles attached to a electrochemically grown ZnO substrate.
62
Thursday 17:40 - 20:10
Poster 005
Complexes of Manganese, Iron and Cobalt with Sterically
Demanding Indenyl Ligands
Miyuki Maekawa ∗ , Constantin Daniliuc† , Matthias Freytag∗ , Peter Jones∗ ,
Marc Walter∗
∗
Institut für Anorganische und Analytische Chemie – TU Braunschweig – Hagenring 30 –
Braunschweig – GER
†
Organisch-Chemisches Institut – Westfälische Wilhelms-Universität Münster –
Corrensstrasse 40 – Münster – GER
[email protected]
Indenyl complexes have been used in wide range applications such as polymerization[1]
and hydrosilylation,[2] and ring substituents can vary their properties. Although indenyl ligands are also monoanionic, formal six-electron ligands that are often considered close analogues of the cyclopentadienyl anion, they have been explored to a
lesser extent. Several substituted indenyl systems have been reported, but examples
with bulky alkyl substituted derivative have relatively limited, e.g. C9H5(iPr)2[3] ,
C9H5(tms)2[3] and C9H6(cHex)[4] .
Here we report on the preparation of the series of manganese, iron and cobalt complexes bearing stericaly demanding 1,3-disubstitueted indenyl ligands, C9H5(tBu)2
(1) and C9H5(cHex)2 (2). The influence of bulky alkyl groups on structure and electronic properties of these metallocene will be presented.[5] Although the cone angles
and electronic properties of each ligands are similar to 1,2,4-(tBu)3C5H2 (Cp’),[6]
indenyl iron half sandwich complexes are only stable at low temperature. This will
be demonstrated for 1-FeI using suitable trapping experiments.[5]
trapping experiment of indenyl iron half sandwich complexwith CO
[1]
T. E. Ready, J. C. W. Chien, M. D. Rausch, J. Organomet. Chem. 1999, 583, 11.
H. Brunner, K. Fisch, Angew. Chem. Int. Ed. 1990, 29, 1131.
[3]
C. A. Bradley, S. Flores-Torres, E. Lobkovsky, H. D. Abruña, P. J. Chirik, Organometallics
2004, 23, 5322.
[4]
C. Krüger, F. Lutz, M. Nolte, G. Erker, M. Aulbach, J. Organomet. Chem. 1993, 452, 79.
[5]
M. Maekawa, C. G. Daniliuc, M. Freytag, P. G. Jones, M. D. Walter, Dalton Trans. 2012, 41,
10317.
[6]
A. Glöckner, H. Bauer, M. Maekawa, T. Bannenberg, C. G. Daniliuc, P. G. Jones, Y. Sun, H.
Sitzmann, M. Tamm, M. D. Walter, Dalton Trans. 2012, 41, 6614.
[2]
Poster 006
Thursday 17:40 - 20:10
63
Compatibility Studies Of Poly(Ether Imide) - Liquid
Crystalline (4-[4-(Dodesiloksi) Benzoyloxy] Benzoic Acid
Mixtures By Viscometry and Fourier Transform Infrared
Spectroscopy
Fatih Cakar , Selma Ozkal, Hale Ocak, Belkıs Bilgin-Eran, Ozlem Cankurtaran,
Ferdane Karaman
Chemistry – Yildiz Technical University – Istanbul – TUR
[email protected]
Liquid crystals (LCs) have more order than isotropic liquid state, but less order
than solid crystalline state and exhibit properties between of them.[1] They have
been studied for many years not only because of their technological importance but
also because of their extraordinary physical properties such as dielectric and optical
anisotropy, flow properties, and response to external fields.[2]
Polyether imides such as Ultem, a well-known class of engineering thermoplastic polymers, offer exceptional thermal, chemical and mechanical stability and are available
in large quantities.[3] Their cost is similar to other thermoplastic polymers that offer
similar performance and significantly more economical than small batch thermoplastic polymers. Polyether imides have higher diffusivity selectivity due to their fused
ring structure and rigid backbone. Their high glass transition temperatures allow
higher pressure and temperature applications without plastic deformation.[4]
Mixing is very important in modern technologies for processing of materials composed
of many different chemical components. Polymer and liquid crystal mixtures are an
important area of interest in science and engineering because of its many applicat
ions in industry. Miscibility can be detected by a number of techniques. Among these
techniques, it is well known that determination of the viscometry of a dilute solution
is a simple and quick method for determining the miscibility. Fourier transform
infrared spectroscopy (FTIR) is one of the many techniques that have been applied
to investigate specific molecular bonding interactions in polymer blends.[5] In the case
of immiscible systems, the spectrum of the blend reflects the appropriate addition of
the IR spectrum of the two individual components. In the case of miscible or partially
miscible polymer blends, the IR spectrum would show formation of new bands as the
results of miscibility; and disappearance of some component bands. Shifts in the
specific bands would give information on the switches from component specific bonds
to the bonds between components.
This study deals with the determination of the miscibility of poly (ether imide) (Ultem) and their mixtures with liquid crystalline (4-[4-(Dodesiloksi) benzoyloxy] benzoic acid (4DBBA)) compounds in dilute solutions. Mixtures of variable compositions
from 0 to 100 wt were prepared by solvent casting. Their miscibility was investigated
by using viscometry and FTIR.
[1]
N. Sen, Current Science 2000, 79(10), 1417.
N.Y. Canli, F. Yakuphanoğlu, B. Bilgin-Eran, Optoelectronics and Advanced Materials-Rapid
Communications 2009, 3(7), 731.
[3]
M.K. Ghosh K. L. Mittal, Polyimides: Fundamentals and Applications, Marcel Dekker, New
York, 1996.
[4]
F. Cakar, O. Cankurtaran, Polymer Bulletin 2005, 55, 95.
[5]
M.T. Kalichevsky, J.M.V. Blanshard, Carbohydrate Polymers 1993, 20, 107.
[2]
64
Thursday 17:40 - 20:10
Poster 007
Synthesis and characterization of InSb nanowires for
thermoelectric applications
Katarzyna Hnida ∗ , William Töllner† , Tim Böhnert† , Kornelius Nielsch† ,
Grzegorz Sulka∗ , Marian Jaskuła∗
∗
Ingardena 3 – Cracow – POL
†
Institute of Applied Physics – University of Hamburg – Jungiusstrasse 11 –
Hamburg – GER
[email protected]
Over the past few years, simulations, theoretical calculations and laboratory tests
suggested that there is a relationship between the size of nanostructures (nanodots,
nanowires and nanotubes) and efficiency of thermoelectric materials.[1, 2] Thus, if developed relatively inexpensive and not very complicated methods for the preparation
of thermoelectric nanostructures they could have a wide practical application.
Electrodeposition is the method of choice to synthesize nanoengineered thermoelectric
materials because of low operating and capital costs, high deposition rates, near
room temperature operation, and the ability to tailor the properties of materials by
adjusting deposition conditions.
Indium antimonide (InSb) is a small band gap semiconductor with high carrier mobility and small effective mass, and is widely use in optical detectors, high-speed electronic devices, and magnetic field sensors. Different methods have been used to fabricate InSb nanowires, such as physical and chemical vapor deposition (PVD, CVD),
vapor-liquid-solid (VLS), and hydrothermal methods. Comparatively, the pulse electrodeposition process using porous anodic aluminum oxide (AAO) templates, is an
effective and inexpensive method of fabricating nanowires.
In this work, we have fabricated a nanowire-based device using laser lithography
to measure the Seebeck coefficient and resistance of an InSb nanowire. The InSb
nanowire was synthesized using template assisted pulse electrodeposition method.
Acknowledgments This work was supported by the International PhD-studies programme at the Faculty of Chemistry Jagiellonian University within the Foundation
for Polish Science MPD Programme co-financed by the EU European Regional Development Fund.
[1]
M. S. Dresselhaus et. al., Low dimensional thermoelectricity, in: T. M. Tritt (Ed.), Semiconductors and Semimetals: Recent Trends in Thermoelectric Materials Research III, vol. 71,
Academic Press, San Diego, CA, 2001, 1-121, Chap. 1
[2]
R. Saito, G. Dresselhaus, M. S. Dresselhaus, Physical Properties of Carbon Nanotubes, Imperial College Press, London, 1998.
Poster 008
Thursday 17:40 - 20:10
65
Synthesis and characterization of new monomer and ATRP
initiators- towards conducting polymer brushes
Karol Wolski, Michał Szuwarzyński, Szczepan Zapotoczny
Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Cracow – POL
[email protected]
Advanced polymeric materials like polymer brushes are very promising for designing
novel organic solar cells. Organic photovoltaic cells are cheaper than commonly used
silicon cells however they are less efficient. The key issue in designing of new efficient materials is undisturbed transport of charge carriers to appropriate electrodes
in the cell. The structure of conductive polymer brushes can provide directional
and effective transport of such charge carriers formed along single polymer chains.
We report here synthesis of essential compounds for Surface-Initiated Atom Transfer
Radical Polymerizations (ATRP) applied for template polymerization of conjugated
polymers.[1] We present the synthesis of a monomer which has both −C=C− and
−C≡C− groups in its structure and the pyridine ring. In addition, two relatively
short ATRP initiators, which can form SAMs on the gold substrate are synthesized.
Physicochemical characterisation of the new compounds is presented. AFM images
of the polymer brushes of the selected monomers obtained by “grafting from” method
with application of the new initiators are also shown.
Acknowledgment: The authors would like to thank Polish Ministry of Science and
Higher Education for the financial support (“Ideas Plus”; grant no. IdP2011 000561).
[1]
66
M. Szuwarzyński, J. Kowal, S. J. Zapotoczny, Mater. Chem. 2012, 22, 20179-20181.
Thursday 17:40 - 20:10
Poster 009
Ring opening polymerization of organic carbonats using CO2
- carbene adducts as effective organo catalyst
Annika Reitz , Dirk Kuckling, René Wilhelm
Chemie – Universität Paderborn – Warburgerstraße 100 – Paderborn – GER
[email protected]
Many modern applications of polymers are in biological systems. Therefore, residual
metals should be avoided and the polymer itself should be degradable. Polytrimethylene carbonate is slightly more stable than polylactide but still biodegradable in reasonable span of time and therefore a good choice for stents or similar applications.
Since the homopolymer of trimethylencarbonate shows a very low glass temperature
copolymerization improves the mechanical properties and multiplies the uses of Polytrimethylencarbonat. Highly reactive carbenes can be used as efficient organo catalyst
but their moisture and air sensibility is a major drawback. Especially their great diversity due to the effect of substituents makes them a great advantage. The use of
adducts, especially those of CO2 , is a major improvement, as they are air stable and
easy to handle.
The polymerization was carried out in bulk with benzylalcohol as initiator and the
CO2 adduct of 1,3 Bis(2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene as
catalyst. To improve the polymerization microwave energy is used. In this microwave
assisted polymerization the turnover increases while the polydispersity stays low.
The polymers are characterized by NMR and IR spectroskopy, ESI-IMS-MS and GPC.
Their molecular weight, polydispersity and end groups will be discussed.
chemical equation of polymerization
Poster 010
Thursday 17:40 - 20:10
67
Investigating Thermodynamic Interactions of
4-[4-((S)-Citronellyloxy) Benzoyloxy] Benzoic Acid (SBBA)
Liquid Crystal with Some Solvents by Inverse Gas
Chromatography
Ismail Erol, Fatih Cakar, Hale Ocak, Belkis Bilgin-Eran, Ozlem Cankurtaran,
Ferdane Karaman
Chemistry – Yildiz Technical University – Istanbul – TUR
[email protected]
Liquid crystals (LCs) represent a fascinating state of matter with wide technical
applications in display industry and optoelectronics, significant importance for the
development of new functional materials, nanopatterning, tissue engineering, sensor
and biosensor applications, and also providing a fundamental concept in biological
self-assembly. This is due to the dual nature of LCs, combining features of anisotropic
crystalline solids and isotropic liquids, enabling their soft self-assembled and ordered
structures to respond to external stimuli, but also to their ability of self-healing of
defects formed.[1]
Inverse gas chromatography (IGC) is now widely used to examine the physicochemical
properties of different materials of both liquid and solid. The term “inverse” indicates
that the examined material, e.g. a polymer blend or modified silica, placed in the
chromatographic column, is of interest in contrast to the common analytical gas
chromatographic experiments. Carefully selected test solutes are injected into the
flow of a carrier gas and transported over the surface of, e.g. fiber. The retention
time and the peak elution profiles of Standard solutes, affected by interactions between
the solute and stationary phase, are used to estimate those interactions.[2]
IGC is an easy, fast and economic method to investigate liquid crystal-solvent interactions. Using IGC to study liquid crystal-solvent interactions is new method and
there are only few study in literature. In IGC process, there is relevance between
liquid crsytal-solvent interactions and specific retention volumes.[3] Thermodynamic
parameters that obtained by using specific retention volume, use to explain liquid
crystal-solvent interactions.
In this study, thermodynamic interactions of 4-[4-((S)-Citronellyloxy ) benzoyloxy]
benzoic acid with some solvents were examined by inverse gas chromatography method.
Firstly, the specific retention volumes of the solvents were determined and the retention diagrams were plotted for liquid crystal-solvent systems. And then, the weight
fraction activity coefficient, Flory-Huggins and equation of state interaction parameters, effective exchange energy parameter, exchange enthalpy and entropy parameters
were calculated at the temperature range which thermodynamical equilibrium occurred.
[1]
Shanker G., Nagaraj M., Kocot A., Vij J.K., Prehm M., Tschierske C., “Nematic Phases in 1,2,4Oxadiazole-Based Bent-Core Liquid Crystals: Is There a Ferroelectric Switching?”, Adv. Funct.
Mater. 2012, 22(8), 1671-1683.
[2]
A. Voelkel, “Inverse gas chromatography in the examination of acid–base and some other properties of solid materials”, in: A. Dabrowski, V.A. Tertykh (Eds.), Adsorption on New and Modified
Inorganic Sorbents, Studies in Surface Science and Catalysis 1996, vol. 99, 465.
[3]
Price G.J., Shillcock I.M., “Investigation of Mesophase Transitions in Liquid Crystals Using
Inverse Gas Chromatography”, Can. J. Chem. 1995, 73, 1883-1892.
68
Thursday 17:40 - 20:10
Poster 011
Synthesis, Thermal, and Electrical Properties of Stilbene
Bridged Polymeric Zinc Phthalocyanine
Muhammet Kasim Sener ∗ , Hilal Yurtseven∗ , Mehmet Arif Kaya∗ , Ahmet Altindal†
∗
Department of Chemistry – Yildiz Technical University – Istanbul – TUR
†
Department of Physics – Yildiz Technical University – Istanbul – TUR
[email protected]
Polymeric phthalocyanines are very interesting materials since they belong to a class
of π-conjugated semiconductor polymers which offer a unique combination of properties. Polymeric phthalocyanines are mainly prepared via polycyclotetramerization reactions of bifunctional monomers such as aromatic tetracarbonitriles, various
oxy-, arylenedioxy- and alkylenedioxy-bridged diphthalonitriles, and other nitriles or
tetracarboxylic acid derivatives in the presence of metal salts or metals. We report
here, the synthesis and characterization of a new zinc containing polymeric phthalocyanine and its precursor. To understand the semiconducting and dielectric properties
of polymeric zinc phthalocyanine, a systematic investigation on dc and ac electrical
properties and their variation with temperature and frequency is attempted. Also,
thermal properties of the polymeric zinc phthalocyanine is investigated by differential
scanning calorimetry (DSC) and thermal gravimetric analysis (TGA).
[1]
[2]
[3]
[4]
[5]
[6]
A.
D.
D.
A.
A.
Y.
Bilgin, C. Yagci, U. Yildiz, E. Ozkazanc, E. Tarcan, Polyhedron 2009, 28, 2268.
Wöhrle, Macromol. Rapid. Commun. 2001, 22, 68.
Wöhrle, U. Marose, R. Knoop, Makromol. Chem. 185, 186, 2209.
Bilgin, C. Yagci, U. Yildiz, Macromol. Chem. Phys. 2005, 206,2257.
Bilgin, A. Mendi, U. Yildiz, Polymer 2006, 47, 8462.
A. Kokshorov, A. I. Sherle, A. N. Tikhonov, Synth. Met. 2005, 149, 19.
Poster 012
Thursday 17:40 - 20:10
69
Use of the oxygen carrier Hemerythrin for development of
blood substitutes
Mariann Kinga Arkosi ∗ , Radu Silaghi-Dumitrescu∗ , Augustin Catalin Mot∗ ,
Denisa Hathazi∗ , Iulia Lupan‡ , Grigore Damian , Eva Fischer-Fodor†
∗
Department of Chemistry and Chemical Engineering – Babes-Bolyai University –
Arany Janos Str. no. 11 – Cluj Napoca – ROU
†
Comprehensive Cancer Center – Ion Chiricuta Cancer Institute –
Republicii Str. no. 34-36 – Cluj Napoca – ROU
‡
Department of Biology – Babes-Bolyai University – Arany Janos Str. no. 11 –
Cluj Napoca – ROU
Department of Physics – Babes-Bolyai University – Arany Janos Str. no. 11 –
Cluj Napoca – ROU
[email protected]
Blood substitutes are used to carry oxygen and increase the fluid volume in the
human cardiovascular system in case of emergencies; they must accomplish numerous
conditions concerning stability, oxygen affinity, toxicity, immunogenic response and
hydrodynamic volume. As opposed to Hemoglobin (Hb) based potential artificial
oxygen carriers, Hemerythrin (Hr) based blood substitutes haven’t been examined and
described extensively and therefore might sound less familiar. My poster presentation
aims to present investigations of this protein as raw material for artificial oxygen
carriers.
Hr is a protein found in marine invertebrates which binds oxygen reversibly by the
use of a non-heme diiron center. It is a very promising alternative to Hb for blood
substitutes because, in contrast to Hb, Hr has distinctly smaller reactivity towards
oxidative and nitrosative stress agents and also shows a remarkably smaller tendency
to generate toxic free radicals in such reactions.
In laboratory, the protein was obtained through overexpression and purification of
recombinant Phascolopsis Gouldii Hr from Escherichia coli strains.[1] Strategies for
conversion of Hr into an effective blood substitute typically involved:
i.) PEGylation of the protein surface (wild type and site directed mutagens) primarily
in order to decrease immunogenicity;
ii.) glutaraldehyde-assisted polymerization and copolymerization (with Human Serum
Albumin and the non-heme iron peroxidase Rubrerythrin) which resulted in high
molecular weight aggregates.[2]
Characterization of the derivatives such as hydrodynamic volume or dioxygen reactivity (oxygen affinity, autooxidation rate) was mainly accomplished using size exclusion
chromatographic and spectroscopic methods (UV-Vis and EPR). As well, aspects related to biological activity have already been investigated. The results of in vitro
cytotoxicity assessments on human lymphocytes and HUVEC cells suggest that in
comparison to Hb derivatives, Hr-based blood substitutes have a better performance
and show a cytoprotective effect.[3]
[1]
C.S. Farmer et al., “A leucine residue "Gates" solvent but not O2 access to the binding pocket
of Phascolopsis Gouldii hemerythrin.” J. Biol. Chem. 2000. 275(22), 17043-17050.
A.C. Mot et al., “Towards the Development of Hemerythrin-Based Blood Substitutes.” Protein
J. 2010 29(6), 387-393.
[3]
E. Fischer-Fodor et al., “Towards hemerythrin-based blood substitutes: Comparative performance to hemoglobin on human leukocytes and umbilical vein endothelial cells.” J. Biosci., 2011,
36(2), 215-221.
[2]
70
Thursday 17:40 - 20:10
Poster 013
Polymers with Phosphor Containing Side Chains via
Modular Conjugation as Potential Flame Retardants
Jördis Eisenblätter ∗ , Leonie Barner† , Ulrich Fehrenbacher∗ ,
Christopher Barner-Kowollik‡
∗
Environmental Engineering – Fraunhofer Institute for Chemical Technology (ICT) –
Joseph-von-Fraunhofer-Strasse 7 – Pfinztal – GER
†
Institute for Biological Interfaces (IBG I) – Karlsruhe Institute of Technology (KIT) –
Herrmann-von-Helmholtz-Platz 1 – Eggenstein-Leopoldshafen – GER
‡
Institut for Chemical Technology and Polymer Chemistry –
Karlsruhe Institute of Technology (KIT) – Engesserstraße 18 – Karlsruhe – GER
[email protected]
Polymers are an indispensable part of our lives. They are used for example in the
construction industry, in electrical engineering, transport, as well as in furniture and
textiles. A major problem with the use of polymers, however, is their high flammability due to their carbon skeleton. Depending on the application high fire safety
requirements are imposed. Often native polymers can not fulfill this. Hence the
equipment of polymers with flame retardants represents a necessary step to reduce
fire damage. Most of the flame retardants used up to now, however, show two main
problems: Firstly, mainly halogenated materials are used today as flame retardants
will be prohibited in the next few years due to an increasing concern about persistence
in the environment and potential negative health effects of these materials. Secondly,
until now most of the flame retardants are incorporated into the polymer as additives to achieve the protection of organic material. A drawback of this method is the
emission of potential environmental harmful substances from the polymer over time.
By binding organo phosphorus compounds covalently to the polymer backbone, no
emission of flame retardant from the polymer over time can occur. These so-called
reactive flame retardants are homogeneously distributed in the polymer, whereby an
agglomeration of the flame retardant component is prevented in the polymer. To gain
reproducible results, the applied polymers have to possess narrow polydispersities and
functional groups in the side chain. Living/controlled polymerization techniques like
the reversible addition-fragmentation chain transfer polymerization (RAFT) give access to excellent control over molecular weight of polymers while being tolerant to a
wide list of functional groups.[1] Therefore it is possible to prepare well-defined polymers containing functional groups in the side chains that can subsequently be modified
further, e.g. to functional groups that can be used for click reactions. Subsequently
functional compounds can be integrated in these polymers by covalent linkages to the
side chains of the polymer. By linking functionalized compounds to appropriate functionalized polymers via 1,3-dipolar cycloaddition described by Huisgen[2] a wide range
of variable polymers can be designed. In this work, various phosphorylated polymers
were prepared via 1,3-dipolar cycloaddition and analyzed via comprehensive thermal analysis to achieve insight into the characteristics of phosphorylated polymers.
The focus was on the determination of the influence of the chemical structure of the
phosphorus esters on the thermal degradation behavior and the formation of a char
layer. It could be shown that even with a small amount of <5 % of phosphorus in
the polymer, high carbonization of > 30 % can be achieved.
[1]
C. Barner-Kowollik, Handbook of RAFT Polymerization, Wiley-VCH, 2008.
R. Huisgen, “Kinetics and reaction mechanisms: selected examples from the experience of
forty years”, Pure and Applied Chemistry 1989, 613.
[2]
Poster 014
Thursday 17:40 - 20:10
71
Metal Nanowire Arrays as Alternative Microelectronic
Interconnectors
∗
Matthias Graf ∗ , Alexander Eychmüller∗ , Klaus-Jürgen Wolter‡
Physikalische Chemie & Elektrochemie – Technische Universität Dresden –
Bergstrasse 66b – Dresden – GER
‡
Electronics Packaging Laboratory – Technische Universität Dresden –
Helmholtzstrasse 10 – Dresden – GER
[email protected]
Since the minaturization of microelectronic structures parallel to the performance increase inside these devices are relevant and ongoing processes, meanwhile established
strategies in connecting ready-made devices have already been pushed to their geometrical limits. Apart, technologies as wire bonding or stud bump soldering start
displaying limitations when it comes to high performance three-dimensional packaging with a conventional demand to device reliability. This shows the necessity of
new strategies being investigated for electronic packaging. Herein, nanomaterials are
considered as promising candidates since they are expected to provide new, possibly
attractive properties for solving upcoming problems in electronic packaging.
We present investigations on electrochemical synthesis and characterization of templateassisted electrochemical growth of one-dimensionally elongated metal (Ag, Ni) nanoparticles. The generated arrays are objected to be applied as macroscopic interconnecting
layers with anisotropic electrical conductivity and sub-µm resolution in the vertical
interconnection of microelectronic chips (Flip-chip architectures or 3D chip stacks).
Metal nanowires (NWs) are synthesized by electrodepositing the desired NW species
into hollow linear pores of anodized Al2 O3 . Geometric features as well as surface
chemistry of Al2 O3 is thereby variable within a decent range and allows the geometrical tuning of the NWs. The regular lateral arrangement of pores enables a
homogeneous NW distribution (and thereby a homogeneous transportable current
density through the film) as well as a very small diameter range. For the integration
of such NW arrays between microelectronic contact structures, the generation of a
reliable contact between contact pad surface and NW is a crucial point. We propose
the utilization of a thin additional adhesive film surrounding freestanding NW tips on
both sides of the film to generate a self-adhesive NW film that can easily be laminated
between two microelectronic chips. The bonding between film and chip is so realized
at the top edge of the pores. Therefore we apply a very strongly binding polymer
(poly cyanurate) being able to establish a covalent bond structure to Si/SiO2 surfaces.
In this contribution we focus on the creation process of NWs and the interferences
between synthesis and properties (such as electrical conductivity or crystallinity).
72
Thursday 17:40 - 20:10
Poster 015
Clarification of the sorption behavior of uranium onto mica
and feldspar
Constanze Richter , Madlen Stockmann, Vinzenz Brendler, Kay Großmann
Helmholtz-Zentrum Dresden-Rossendorf e.V. – Institute of Resource Ecology –
P.O.Box 51 01 19, 01314 Dresden – Dresden – GER
[email protected]
As part of long-term safety assessments for radioactive waste disposals, scenarios have
to be considered, which lead to the mobilization of radionuclides from the waste and to
their transport through the repository system. Any repository sites (such as Gorleben)
the sedimentary overburden is an important barrier for radionuclide transport. For
most radionuclides the transport is retarded by sorption on mineral phases. Mica
and feldspars are major components of the Gorleben sediments. However, almost no
sorption parameters are available (www.hzdr.de/res3 t [1] ) for these systems.
The WEIMAR-project (Further Development of the Smart Kd-Concept for LongTerm Safety Assessment) shall address these shortcomings. Batch sorption experiments and spectroscopic investigations will allow the assessment, the evaluation as
well as the processing of sorption data for U, Np, La(III) onto muscovite and orthoclase. Generally, the amount of sorption can depend on the pH-value, ionic strength,
redox potential, concentrations of the contaminant as well as of the sorbent, of complexing ligands and competing ions. All batch experiments are carried out under
ambient atmosphere and with 0.01 M NaClO4 as background electrolyte.
For muscovite and orthoclase the background concentration of the sorbing elements,
the tendency of wall sorption and the dissolution behavior has to be determined. For
both minerals an optimal solid-to liquid ratio has to be optimized. This means that
the sorption is neither too low nor too high, so the sorption has to be between 5 and
95%. All those problems will be illustrated for the case of U(VI) sorption.
This project is funded by the German Federal Ministry of Economics and Technology
(BMWi) under contract number 02 E 11072B
[1]
V. Brendler et al., J. Cont. Hydrol. 2003, 61, 281-291.
Poster 016
Thursday 17:40 - 20:10
73
Carbon dioxide - a suitable material for hydrogen storage
Peter Sponholz , Dörthe Mellmann, Henrik Junge, Matthias Beller
Leibniz-Institute for Catalysis Rostock – Albert-Einstein-Str. 29a – Rostock – GER
[email protected]
Advancements in hydrogen technology such as the generation of hydrogen, its storage and its conversion to electrical energy are the prerequisite for the application of
hydrogen as power source (Figure 1). Recently, the use of carbon dioxide or bicarbonate as suitable storage materials for hydrogen has received considerable attention.
As a significant advantage this cycle is reversible and sustainable. The liquid formic
acid affiliates high hydrogen content (4.4% by mass) with a good stability. A cycle
comprising of the storage of hydrogen in formic acid or formate salts by catalytic
hydrogenation of carbon dioxide or bicarbonate and the release from it by catalytic
dehydrogenation could be realized. We have recently demonstrated for the first time
that both reactions can be coupled leading to a closed carbon cycle for hydrogen
storage applying a ruthenium-based catalyst system for the selective hydrogenation
of bicarbonates as well as the selective dehydrogenation of formats.[1] Further we
could show a setup of a “hydrogen-battery” based on hydrogenation of CO2 to formic
acid and its dehydrogenation back to CO2 .[2] For the latter reaction in a continuous flow setup turnover numbers and turnover frequencies are achieved, which meet
already the requirements of hydrogen supply for applications in the 100 W range.
Moreover besides the ruthenium based systems both reactions, hydrogenation and
dehydrogenation, can also be catalyzed by more abundant iron catalysts.[3]
Figure 1: Energy cycle with hydrogen production, storage and usage.
[1]
A. Boddien, F. Gärtner, C. Federsel, P. Sponholz, D. Mellmann, R. Jackstell, H. Junge, M.
Beller, Angew. Chem. Int. Ed. 2011, 50, 6411-6414.
[2]
A. Boddien, C. Federsel, P. Sponholz, D. Mellmann, R. Jackstell, H. Junge, G. Laurenczy, M.
Beller, Energy Environ. Sci. 2012, 5, 8907.
[3]
A. Boddien, D. Mellmann, F. Gärtner, R. Jackstell, H. Junge, P. J. Dyson, G. Laurenczy, R.
Ludwig, M. Beller, Science 2011, 333, 1733-1736.
74
Thursday 17:40 - 20:10
Poster 017
Functionalization of Monodisperse Iron Oxide Nanoparticles
with Aromatic Dendrons
Ekaterina Yu. Yuzik-Klimova ∗ , Nina V. Kuchkina∗ , Lyudmila M. Bronstein† ,
Zinaida B. Shifrina∗
∗
Group of Macromolecular Chemistry –
A.N. Nesmeyanov Institute of Organoelement Compounds RAS – Vavilov St. 28 –
Moscow – RUS
†
Department of Chemistry – Indiana University – 800 E. Kirkwood Av. –
Bloomington – USA
[email protected]
Magnetic nanoparticles (NPs) have been widely studied because of their potential applications in magnetic storage media, electronic devices, ferrofluids, biosensors, contrast enhancement agents for magnetic resonance imaging, bioprobes, and catalysis.
The last application, i.e. magnetically recoverable catalysts, attracted considerable
attention because they allow easy separation of catalysts from reaction mixtures and
their repeated use, thus leading to energy conservation, more environmentally friendly
processes and cheaper target products.
As is known, iron oxide NPs are well stabilized by fatty acids, such as oleic acid,
containing a single double bond, but normally more functional groups are required if
catalytic complexes or NPs have to be formed in the magnetic NP shell.[1] Here we
report functionalization of iron oxide NPs prepared by thermal decomposition of iron
acetyl acetonate in the presence of the second and third generations of rigid aromatic
dendrons bearing the pyridine moieties and carboxyl focal point. Functionalization
of as-synthesized magnetic NPs was followed using transmission electron microscopy
including HRTEM, energy dispersive spectroscopy, thermal gravimetric analysis and
Fourier transform infrared spectroscopy.
This work was financially supported by European Community’s Seventh Framework
Programme [FP7/2007-2013] under grant agreement no. CP-IP 246095 and the Russian Foundation for Basic Research (RFBR) grants (projects No. 11-03-00064 and
12-03-31057).
Structures of second and third generation aromatic dendrons with a carboxyl focal group
and pyridine moieties
[1]
S.H. Gage, B.D. Stein, L.Zh. Nikoshvili, V.G. Matveeva, M.G. Sulman, E.M. Sulman, D.G.
Morgan, E.Yu. Yuzik-Klimova, W.E. Mahmoud, L.M. Bronstein, Langmuir, Accepted.
Poster 018
Thursday 17:40 - 20:10
75
Bright and tunable up-conversion luminescence through
cooperative energy transfer in Yb3+ , Tb3+ and Eu3+
co-doped LaPO4 nanocrystals
Tomasz Grzyb
Department of Rare Earths – Adam Mickiewicz University – Grunwaldzka 6 – Poznan –
POL
[email protected]
Up-conversion (UC)[1] of Eu3+ ions is relatively rare and ineffective through to their
optical properties. Also the way of Eu3+ excitation require a cooperative energy
transfer (CET)[2] between Yb3+ acting as donors and Eu3+ acceptors, which is
highly dependent on both the properties of the matrix used ions. To increase the
intensity of Eu3+ UC we have used Tb3+ ions as co-dopants involved in the energy
transfer between Yb3+ and Eu3+ . By changing the Tb3+ to Eu3+ molar ratio it
was possible to tune the color of emission from green in Tb3+ -only doped system
through yellow, orange and red with increasing concentration of Eu3+ ions in this
system. Lanthanum phosphate is a good candidate for CET systems and has been
used as host for dopants ions. Nanomaterials were prepared by a microwave assisted
hydrothermal method in the presence of ethylenediaminetetraacetic acid. Obtained
products showed UC emission only after their heating at 900o C what resulted in
change of crystallographic structure from hexagonal to monoclinic and the removal
of all water from the system. Also morphology was changed in this way. Nanorods
were transformed into spherical-shaped nanocrystals with average sizes around 50
nm. The synthesized nanomaterials were analyzed by X-ray diffraction (XRD) and
transmission electron microscopy (TEM). Spectroscopic properties were determined
from excitation and emission spectra. Measured luminescence decays showed the
energy transfer processes that occurred. The mechanism lying behind the observed
spectroscopic properties was proposed.
Funding for this research was provided by the National Science Centre (grant no.
DEC-2011/03/D/ST5/05701).
[1]
F. Auzel, Chem. Rev. 2004, 104 139-173.
T. Grzyb, A. Gruszeczka, R.J. Wiglusz, Z. Śniadecki, B. Idzikowski, S. Lis, J. Mater. Chem.
2012, 22, 22989-22997.
[2]
76
Thursday 17:40 - 20:10
Poster 019
Comparing the Mechanical Properties of Unsaturated
Polyester Composites Contain Different Additives and Fillers
Özgür Ceylan, Mehmet Arif Kaya, Mithat Çelebi, Hüseyin Yıldırım
Polymer Engineering – Yalova Üniversitesi – Rahmi Üstel Caddesi – Yalova – TUR
[email protected]
Unsaturated polyester resins are low molecular weight thermosetting materials containing double bonds and derived from unsaturated dibasic acid (or anhydride) and
glycols. It was known that first composite plastics were produced by using glass fiber
and unsaturated polyester resins in 1940.[1]
Nowadays, researchers have been performing studies on especially mechanical properties of unsaturated polyester based composites that contain different additives and
fillers. However, most researches were based on only one kind of additive or filler.[2,3]
It was not general that comparing mechanical properties caused by different fillers and
additives in the same study. Thus, in this study our aim is to compare the effects of
different additives and fillers on mechanical properties. A serie of polyester composites which contain different additives and fillers were prepared and their mechanical
properties such as tensile strength, modulus of elasticity, charpy and flexural strength
were evaluated and compared. In this study we used different fillers and additives
such as calsium carbonate, nanoclay, carbon fiber and SBR rubber. SBR rubber dried
in oven (50◦ C) prior to use. Also we have investigated the effect of different fillings
and additives mixtures on mechanical properties of samples prepared. The samples
were prepared by using same mold.
Key words: Unsaturated Polyester Resin, Fillers, Composit, Mechanical Properties
[1]
Kirk-Othmer Encyclopedia of Chemical Technology ISBN: 9780471238966
L. Xu, L. J. Lee “Kinetic analysis and mechanical properties of nanoclay reinforced unsaturated
polyester (UP) resins cured at low temperatures”, Polymer Engineering & Science 2005, 45 (4),
496-509.
[3]
M. Monti, M. Natali, R. Petrucci, J. M. Kenny, L. Torre, “Carbon Nanofibers for Strain and
Impact Damage Sensing in Glass Fiber Reinforced Composites Based on an Unsaturated Polyester
Resin” Polymer Composites, 32 (5), 766-775.
[2]
Poster 020
Thursday 17:40 - 20:10
77
Phase transfer of gold nanoparticles from aqueous to organic
solution
Beata Tkacz-Szczesna, Marcin Rosowski, Katarzyna Soliwoda, Grzegorz Celichowski,
Jaroslaw Grobelny
Department of Materials Technology and Chemistry – University of Lodz –
Pomorska 163 St., 90-236 Lodz – Lodz – POL
[email protected]
Gold nanoparticles (AuNPs) have potential application in the areas of electronic,
optics, optoelectronics, catalysis, biomedicine etc., because of their size and shapedependent chemical, optical and electrical properties. Some of the application require water based colloids while the other ones organic. The simple and reproducible
method for obtaining organic colloids is a phase-transfer of AuNPs from water solution to nonpolar solvent. In order to transfer nanoparticles to organic media it is
necessary to use a modifier – a compound that physically or chemically binds to the
AuNPs surface. It’s role is to provide stabilization of the nanoparticles in the organic phase. Moreover, this technique allows to use well-characterized nanoparticles,
various modifiers (e.g. thiol, alkylamines, carboxy acids, dithiophosphoric acids) and
solvents (e.g. hexane, toluene, chloroform, dichlorobenzene). In this presentation
the main idea of phase-transfer method will be shown. The size, size distribution
and stability of gold nanoparticles in organic media were tested by Dynamic Light
Scattering (DLS) measurements. UV-Vis spectroscopy was used to determinate the
efficiency of described method. By the use a phase-transfer method it is possible to
obtain AuNPs in organic solvents. Nanoparticles in organic media can be used as ink
component for printing electronics or spin coated layers.
Scientific work supported by MNiSW, funds for science in 2011-2014 allocated for the cofounded international project
[email protected]
78
Thursday 17:40 - 20:10
Poster 021
Molecular magnetism in cage-like silsesquioxanes containing
3d-transition metal atoms
Marina Dronova ∗ , Oksana Koplak‡ , Elena Shubina∗ , Aleksey Kirilin† ,
Mikhail Levitsky∗ , Aleksey Bilyachenko∗ , Aleksey Dmitriev‡ , Artem Talantsev‡
∗
Laboratory of metal hydrides –
A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences –
Vavilova/28 – Moscow – RUS
†
Department of hetero-organic chemistry –
Lomonosov Moscow University of Fine Chemical Technology –
prospect Vernadskogo/86 – Moscow – RUS
‡
Laboratory of magnetochemistry and spin dynamics –
Institute of Problems of Chemical Physics of Russian Academy of Sciences –
prospect Akademika Semenova/1 – Chernogolovka, Moscow region – RUS
[email protected]
Cage-like silsesquioxanes containing Cr(III), Fe(III), Mn(II) and Cu(II) ions, have
been prepared by common method of partial nucleophilic cleavage of polymeric metallasiloxanes.
All synthesized compounds have been structurally characterized by X-ray diffraction
analyses. We have established dependence of magnetic properties of the compounds
on quantity and type of metal ions as well as structural peculiarities of the cage.
There was made a comparison of magnetic properties for polymeric and cage-like
cobalt-containing silsesquioxanes. A correlation between metal content and value of
intradimeric exchange interaction J has been found out.
This work was supported by RFBR (project 11-03-00646)
Poster 022
Thursday 17:40 - 20:10
79
Fabrication of Ordered and Bamboo-type TiO2 Nanopore
Arrays via Pulse Anodization
Joanna Kapusta-Kołodziej , Grzegorz D. Sulka, Marian Jaskuła
Faculty of Chemistry, Department of Physical Chemistry and Electrochemistry –
Jagiellonian University – Ingardena 3 – 30-060 Kraków – POL
[email protected]
Nowadays, nanotechnology is interdisciplinary branch of sciences, which develops
rapidly and intensively. Among all new nanomaterials, enormous efforts have been
devoted to titanium dioxide (TiO2 ) especially in nanoporous/nanotubular forms due
to a successful combination of functional chemical and physical properties with a
well controllable nanoarchitecture, which make its one of the most important material highly desirable for diverse applications. Titanium dioxide it is now the subject
of intensive studies because of its potential and promise usefulness in bone growth
and regeneration, environmental applications, solar cells, catalysis, lithium insertion
and extraction, dielectrics, optoelectronics and sensors. Taking into the above mentioned importance of this nanostructured material, fabrication of titanium dioxide on
a nanometer size scale has fundamental and practical importance and, therefore these
materials have gained a lot of attention of the scientific community.[1]
It is well known that among all synthetic procedures, anodic oxidation is an excellent approach to fabricate TiO2 nanopore arrays due to its simplicity, low cost,
self-ordering process and facility of morphology control. Under the right conditions,
this technique leads to highly ordered nanopore or nanotubube arrays. A typical
nanostructured anodic titania film, fabricated in this way, exhibits close-packed array of hexagonally arranged tubes or cells containing pores in each cell center.[2] A
particular advantage for many further purposes is that grown oxide layers formed via
electrochemical anodization can be directly used as nanostructured electrodes.
Multi-sectional anodic titanium dioxide, consisting of alternating bamboo-shaped and
smooth-walled sections, different from the typical nanopore/nanotube arrays, could
be obtained by changing the anodization potential during the pore growth process. In
this work we report multi-sectional TiO2 nanopore arrays with bamboo-like features
fabricated by pulse anodization (PA) carried out under specific alternating-voltage
conditions. The anodic oxide layers with a structural modulation of pores were formed
by the two-step electrochemical anodization at room temperture in an ethylene glycol
solution containing NH4 F (0.38 wt%) and H2 O (1.79 wt%). It is expected that these
novel nanostructured architectures with a higher surface area, compared to the typical
TiO2 nanopore/nanotube arrays, could have various applications in the area of energy
conversion and storage.
Acknowledgments
This research was partially supported by the Polish Ministry of Science and High
Education (Grant No. N N204 213340).
[1]
M. Bayoumi, B. G. Ateya, Electrochem. Commun. 2006, 8, 38-46.
G. D. Sulka, J. Kapusta-Kołodziej, A. Brzózka, M. Jaskuła, Electrochim. Acta 2010, 55,
4359-4367.
[2]
80
Thursday 17:40 - 20:10
Poster 023
Synthesis of Substituted
5,6,7,8-Tetrahydroquinazolin-2-amine Compounds via
One-Pot Method
Ece Tosun, Fatma Tülay Tugcu
TUR
[email protected]
Quinazoline derivatives, as the nitrogen-containing heterocycles, are extremely important compounds with high biological activities as antimicrobial, antiinflammatory,
antihyperlipidemic, antihypertensive and anticonvulsant properties.[1-3] They have an
important place in the area of heterocyclic compounds because of their presence in
the structures of macrocyclic complex drugs, their applications in industry and usage
in pharmaceutical researches due to their biological properties.
Therefore, in this study, some new substituted quinazoline derivatives which are considered that may possess biological activity have been obtained via one-pot multicomponent method by using hetaryl carboxaldehydes, guanidine carbonate and 4methylcyclohexanone; and the structures of all these synthesized compounds have
been clarified with spectral data:[4]
Thanks for Yıldız Technical University Scientific Research Projects Coordination’s support in this study. Project No: 2012-01-02-GEP05.
[1]
S. Muthadı, J. Bandı, M. Chıdara, S. R. Muthadı, K.U. Sankar, V.M. Reddy, Scientific Journal
of Pharmacy 2011, 1(1), 30-37.
[2]
X. Li, M. Hilgers, M. Cunningham, Z. Chen, M. Trzoss, Z. Zhang, L. Kohnen, T. Lam, C.
Creighton, G. C. Kedar, K. Nelson, B. Kwan, M. Stidham, V. Brown-Driver, K. J. Shaw, J. Finn,
Bioorganic & Medicinal Chemistry Letters 2011, 21, 5171-5176.
[3]
N. M. Abdel Gawad, H. H. Georgey, R. M. Youssef, N. M. El-Sayed, European J. of Medicinal
Chemistry 2010, 45, 6058-6067.
[4]
L. Rong, H. Han, H. Wang, H. Jiang, S. Tu, J. Heterocyclic Chem. 2009, 46, 152,.
Poster 024
Thursday 17:40 - 20:10
81
Towards bionanotechnology diatom biosilica for nanoparticle assembly
Anne Jantschke ∗ , Cathleen Fischer∗ , Alexander Eychmüller† , Eike Brunner∗
∗
Bioanalytische Chemie – TU Dresden – Bergstr. 66 – Dresden – GER
†
Physikalische Chemie – TU Dresden – Bergstraße 66b – Dresden – GER
[email protected]
Nanoparticle arrays are of increasing interest owing to their various potential applications in optics, (opto)electronics, photovoltaics, and catalysis. The combination
of metal and semiconductor nanoparticles with biological materials, especially materials with ordered structures, provides various opportunities for the design of new
materials that combine natural structural characteristics with the special properties
of nanoparticles.
Diatom biosilica offers a number of advantageous properties: It consists of microand nanostructured amorphous silica. The shape and patterning of diatom biosilica
is genetically controlled and precisely reproduced from generation to generation. Approximately 200 000 diatom species are found in nature and provide us with a huge
variety of different structures.
The poster will give an overview about ongoing research on diatom based bionanotechnology:
i) Assembly, characterization and applications of diatom biosilica decorated with
noble metal and semiconductor nanoparticles
ii) Regioselective assembly of nanoparticles onto diatom biosilica
iii) DNP-NMR-measurements on diatom biosilica using TOTAPOL to characterize
the diatom surface
iv) Growing diatoms with Au@SiO2 -nanoparticles: in-vivo-studies
v) Depositing thin metal films
CLSM image of CdTe nanoparticles regioselectively
assembled onto diatom biosilica of Stephanopyxis turris
A. Jantschke, A.-K. Herrmann, V. Lesnyak, A. Eychmüller, E. Brunner, “Decoration of Diatom
Biosilica with Small (<10 nm) Noble Metal and Semiconductor Nanoparticles: Assembly, Characterization and Applications”, Chemistry - An Asian Journal 2011, DOI: 10.1002/asia.201100563
82
Thursday 17:40 - 20:10
Poster 025
Deposition of gold nanoparticles by the use of electrospray
technique
Marcin Rosowski , Beata Tkacz-Szczesna, Katarzyna Soliwoda, Grzegorz Celichowski,
Jaroslaw Grobelny
Pomorska 163 St – Lodz – POL
[email protected]
One of the novel method of gold nanoparticles (AuNP) deposition from water colloid
is electrospraying. The technique is based on spraying of liquid, controlled by electrical forces. An important feature and advantage of this method is that the evaporation
of solvent is very quick that it is possible to deposit particles in dry conditions. It can
be extremely important when solvents can cause damage of the structure of a solid
substrate. The surface density of nanoparticles on the sample can be controlled by
changing different electrospraying parameters e.g. flow rate, time, voltage, distance
between a nozzle and substrate, operation mode (single jet/ multi jet), nanoparticles
concentration and a solvent system in sprayed solution The influence of these parameters on the coverage of AuNP on the sample coverage was investigated. By the use
of electrospray deposition method it is possible to obtain sample coverage up to 90
percent and even more (multiple layer) if it will be necessary. Deposited in this way
AuNP can be used in a wide range of application such as electronics, biomedicine,
optics, optoelectronics and catalyze.
Scientific work supported by MNiSW, funds for science in 2011-2014 allocated for the cofounded international project.
[email protected]
Poster 026
Thursday 17:40 - 20:10
83
Optimization of operating parameters for sensitive and rapid
detection of hydrogen peroxide using a silver nanowire array
sensor
Elżbieta Kurowska, Grzegorz D. Sulka, Marian Jaskuła
Department of Physical Chemistry and Electrochemistry – Jagiellonian University –
Ingardena 3 – Krakow – POL
[email protected]
Nanoelectrochemistry is a relatively new branch of science that combines broad spectrum of fast and inexpensive, highly selective and sensitive electrochemical research
with a fabrication and testing of nanomaterials. A rapid development of nanoelectrochemistry is a consequence of a faster transfer of electrons between the electrode
based on nanomaterials and test substances (faster current response), and a high surface to volume ratio of nanomaterials that increases the sensitivity of chemical sensors
(lower detection and determination limits than those achieved for sensors based on
bulk materials). The development of nanotechnology requires fabrication of novel
nanomaterials and miniaturization of devices, that is particularly important in application areas such as bioanalysis and medicine, where a small size, high diagnostic
device sensitivity and selectivity are highly desirable features.
This research was focused on optimization of fabricating method used for the synthesis
of a non-enzymatic electrochemical sensor based on silver nanowire arrays for determination of hydrogen peroxide in the presence of interfering substances. Such sensors
are characterized by a low determination limit, rapid current response, high sensitivity, high selectivity and long-term stability. In real systems such as human blood, a
determined substance is usually accompanied by a very diverse mixture of chemical
compounds, which often disturb significantly a signal of the electrochemical sensor.
We believe that the fabricated hydrogen peroxide sensors based on silver nanowire
arrays or nanoporous thin films will be insensitive to interfering substances. Moreover, they can accurate determine the actual concentration of H2O2 in test samples
and allow to control the appropriate level of blood glucose in test patients.
The nanostructured electrochemical H2 O2 sensors were prepared by cathodic electrodeposition of silver inside the nanoporous anodic aluminum oxide (AAO) templates. The AAO templates were synthesized via a simple and cost-effective two-step
anodization of aluminum. After suitable treatment, free standing silver nanowire arrays were obtained and investigated as amperometric sensors for the detection and
determination of hydrogen peroxide. Typical electrochemical techniques, including
cyclic voltammetry and chronoamperometry were applied for examination of nanostructured sensors. The CV tests were used to select an appropriate potential for the
reduction of hydrogen peroxide. The chronoamperometric measurements carried out
in a phosphate buffer solution were used to study the response of electrochemical sensors to different concentrations of H2 O2 . The effects of the temperature, pH, volume
of added portions, concentration of hydrogen peroxide in a single portion and the
time interval between successive adding portions were studied.
Acknowledgements
The research was partially carried out with the equipment purchased thanks to the
financial support of the European Regional Development Fund in the framework of
the Polish Innovation Economy Operational Program (contract no. POIG.02.01.0012-023/08).
84
Thursday 17:40 - 20:10
Poster 027
Enzymatic regulation of adhesive functions of
peptide-polymer conjugates
Maria Meißler ∗ , Andreas Taden† , Hans G. Börner∗
Department of Chemistry, Laboratory for Organic Synthesis of Functional Systems –
Humboldt-Universität zu Berlin – Brook-Taylor-Str. 2 – Berlin – GER
†
Adhesive Technologies – Henkel AG und Co.KG aA – Henkelstr. 67 – Düsseldorf – GER
∗
[email protected]
Functional peptide-polymer conjugates are of great importance in material science.
Combination of peptides that bind specific inorganic surfaces with synthetic polymers
results in bioconjugates for a broad scope of industrial applications. Furthermore, it
is of peculiar interest to control and regulate the adhesive process of the bioconjugates
on the surface. A possibility of enzyme-activated peptide-polymer conjugates could
be presented already, whereas Tyrosinase is used to “switch on” adhesive functions
of a mussel-glue derived peptide segment, leading to bioconjugates that adhere to
steel.[1]
Herein, we present an approach for the specific suppression of adhesive functions of
bioconjugates on inorganic surfaces. Synthesis of peptide-PEO conjugates containing
a known metal binding peptide sequence leads to an efficient coating of a specific
material, which can be measured with quartz crystal microbalance (QCM). Introduction of a designed domain into the system results in negation of the adhesive
process by interference with the active binding site (Figure 1). Enzymatic treatment
“switches on” the binding domain and therefore recovers the adhesive properties of
the peptide-polymer conjugates.
Figure 1: Schematic representation of enzymatic regulation of adhesive functions of
peptide-polymer conjugates.
[1]
Patrick Wilke, Hans G. Börner, ACS Macro Lett. 2012, 1, 871-875.
Poster 028
Thursday 17:40 - 20:10
85
About nano- magnetic- photopolimerized microvessels in
controlled drug delivery
Adam Budniak , Maciej Mazur
Faculty of Chemistry – University of Warsaw – Pasteura 1 – Warsaw – POL
[email protected]
The possibility of delivery medication just to specific, diseased tissue would be a great
change in medicine, especially for treatment of cancer. It would not only enable to
limit intoxication of organism and improve effectiveness of therapy, but it also ease
to use well-known, strong drugs, which are too noxious to arrange them in great scale.
The way to solve this problem could be the encapsulation of medicine by neutral
to health polymer in order to decrease the initial contact of patient with the cure.
For specific directing drug-carrier, it is crucial to modify it and as the result enable
to affect with external magnetic field. At the end, microvessels must be opened in
special way, harmless for patient.
During the presentation, there will be introduced the method of synthesis of pollypyrole microvessels[1] with adsorbed magnetic nanoparticles[2] and exemplary way
for selective release of medicine. The author will also present advantages of application of photopolymerization method in comparison to chemical synthesis with use of
template.[3]
Fig. 1. Polypyrolle microvessels with adsorbed magnetic nanoparticles.
[1]
K. Kijewska, G. J. Blanchard, J. Szlachetko, J. Stolarski, A. Kisiel, A. Michalska, K.Maksymiuk,
M. Pisarek, P. Majewski, P. Krysiński, M. Mazur, Chem. Eur. J. 2012, 18, 310-320.
P. Majewski, "Sythesis, sorting and chemical modifications of the surface of magnetic ferrite
nanoparticles", Master thesis at Chemistry Faculty in the field of physical chemistry, Warsaw,
June 2007.
[3]
D.Kubacka, P. Krysiński, G. J. Blanchard, J. Stolarski, M. Mazur, J. Phys. Chem. B 2010,
114, 14890–14896.
[2]
86
Thursday 17:40 - 20:10
Poster 029
Nitroxide-Mediated Controlled Radical Polymerization as a
Method of Synthesis of the Novel Amphiphilic Polymers
Joanna Szafraniec, Szczepan Zapotoczny, Maria Nowakowska
Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry –
Jagiellonian University – Ingardena 3 – 30-060 Cracow – POL
[email protected]
Nitroxide-mediated controlled radical polymerization (NMP) is rapidly developed
technique in response to increasing need for new polymeric materials. It is metal
free technique which enable effective polymerization of a broad range of monomers
with control of molecular weight and structure of polymers.
Amphiphilic polyelectrolytes attract attention due to their wide range of practical applications resulting from the presence of hydrophilic groups which make them soluble
in water and chromophores which make them photoactive. To reduce the contact of
hydrophobic with hydrophilic medium, polymer spontaneously aggregates in aqueous
solution forming domains consisted of packed chromophores in which poorly soluble organic compounds can be solubilized. It makes such systems can be used as
nanocontainers or nanoreactors. For applications of the copolymer it is important
to have stable core of the micelle. It is believed that the core is better stabilized by
many short arms than by one long block of chromophores.
Novel amphiphilic polymers were synthesized via nitroxide-mediated controlled radical polymerization using 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy (HTEMPO)
free radical. The polymers dissolved in water self-assembly forming hydrophobic domains, which consist of highly packed hydrophobic arms. Presented results include
characterization of such aggregates.
Acknowledgements
Joanna Szafraniec acknowledges the financial support from the project Interdisciplinary PhD Studies “Molecular sciences for medicine” (co-financed by the European
Social Fund within the Human Capital Operational Programme).
Poster 030
Thursday 17:40 - 20:10
87
Synthesis of Aryl Iminothiazolidinone Compounds via
Multicomponent Reaction (Non-solvent) That is Suitable for
The Green Chemistry
Gizem Kahraman, Fatma Tülay Tugcu
TUR
[email protected]
Heterocyclic compounds and derivatives, showing very rapid development of organic
chemistry and constitute a part of increasing importance day by day. As a member
of the ring containing heteroatoms such as nitrogen, sulfur and oxygen thiazolidinone
derivative compounds are gaining importance due to antifungal, antitubercular, anticancer, anti-inflammatory, and antimicrobial activities.[1-3] Therefore, in this case,
the synthesis of such compounds is extremely important.
At the same time, the biologically active compounds very useful in the identification and optimization of the multicomponent reaction type is provided significant
improvements in the discovery of pharmaceutical products using.[4]
Therefore, the study was initiated, may be considered to possess biological activity,
a new aryl substituted iminothiazolidinone derivatives; thiophene-2-carboxaldehyde,
aryl thiourea, and chloroacetic acid are obtained using the multicomponent reaction
method,[5] structures of all compounds is illuminated with spectral data:
Thanks for Yıldız Technical University Scientific Research Projects Coordination’s support in this study. Project No: 2010-01-02-GEP01.
[1]
S. P. Singh, S. S. Parmar, K. Raman, V. I. ve Stenberg, Chemical Reviews 1981, 81, 175-203.
A. Verma, K. S. Saraf, European Journal of Medicinal Chemistry 2008, 43, 897-905.
[3]
M. Rahman, S. Mukhtar, W. Ansari, G. Lemiere, European Journal of Medicinal Chemistry
2005, 40, 173-184.
[4]
A. Dömling, I. Ugi, Angewandte Chemie International Edition 2000, 39, 3169-3210.
[5]
S. Kasmi-Mir, A. Djafri, L. Paquin, J. Hamelin, M. Rahmouni, Molecules 2006, 11, 597-602.
[2]
88
Thursday 17:40 - 20:10
Poster 031
Silicone membranes as a new corneal epithelial culture bed
Maria Grolik ∗ , Danuta Kuźmicz∗ , Krzysztof Szczubiałka∗ , Bogumił Wowra† ,
Dariusz Dobrowolski† , Edward Wylęgała† , Maria Nowakowska∗
∗
Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Cracow – POL
†
Department of Ophthalmology – District Railway Hospital – Panewnicka 65 –
Katowice – POL
[email protected]
The main aim of the project is development of novel biodegradable and resorbable
polymeric supports for corneal epithelial cells and to determine their physicochemical,
mechanical and biological properties. The diseases of cornea each year affect 15
million people worldwide according to World Health Organization (WHO) estimates
and are often sight-threatening. At present, the only generally accepted therapy
is the transplantation of the cornea from human donors. However, this treatment
has several drawbacks. The main one is limited number of human donors therefore
the science is looking for some alternatives. Regeneration of epidermal tissue can
restore and life-save cornea. Corneal tissue is usually cultured on human amniotic
membrane (AM).[1] The supports obtained from AM show good properties, however,
AM is difficult to obtain, expensive, and therefore cannot be used on a large scale.
The new hybrid organic - inorganic materials used to synthesize the supports are
natural polymers, with chitosan as the main component crosslinked with genipin and
EG Dundecyl ). Finding
by the addition of collagen and new silicone surfactant (DAP
2
2
an alternative support for culturing corneal cells would be a great breakthrough in the
surgery of the cornea and would certainly result in an increased number of sight-saving
surgeries performed.
[1]
D. Dobrowolski, E. Wylęgała, B. Wowra, A. Nowińska, “Application of autologous cultivated
corneal epithelium for restoring of corneal surface.” Acta Ophthalmol. 2010, 88, 246.
[2]
M. Grolik, K. Szczubiałka, B. Wowra, D. Dobrowolski, B. Orzechowska-Wylęgała, E. Wylęgała,
M. Nowakowska, “Hydrogel membranes based on genipin-cross-linked chitosan blends for corneal
epithelium tissue engineering.” J Mater Sci: Mater Med 2012, 23, 1991-2000.
Project operated within the Foundation for Polish Science Team Programme co-financed by the
EU European Regional Development Fund, PolyMed, TEAM/2008-2/6 and the National Science
Centre for funding of research project no 2011/01/N/ST5 /05544.
Poster 032
Thursday 17:40 - 20:10
89
Silver nanoparticles adsorption on solid surfaces for various
ionic strengths
Katarzyna Kubiak , Zbigniew Adamczyk
Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy of Sciences –
Niezapominajek 8, 30-239 – Cracow – POL
[email protected]
Silver nanoparticles exhibit a number of unique properties involving high antibacterial and catalytic activities in oxidation processes. Silver particle monolayers also find
practical applications in medicine, biology, pharmacology and catalysis, in surfaceenhanced Raman scattering (SERS) and metal-enhanced fluorescence (MEF) [1,2].
Stable silver nanoparticle sol was synthesized by the reduction of silver nitrate with
sodium borohydride and sodium citrate. Characterization of this sol involved the
extinction spectrum and solid weight content. Electrophoretic mobilities and the diffusion coefficient (hydrodynamic diameter) of particles were also measured using the
dynamic light scattering - DLS. It was determined that the hydrodynamic diameter
of particles was constant and equal to 11 nm for ionic strengths in the range of 10−5
M NaCl to 3 x 10−2 M NaCl (for pH=5.5), confirming a high stability of the sol. On
the other hand, the zeta potential of particles (calculated using the Henry’s model)
varied between -48 mV for 10−5 M to -39 mV for ionic strength of 3·10−2 M NaCl and
the same pH. Additionally, the UV-Vis method was used to study the stability of the
silver particle sol as a function of its bulk concentration. Particle shape and size distribution were also measured by the Atomic Force Microscopy (AFM) and Scanning
Electron Microscopy (SEM). Using these methods the kinetics of particle adsorption
on mica and silicon modified by cationic polyelectrolyte: poly(allylamine hydrochloride) - PAH was quantitatively evaluated. The influence of the ionic strengths and
the sol concentration was systematically studied. The kinetic runs obtained in these
measurements were adequately reflected for the entire range of times and bulk concentration by the random sequential adsorption (RSA) model.
[1]
[2]
90
M. Oćwieja, Z. Adamczyk, K. Kubiak, J. Colloid Interface Sci. 2012, 376, 1.
K. Aslan, J.R. Lakowicz, Ch.D. Geddes, J. Phys. Chem. B. 2005, 109, 6247.
Thursday 17:40 - 20:10
Poster 033
Liquid crystals - synthesis and properties of mesogenic Ni(II)
complexes
Katarzyna Purtak , Adam Krówczyński, Ewa Górecka
Department of Chemistry – University of Warsaw – Żwirki and Wigury St. 101 –
Warsaw – POL
[email protected]
New Ni(II) metallomesogens are described, having their chelating centre constructed
from two non-identical fragments: enaminoketone and barbiturylidenomethylenoamine rings, thus low Cs symmetry. Various side chains were attached to the mesogenic core. Despite a triangular molecular shape, almost all synthesised coupounds
exhibit a liquid crystalline hexagonal disordered columnar phase (Colh) with high
clearing temperature. The ability to create the columnar phase is propably connected with the permanent dipole moment appearing in the non-symmetric molecules
and dipole-dipole interactions between molecules in columns.
Discotic liquid crystal phase
A. Krówczyński, P. Krzyczkowska, M. Salamończyk, E. Górecka, D. Pociecha, J. Szydłowska,
“Mesogenic Ni(II) complexes of Cs symmetry forming Colh phase by dipole-dipole interaction”,
Liquid Crystals 2012, 39(6), 729-737
Poster 034
Thursday 17:40 - 20:10
91
Regioselective synthesis of highly functionalized
1,3-oxazin-2-ones via electrophilic cyclization of N -Cbz
protected propargylic amines
Alicia Monleón, José Ramón Pedro, Gonzalo Blay
Química Orgànica – Universitat de València – Doctor Moliner, 50 – Burjassot – ESP
[email protected]
The activation of a carbon-carbon triple bond towards a nucleophilic attack has been
widely carried out using transition metals as catalysts[1] or electrophiles as reagents.
The utilization of this latter activation method leads to functionalized structures with
high synthetic value.[2]
We have recently reported a convenient strategy for the synthesis of chiral nonracemic
N -Cbz protected propargylic amines 1 by the addition of terminal alkynes to imines
generated in situ from α -amidosulfones catalyzed by diethylzinc and a BINOL-type
ligand.[3]
The electrophilic activation of the triple bond in this kind of compounds 1 followed
by the intramolecular nucleophilic attack of the carbamate group should allow the
synthesis of highly functionalized cyclic structures. A 6-endo cyclization process
should lead to oxazinone moieties, a very important type of scaffold present in a great
variety of biologically active compounds.[4] Despite the increased attention on these
6-membered ring heterocyclic structures, only a few synthetic strategies have been
developed.[5]
In this communication, we present the regioselective electrophilic cyclization of N -Cbz
protected propargylic amines 1 to afford highly functionalized 3,4-dihydro-2H -1,3oxazin-2-ones 2 which are suitable starting materials for further desirable reactions.
Financial support from the Ministerio de Ciencia e Innovación and FEDER (CTQ200913083), Generalitat Valenciana (ACOMP/2012/212) and ISIC/2012/001is acknowledged.
A M thanks the Generalitat Valenciana for a pre-doctoral grant.
[1]
a) T. Saito, S. Ogawa, N. Takei, N. Kutsumura, T. Otani, Org. Lett. 2011, 13, 1098-1101; b)
M. Bian, W. Yao, H. Ding, C. Ma, J. Org. Chem. 2010, 75, 269-272.
[2]
A. K. Verma, S. P. Shukla, J. Singh, V. Rustagi, J. Org. Chem. 2011, 76, 5670-5684.
[3]
G. Blay, A. Brines, A. Monleón, J.R. Pedro, Chem. Eur. J. 2012, 18, 2440-2444.
[4]
a) R. Nicoletti, E. Buommino, A. De Filippis, M. P. Lopez-Gresa, E. Manzo, A. Carella, M.
Petrazzuolo, M. A. Tufano, World J. Microbiol. Biotechnol. 2008, 24, 189-195; b) M. Inami,
I. Kawamura, S. Tsujimoto, F. Nishigaki, S. Matsumoto, Y. Naoe, Y. Sasakawa, M. Matsuo, T.
Manda, T. Goto, Cancer Lett. 2002, 181, 39-45.
[5]
a) A. Arfaoui, I. Beltaïef, H. Amri, Synthetic Communications 2011, 41, 1536-1543; b) M.
Pattarrozzi, C. Zonta, Q. B. Broxterman, B. Kaptein, R. de Zorzi, L. Randaccio, P. Scrimin, G.
Licini, Org. Lett. 2007, 9, 2365-2368. R. Robles-Machín, J. Adrio, J. C. Carretero, J. Org.
Chem. 2006, 71, 5023-5026.
92
Thursday 17:40 - 20:10
Poster 035
Synthesis of Oleate Capped Gadolinium Oxide Nanocrystals
Madlen Schmudde, Christian Goroncy, Christina Graf
Institut für Chemie und Biochemie –
Physikalische und Theoretische Chemie, Freie Universität Berlin – Takustr. 3 –
[email protected]
Nowadays magnetic resonance imaging (MRI) is widely used in modern medicine.
Unfortunately, the resolution and sensitivity of this technique are quite low, so that
contrast agents are necessary to improve the results of MRI.[1] Quite promising results
as new contrast agents for MRI give gadolinium oxide nanoparticles, which could be an
alternative to today clinically mainly used gadolinium chelates.[2] These nanoparticles
could give a higher contrast because of their higher ion concentration and provide
superior possibilities for functionalization.[3]
In the present study a simple synthetic route for the preparation of oleate capped
gadolinium oxide nanocrystals was developed. This synthesis is based on the thermal
decomposition of a metal oleate precursor in a high boiling solvent, which is already well established for the preparation of many other metal oxide nanoparticles.[4]
Accordingly, a gadolinium oleate precursor was decomposed in octadecene or alternatively in trioctylamine at 320◦ C or 350◦ C to yield 2.5 nm to 3.5 nm diameter
spherical gadolinium oxide nanoparticles. The nanoparticles were characterized by
high-resolution transmission electron microscopy (HRTEM) and dynamic light scattering (DLS). By using X-ray powder diffraction (XRD) measurements show that
the particles are highly crystalline. The surface functionalization with the capping
agent oleate was verified by IR spectroscopy. This simple preparation method for
highly stable gadolinium oxide nanoparticles provides a wide scope for further surface modifications by ligand exchange reactions as well as the opportunity for doping
the inorganic core with other rare metal ions providing an additional fluorescence
function.
[1]
H. B. Na, I. C. Song, T. Hyeon, Adv. Mater. 2009, 21, 2133-2148.
G. H. Lee, Y. Chang, T.-J. Kim, Eur. J. Inorg. Chem. 2012, 1924-1933.
N. J. J. Johnson, W. Oakden, G. J. Stanisz, R. S. Prosser, F. C. J. M. van Veggel, Chem. Mat.
2011, 23, 3714-3722.
[4]
J. Park, K. J. An, Y. S. Hwang, J. G. Park, H. J. Noh, J. Y. Kim, J. H. Park, N. M. Hwang,
T. Hyeon, Nat. Mater. 2004, 3, 891-895.
[2]
[3]
Poster 036
Thursday 17:40 - 20:10
93
Up-conversion of REPO4 nanocrystals doped with
Yb3+ /Er3+ , Yb3+ /Tm3+ and Yb3+ /Tb3+ ions
Dominika Przybylska ∗ , Rafał Wiglusz†
Department of Rare Earths, Faculty of Chemistry – Adam Mickiewicz University –
Grunwaldzka 6, 60-780 Poznan – Poznań – POL
†
Institute for Low Temperature and Structure Research – Polish Academy of Sciences –
P.O. Box 937, 50-442 Wroclaw – Wroclaw – POL
∗
[email protected]
Up-conversion is one of the most investigated phenomenon in lanthanide doped nanomaterials. Luminescent properties of lanthanide ions (Ln3+ ) are the result of energy
transfer (ET) processes between them. Lanthanide ions may convert energy from the
ultraviolet range to the visible light (down-conversion). However, reversed process
is also possible, where absorbed light from the near-infrared range is converted into
visible wavelengths due to up-conversion. Up-conversion (UC) it is a phenomenon in
which the sequential absorption of two or more photons leads to the emission of light
at shorter wavelengths than the excitation wavelength (anti-Stokes type emission)[1]
In recent years, UC was intensively studied in nanocrystalline systems.[2,3] They have
a high potential for industrial and biological applications, e.g. can be used as biological assays.[4,5]
Rare earth (RE = Y, La or Gd) phosphates are especially interesting for bioapplications and as hosts for luminescent Ln3+ ions because of their relatively high
biocompatibility. Also up-conversion in this systems could be effective.[6] REPO4
nanocrystals doped with Yb3+ /Er3+ , Yb3+ /Tm3+ and Yb3+ /Tb3+ ions were synthesized by co-precipitation method. The best reaction conditions, in order to obtain
small size of the crystals, were estimated and glycerin solution was used as the reaction medium. The result of this reaction ware nanocrystals composed from nanorods
with thickness up to 10 nm and length around 500 nm. Measured excitation and
emission spectra as well as luminescence decays were base for spectroscopic studies
and were used to investigate energy transfer processes. Structural and morphological
properties were examined using X-ray diffraction (XRD) and transmission electron
microscopy (TEM). Synthesized nanomaterials showed bright yellow (Yb3+ /Er3+ ),
blue (Yb3+ /Tm3+ ) and green (Yb3+ /Tb3+ ) up-conversion emission.
Funding for this research was provided by the National Science Centre (grant no.
DEC-2011/03/D/ST5/05701).
[1]
F. Auzel, Chem. Rev. 2004, 104, 139-73.
S. Heer, O. Lehmann, M. Haase, H.-U.H.-U. Güdel, Angew. Chem. Int. Ed. 2003, 42,
3179-3182.
[3]
S. Zeng, J. Xiao, Q. Yang, J. Hao, J. Mater. Chem. 2012.
[4]
F. Wang, D. Banerjee, Y. Liu, X. Chen, X. Liu, Analyst 2010, 135, 1839-54.
[5]
M.E. Lim, Y.-ling Lee, Y. Zhang, J.J.H. Chu, Biomaterials 2011, 3-11.
[6]
T. Grzyb, A. Gruszeczka, R.J. Wiglusz, Z. Śniadecki, B. Idzikowski, S. Lis, J. Mater. Chem.
2012, 22, 22989-22997.
[2]
94
Thursday 17:40 - 20:10
Poster 037
Synthesis and characterization of polysiloxanes thin films
Agnieszka Puciul-Malinowska, Vladyslav Kuryltso, Szczepan Zapotoczny
Department of Chemistry – Jagiellonian Uniwersity – Ingardena 3 – Krakow – POL
[email protected]
During the last few years the interest of the formation of microcapsules that may serve
as containers for drug delivery or photorectors for conversion of sunlight energy is still
growing. Due to that there is a very great interest of formation of flexible coatings
for that microcapsules. For that purpose the great material are polysiloxanes because
of their biocompability and very high flexibility of the chains. Their water-soluble
properties also cause that these polymers are very well suited for that purpose. .
This work presents the polysiloxane film formation on model surfaces obtained by
Electrostatic Self-Assembly “layer-by-layer” method and its characterization. Atomic
Force Microscopy and Spectroscopic Ellipsometry were used to determine dependence
of the film thickness from the number of bilayers. In addition the impact on film
topography of different types of rising, namely stream of the water and sonication,
was observed. The films will be further used as functional coatings for photochemical
applications.
The authors would like to thank Polish Ministry of Science and Higher Education for
the financial support (“Ideas Plus” grant no. IdP2011 000561).
Poster 038
Thursday 17:40 - 20:10
95
Selective Growth of Trigonal and Hexagonal Shaped Silver
Micro Nano Platelets at the Water/Oil Interface
Eike Gericke ∗ , Stefan Weidemann† , Roman Bansen‡ , Torsten Boeck‡ ,
Franziska Emmerling , Klaus Rademann∗
∗
Institute for Chemistry – Humboldt-Universität zu Berlin – Brook-Taylor-Str. 2 –
Berlin – GER
†
Institute for Physics – Humboldt-Universität zu Berlin – Newtonstr. 15 – Berlin – GER
‡
Leibniz-Institute for Crystal Growth – Max-Born-Str. 2 – Berlin – GER
BAM Bundesanstalt für Materialprüfung – Richard-Willstätter-Str. 11 – Berlin – GER
[email protected]
A particle synthesis method for the shape selective growth of thin silver micro nano
platelets at the water/oil interface is presented. In this case no additives are needed
to reach the shape selectivety. The seed dependence of the growth, as well as the
ripening kinetics, give the full procedure control.
This method pursues former results for shape selective growth in particle dimensions[1]
and proposses a more detailed mechanistic model[2] than before.
The experiments were evaluated for reagent concentrations between 10−3 and 10−2
mol/l and in a reaction time window from 30 minutes to 3 days with ESEM, FESEM,
AFM and XRD.
We show that the shape selective production of silver particles in this set up is possible
and give a detailed machanistic propose. Possible applications could be oxidation and
oxygenation catalysis, microelectronics ore analytical usages for SERS.
[1]
A. Wang, H. Yin, M. Ren, Y. Liu, T. Jiang, Appl. Surf. Sci. 2008, 254, 6527.
[2]
M. S. Jin, Q. Kuang, X. G. Han, S. F. Xie, Z. X. Xie, L. S. Zheng, J. Solid State Chem. 2010,
183, 1354.
96
Thursday 17:40 - 20:10
Poster 039
Asbestos in environmental soil samples
Sylwia Lipiecka, Katarzyna Makowska, Zuzanna Kowalkiewicz, Włodzimierz Urbaniak
Faculty of Chemistry – Adam Mickiewicz University in Poznan –
Umultowska Street 89 B – Poznan – POL
[email protected]
Asbestos as well-known harmful material[1] should be controled in environment. Admittedly, the largest health risk is related with presence of this mineral in the air, but
other elements of environment, e.g. soil or water, could be also contaminated with
asbestos fibers and cause secondary fibers emission into atmosphere and exposure. [2]
Asbestos analyses, practically limited only to air samples, base mainly on obsolete
methods and the new solutions, especially for liquid and soil samples despite the
market requirements, aren’t sufficiently developed.
Asbestos contamination in soil could be the result of precipitation with fibers from the
air, elution from asbestos-cement materials for example roof sheets, from debris during
removal work and asbestos-waste disposal. For confirmation of correctness of executed
work and safety for people health is required the environmental monitoring.[3] Results
of analyses are also important by administrative decisions regarding the sites.
The elaborated method[4] enables the asbestos determination in soil and liquid samples with use the phase contrast optical microscope. This is a relatively fast and easy
and not expensive analysis. The suitable sample preparation, all asbestos characteristics considered, assures increasing of investigations.[5]
We would like to present the study of asbestos separation from soil samples, which
have a very complex matrix and findings for quantitative asbestos determination by
phase contrast microscopy. With use the proposed method since 2009 the environmental monitoring of area next to farm building with asbestos cement roof is made
and the results would be the part of the presentation.
[1]
Virta R. L., “Asbestos: Geology, Mineralogy, Mining, and Uses”, U.S. Geological Survey, OpenFile Report 02-149, Version 1.0, 2002.
[2]
A. Domaszewicz, S. Lipiecka, W. Urbaniak, “Problems in asbestos analyses in environmental
and bulk samples, Integrated waste management”, PZiTS, Poznan, 2009.
[3]
Lipiecka S., Szeflińska K., Narożny M., Eitner K., Urbaniak W. “Asbestos dust in municipal
environment”, Przegląd Komunalny, 3/2012 (246), Publisher Abrys, 2012.
[4]
S. Lipiecka, A. Domaszewicz, B. Staniszewski, W. Urbaniak, “Asbestos Determination”, Polish
Patent 2012 (Application P-389368, 2009).
[5]
S. Lipiecka, A. Domaszewicz, K. Szeflińska, W. Urbaniak, “Method of asbestos separation in
soil samples and determination by optical microscope”, Ars Separatoria Acta 2009/2010, ISSN
1731-6340, No. 07, 85-98.
Poster 040
Thursday 17:40 - 20:10
97
Antioxidant characteristics of the plant extracts from traffic
polluted and unpolluted areas
Marija Ilic ∗ , Snezana Jovanovic∗ , Strahinja Simonovic∗ , Violeta Mitic∗ ,
Vesna Stankov-Jovanovic∗ , Snezana Nikolic-Mandic†
∗
Department of Chemistry – University of Niš, Faculty of Sciences and Mathematics –
Visegradska 33 – Nis – SER
†
Department of Analytical Chemistry – University of Belgrade, Faculty of Chemistry –
Studentski trg 12-14 – Belgrade – SER
[email protected]
Plants have specific chemical composition which depends on plant species, habitat and
series of environmental factors. Certainly, one of the major factors is traffic pollution.
Term traffic pollution refers mostly to the form of air pollution coming from vehicles. Several studies have confirmed link between pollution and plants metabolism,
which means changes in production of certain compounds by permanently exposure
to pollutants. The aim of the present research study was examination of antioxidant
activity, total phenol and total flavonoid content in plants from two localities: near
main road (polluted environment, Sicevacka gorge, route Nis-Sofia) and natural environmental (Ploce, unpolluted nearby area). The plant species: Anthemis tinctoria,
Stenactis annua, Crepis foetida and Artemisia vulgaris were the most abundant in
polluted area, recognized as remedies in traditional medicine and therefore have become the subject of the study. In estimation of antioxidant characteristics, DPPH and
ABTS assays (based on free radical scavenging) and Total reducing power of ferrous
to ferri ion were used (TRP). Determination of total phenols was performed by FolinCiocalteau assay, and determination of total flavonoids was based on usage of AlCl3
which forms colored complexes with flavonoids. Investigated methanol extracts were
obtained by ultrasonic extractions. The results which expressed ability of samples to
scavenge DPPH radical (EC50 values) and ABTS radical cation (Trolox equvalents)
are very similar; extract samples from polluted area, showed higher activity except
for C. foetida against DPPH, where the reverse dependence was registered. In regard
to TRP, higher values for samples from polluted area in comparison to those from
natural environmental were obtained. Contents of phenols and flavonoids were higher
in plants which grew near magistral road. Surprisingly, obtained results showed that
plants in potentially polluted environment possessed higher antioxidant activity and
higher flavonoids and phenols content.
Acknowledgements: The research was supported by the Serbian Ministry of Education, Science and Technology Development (Grant no 172051).
Keywords: Traffic polluted, antioxidant characteristics, Anthemis tinctoria, Stenactis
annua, Crepis foetida, Artemisia vulgaris
98
Thursday 17:40 - 20:10
Poster 041
Changes in gene expression in frog heart after exposition to
heavy metal ions
Marta Kaczor-Kamińska
Chair of Medical Biochemistry – Jagiellonian University Medical College – Kopernika 7 –
Krakow – POL
[email protected]
Heavy metal ions (Cd, Hg, Pb) are environmentally persistent toxins. There are
three main reasons contributing into their high toxicity in living organisms: 1) high
affinity for thiol-, histydyl-, amino- and carboxyl groups of amino acid residues in
proteins (changes in structural and catalytic properties of proteins), 2) effect on the
antioxidant potential of cells - a reduced level of glutathione can ultimately produce
oxidative stress, 3) their competing with metal cations of active sites of proteins, what
leads to inhibition or modification of a protein activity. The main objective of the
study was to investigate changes in the activity and expression of γ-cystathionase
(CST) and sulfurtransferase 3-mercaptopyruvate (MPST), enzymes participating in
the non-oxidative metabolism of cysteine, and the expression of mitochondrial and
cytoplasmic superoxide dismutase in hearts of frogs - Pelophylax ridibundus exposed
to lead (28 mg Pb/l;10 days) and cadmium (40 and 80 mg Cd/l; 4 or 10 days) and
Xenopus laevis (X. tropicalis) exposed to mercury (1.353 mg Hg/l; 7, 10 or 14 days).
The results confirmed changes in the expression of genes encoding for CST and MPST
in the heart. An increased expression of the CST gene was observed in hearts of frogs
exposed to mercury ions, while lead and cadmium ions had no effect and the expression
was comparable to that seen in the control group. The expression of the MPST gene
in the heart was decreased in response to exposure to all of the investigated ions.
Furthermore, changes in expression were correlated with a decrease in MPST specific
activity accompanied by a decrease in the level of sulfane sulfur. The exposition to
cadmium and lead ions resulted in the increase in the content of total glutathione and
the ratio of GSH/GSSG in the heart. These effects all together suggest that cysteine is
directed to the synthesis of glutathione and is less readily available for the production
of sulfane sulfur through the MPST-dependent pathway. It was also observed that
the expression of gene for the cytosolic superoxide dismutase was increased after the
exposure to the investigated ions, possibly in response to an elevated level of reactive
oxygen species.
Poster 042
Thursday 17:40 - 20:10
99
Synthesis and Photophysicochemical Properties of Novel
Zinc Phthalocyanines
Ali Erdogmus, Erkan Kırbac, Goknur Yasa, A. Lütfi Ugur, Ibrahim Erden
Chemistry – Yildiz Technical University – Davutpasa Campus – Istanbul – TUR
[email protected]
Phthalocyanines (Pcs) are remarkable macrocyclic compounds having magnificent
physical and chemical properties. They are usually synthesized starting from the
appropriate phthalonitriles and their derivatives or their substitution yield as metalfree phthalociyanine and metallophthalocyanines which obtained especially in high
temperatures with the presence of a suitable anhydrous metal salt.[1,2] Metallophthalocyanines (MPcs) have potential applications in many areas such as in medicinal
and material science.[3,4] MPcs enjoy usage in printing inks, catalysis, display devices, data storage, chemical sensors, gas sensors, solar cells, organic light emitting
devices (OLED), PDT and photonic devices.[5,6] In this study, we report the synthesis,
characterization of different substituted zinc phthalocyanines. The new compounds
have been characterized by elemental analysis, UV, FT-IR, 1H-NMR spectroscopy
and mass spectra. The effect of fluorine, bromine and chlorine substitituents on
photophysical and photochemical properties were reported. The singlet oxygen, photodegradation, fluorescence quantum yield, triplet quantum yield and triplet life time
of the complexes in DMF, THF, DMSO were determined. Fluorescence quantum
yields for the complexes ranged from 0.19 to 0.30.
[1]
C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyanines -Properties and Applications, vols. 1-4,
VCH, New York, 1989-1996.
[2]
N.B. McKeown, Phthalocyanine Materials-Synthesis, Structure and Function, Cambridge
University Press, New York, 1998.
[3]
K. Kadish, K. M. Smith, R. Guilard, editors. The porphyrin Handbook, vol. 15-20, Boston:
Academic Press, 2003.
[4]
K. Morishige, S. Tomoyasu, G. Iwani, “Adsorption of CO, O2, NO2, and NH3 by metallophthalocyanine monolayers supported on graphite”, Langmuir 1997, 13, 5184-5188.
[5]
F. H. Moser, L. R. Thomas, Phthalocyanine compounds, New York: Reinhold, 1963, 123-145.
[6]
T. Tominaga, K. Hayashi, N. Toshima “Construction of a ‘sequential potential field’ by [Cu(pc)]/
[Zn(pc)] double-layered thin film: application to electrochromic and electroluminescent devices”,
J. Porphyr. Phtalocyan. 1997, 1, 239-249.
100
Thursday 17:40 - 20:10
Poster 043
Spectroscopic analysis of Xylella fastidiosa biofilms
Bärbel Abt ∗ , M.A. Cotta† , D.M. Murillo Munar† , R. Janissen† , B.C. Niza Silva‡ ,
A.A. de Souza‡ , G.S. Lorite , C. Kranz∗ , B. Mizaikoff∗
∗
Analytische und Bioanalytische Chemie – Universität Ulm – Ulm – GER
†
Instituto Física Gleb Wataghin – UNICAMP – Campinas – BRA
‡
Instituto Agronômico – Centro de Citricultura Sylvio Moreira – Cordeiropolis – BRA
Institute of Biomedicine – University of Oulu – Oulu – FIN
[email protected]
Xylella fastidiosa (Xf) is a gram-negative phytopathogen bacterium that particularly
affects the xylem vessels of citrus plants by vascular occlusion. This causes diseases
such as Pierce’s disease or citrus variegated chlorisis (CVC).[1] Substantial economic
losses of annually exceeding $ 100 million for the citrus industry may be attributed
to Xylella fastidiosa. As an important step toward fully understanding this bacterium, the genome of Xylella fastidiosa has recently been sequenced in part by our
collaborators.[2] Yet, the molecular mechanisms involved in colonization of the xylem
by this phytopathogen, and in particular the involved biofilm formation remain little
understood.
A vested interest in the role of biomolecules during biofilm formation is not only
limited to agricultural aspects. Considering that biofilms play an important role
for many bacterial-caused diseases, the relevance of investigating the adsorption and
colonization of bacteria at surfaces, and the associated biofilm formation with respect
to the involved proteins and biomolecules is evident.[3-5] For this purpose disulfide
bonds play an important role for the formation of biofilms.[6]
In the present study, spectroscopic techniques were used to investigate the chemical and structural properties of the biomolecules involved in Xf biofilm formation.
Spectroscopic techniques and in particular infrared attenuated total reflection (IRATR) spectroscopy were used to characterize in detail the growth media of Xf and
its molecular components. On the basis of the characterization of the media, a better understanding on the formation of biofilms by Xf and the molecular components
may be derived. Experimental and analytical procedures will be accompanied by
first results on the characterization of growth media with IR-ATR spectroscopy and
complementary spectroscopic techniques.
[1]
A. H. Purcell and D. L. Hopkins, “Fastidious xylemlimited bacterial plant pathogens”, Annual
review of phytopathology 1996, 34(c), 131-151.
[2]
The Xylella fastidiosa Consortium of the Organization for Nucleotide Sequencing and Analyisis,
“The genome sequence of the plant pathogen Xylella fastidiosa”, Nature 2000, 406(13), 151-159.
[3]
G. S. Lorite, A. A. de Souza, D. Neubauer, B. Mizaikoff, C. Kranz, and M. A. Cotta, “On the role
of extracellular polymeric substances during early stages of Xylella fastidiosa biofilm formation.”
Colloids and surfaces. B, Biointerfaces 2013, 102, 519-25.
[4]
G. S. Lorite, C. M. Rodrigues, A. A. de Souza, C. Kranz, B. Mizaikoff, and M. A. Cotta, “The
role of conditioning film formation and surface chemical changes on Xylella fastidiosa adhesion
and biofilm evolution.”, J Colloid Interface Sci 2011, 359(1), 289-295.
[5]
R. M. Donlan and J. W. Costerton, “Biofilms: Survival Mechanisms of Clinically Relevant
Microorganisms”, Clinical Microbiology Reviews 2002, 15(2), 167-193.
[6]
C. A. Santos, M. A. S. Toledo, D. B. B. Trivella, L. L. Beloti, D. R. S. Schneider, A. M. Saraiva,
A. Crucello, A. R. Azzoni, A. A. Souza, R. Aparicio, and A. P. Souza, “Functional and structural
studies of the disulfide isomerase DsbC from the plant pathogen Xylella fastidiosa reveals a redoxdependent oligomeric modulation in vitro.” The FEBS journal 2012, 279(20), 3828-3843
Poster 044
Thursday 17:40 - 20:10
101
New Diselenooxalato Complexes
Structure, EPR and TG/DTA studies
∗
Mike Neumann ∗ , Uwe Schilde† , Peter Strauch∗
Institute of Chemistry, Inorganic Material Chemistry – University of Potsdam –
Karl-Liebknecht-Str. 24-25 – Potsdam – GER
†
Institute of Chemistry, Inorganic Chemistry – University of Potsdam –
Karl-Liebknecht-Str. 24-25 – Potsdam – GER
[email protected]
The chemistry of coordination compounds with thiooxalato ligands and in particular
with the dithiooxalato ligand is well-investigated.[1] In contrast the synthesis and
characterisation of selenium and tellurium analogs is widely unexplored. Only the
synthesis of two diselenooxalato complexes, bis(benzyltriphenylphosphonium)bis(1,2diselenooxalato)metallate(II) (M = Ni, Cu), and the structure of the Ni-complex as
well as the preparation of the diselenooxalato ligand in form of the potassium salt
have been published yet.[2,3]
Here we present new complexes of the [cation]2 [Ni(dso)2 ] type, as well as the related
diselenosquarato analogs, and their structures (Fig. 1). The paramagnetic copper(II)
complexes (S = 1/2, I = 3/2) are well-suited to be studied by EPR-spectroscopy.
TG/DTA and XRD measurements will give information about the thermal behaviour
of the complexes and their potential as possible precursors in material science.
Figure 1: X-Ray structure of the mononuclear (K(18-Crown-6))2 [Pd(dso)2 ] complex.
[1]
W. Dietzsch, P. Strauch, E. Hoyer, Coord. Chem. Rev. 1992, 121, 43. [2] P. Strauch,
S. Abram, U. Drutkowski, Inorg. Chim. Acta 1998, 278, 118. [3] C. Matz, R. Mattes, Z.
Naturforsch. 1978, 33b, 461.
102
Thursday 17:40 - 20:10
Poster 045
Ultrasound effects on adsorption of Cu(II) on
methyl-sulfonated Lagenaria vulgaris shell
Maja Stanković, Nenad Krstić, Jelena Mitrović, Ružica Nikolić, Miljana Radović,
Danijela Bojić, Aleksandar Bojić
Department of Chemistry – Faculty of Sciences and Mathematics, University of Niš –
Visegradska 33 – Niš – SRB
[email protected]
The rapid industry development leads to rising of the contamination of available water
resources, while increasing of global population requires new sources of drinking water.
Therefore, the challenge for scientists is to find cheap, efficient, environmental-friendly
materials for removal of pollutants from industrial and communal/atmospheric wastewaters. In this study, methyl-sulfonated shell of Lagenaria vulgaris (msLVB) was investigated as a novel, low-cost biosorbent for the removal of copper from aqueous
solutions with and without the assistance of ultrasound. Lagenaria vulgaris shell
represents a lignocellulosic material with ability for binding metal cations due to
presence of hydroxyl, carboxylic, lactonic and phenolic groups in its structure, while
treatment with formaldehyde and sodium-sulphite was used to introduce sulphonic
groups, known by significant ion-exchanging capacity. Sorption kinetics was investigated in batch conditions, using 125 mL of the solution with 50.0 mg L-1 of Cu(II)
ions, 4.0 g L-1 of msLVB, at pH 5.0 and 25 o C. The experiments were performed
using magnetic stirrer on 200 rpm or ultrasonic bath with the frequency of 40 kHz.
The sorption was considerably increased in the presence of ultrasound (Fig. 1). The
kinetic data fitted very well the pseudo-second-order kinetic model.
Effect of mixing on adsorption capacity of msLVB for Cu(II) ions
Poster 046
Thursday 17:40 - 20:10
103
Treatment of Basic Dye from Textile Wastewaters by
Sulfonated Polymers
Mehmet Arif Kaya, Mithat Çalebi, Özgür Ceylan, Hüseyin Yildirim
Polymer Engineering – Yalova University – Yalova – TUR
[email protected]
The textile industry consumes huge volumes of water in different wet processes and as
a result it was obtained significant amount of colourful wastewater from dye process.
In dying process, various dyes can be used such as acidic, reactive, basic, disperse,
azo, diazo, antraquionone-based and metal complex dyes according to fabric types.[1]
Basic dyes are cationic soluble salts of coloured bases. Basic dyes are applied to
substrate with anionic character where electrostatic attractions are formed. Basic
dyes are powerful colouring agents. It’s applied to polyacrylonitrile, modified nylons,
modified polyesters, paper. They are generally water soluble.[2]
In this study, treatment of basic dye (Basic Red 481) from local textile mill was
investigated by different sulfonated polymers at different pHs.
Key words: basic dye, textile dye, decolorization, sulfonated polymer
Removal of Basic Red 46 by sulfonated polymers after 2 hour. K: Control.
[1]
A. Tuba, G.Tuğba, G. Afife, D Gönül, M. Ülkü, “Decolorization of textile azo dyes by ultrasonication and microbial removal”, Desalination 2010, 255, 154-158.
[2]
V.K. Gupta, Suhas, “Application of low-cost adsobents for dye removal-A review”, Journal of
Environmental Management 2009, 90, 2313-2342.
104
Thursday 17:40 - 20:10
Poster 047
Removal of Phenolic Derivatives from Wastewater using
Photocatalytic Membranes
Cristina Orbeci, Gheorghe Nechifor, Ion Untea
Department of Analytical Chemistry and Environmental Engineering –
“Politehnica” University of Bucharest – 1-7 Gh. Polizu Street – Bucharest – ROU
[email protected]
The presence of phenol and phenolic derivatives in water induces toxicity, persistence
and bioaccumulation in plant and animal organisms and is a risk factor for human
health. In consequence, the identification and monitoring of these compounds detectable in drinking water and surface waters are imperative.
Available technologies dealing with phenolic compounds include the advanced oxidation processes (AOPs), based on the formation of very active hydroxyl radicals,
which react quickly with the organic contaminant. AOPs present the advantage of
completely removing organic contaminants from the environment, not only from the
aqueous phase, by transforming them into other organic compounds with low toxicity
and finally into innocuous inorganic species. The technologies for removing phenolic derivatives based on membranes and photocatalytic processes play an important
role.[1] Among the AOPs, the photocatalytic process is one of the most attractive
methods because the reagent components are easy to handle and non-toxic to the
environment.[2] Separation membranes have become essential parts of human life because of their growing industrial applications in high technology such as biotechnology,
nanotechnology and membrane based separation and purification.[3-5]
This paper presents a hybrid method for an advanced removal of low biodegradable
organic compounds from water, by combining the separation selectivity of membranes
with the high oxidation efficiency of the photocatalytic process. The hybrid process for
the disposal of phenolic compounds from aqueous solutions combines the selectivity
of membranes with high efficiency and the photocatalytic process.
[1]
Fei Feng, Zhenliang Xu, Xiaohuan Li, Wenting You, Yang Zhen Advanced treatment of dyeing
wastewater towards reuse by the combined Fenton oxidation and membrane bioreactor process,
Journal of Environmental Sciences 2010, 22 (11), 1657-1665;
[2]
Lifen Liu, Guohua Zheng, Fenglin Yang, Adsorptive removal and oxidation of organic pollutants
from water using a novel membrane, Chemical Engineering Journal 2010, 156 (3), 553-556;
[3]
Bui Xuan Thanh, Vo Thi Kim Quyen, Nguyen Phuoc Dan, Removal of Non-Biodegradable
Organic Matters from Membrane Bioreactor Permeate By Oxidation Processes, Journal of Water
Sustainability 2011, 1 (3), 289–299;
[4]
Xiaobin Wanga, Xiongfu Zhanga, Haiou Liua, King Lun Yeungb, Jinqu Wang, Preparation
of titanium silicalite-1 catalytic films and application as catalytic membrane reactor, Chemical
Engineering Journal, 2010, 156, 562-570;
[5]
Huabing Jianga, Guoliang Zhanga, Tao Huanga, Jinyuan Chena, Qidong Wangb, Qin Mengc,
Photocatalytic membrane reactor for degradation of acid red B wastewater, Chemical Engineering
Journal 2010, 156, 571-577.
Poster 048
Thursday 17:40 - 20:10
105
The impact of the extraction of magnesium on changing of
the optical properties of chrysotile fibers
Katarzyna Makowska, Sylwia Lipiecka, Zuzanna Kowalkiewicz, Włodzimierz Urbaniak
Faculty of Chemistry – Adam Mickiewicz University – Umultowska 89B – Poznań – POL
[email protected]
Chrisotile is an inorganic fibrous mineral naturally occuring in the nature. A single
fiber is composed of two layers - hexagonal magnesium hydroxide layer and tetragonal
silicalayer forming a “tube” with a diameter of 25-30 nm and a center channel with a
diameter of about 5 nm. Chrysotile fibers are present in tightly packed bundles, but
are bound together only by weak van der Waals interactions, and therefore can be
readily separated by mechanical actions.[1]
Chrysotile has specific optical properties which can be observed in Polarised Light
Microscopy (PLM). It is a very simple method of identification of asbestos fibers.
PLM allows, not only, to distinguish asbestos from other materials, but also the
various types of asbestos from each other. Using liquid of known refractive index
(for chrysotile nc = 1.55) can be seen optical properties such as: dispersion staining,
pleochroism, birefringence, extinction, extinction angle and sign of elongation.[2] If
the tested fibers do not display any of these characteristics can exclude presence of
asbestos in the material.
This study presents how extraction of magnesium from brucite layer has changed the
optical properties of chrysotile asbestos. In the experiment were tested pure chrisotile
fibers and chrysotile fibers after incubation with inorganic acids, organic acid and also
with the addition of fluoride ions.
[1]
J. Addison “Asbestos , Analysis of”, Meyers R. A. Environmental analysis and remediation.
USA N.Y., John Wiley & Sons, Inc., 1998, 1, 413-434.
[2]
G. Stroszejn-Mrowca “Identification of asbestos in bulk materials by polarysed light microscopy
and phase contrast: method and results”, Occupational Medicine, 2003, 54 (6), 567-572
106
Thursday 17:40 - 20:10
Poster 049
Study of the PM10 concentration variations at the crossroad
of busy roads in Poznan
Maciej Narozny, Krystian Eitner, Wlodzimierz Urbaniak
Department of Analytical Chemistry – Adam Mickiewicz University – Grunwaldzka 6 –
Poznan – POL
[email protected]
The movement of motor vehicles is one of the main sources of suspended matter in
urban areas. Additionally the lack of adequate monitoring stations of this type of air
pollution causes impossibility to estimation the risks and analysis of the situation.
During the period from October 2011 to June 2012, PM10 concentrations were measured in the center of Poznan, at the crossroad of busy roads. The measurements
took place in four series, each with a different time of year (fall, winter, spring, summer) and lasted seven days. Measurement time was 8 hours from 8 am to 16 pm.
Sampling was carried out using portable real - time aerosol monitor the DustTrak II
8530. Additionally were measured meteorological factors such as temperature, humidity, pressure, wind strength and direction using a weather station Oregon Scientific
WMR 200th. During the measurements also identified the internal combustion car
traffic passing through crossroad. Mean daytime concentration of PM 10 ranged from
17 µg/m3 to 421 µg/m3 . The study shows that the concentration of PM10 is strongly
dependent on the weather and the number of vehicles. This shows how much the people of urban areas are exposed to the effects of dust, which in the long term negative
impact on human health.
Poster 050
Thursday 17:40 - 20:10
107
Ultrasound-assisted Synthesis of Naphthapyranes Catalyzed
by Copper Triflate
Kadir Turhan, S. Arda Ozturkcan, Zuhal Turgut
Department of Chemistry – Yildiz Technical University – Davutpasa Street –
34210 Esenler, Istanbul – TUR
[email protected]
Active oxygen heterocycles takes interest because they are an important class of natural compounds such as Mollugin and Nigrolinea benzopyranes which exhibiting a
wide spectrum of pharmaceutical and biological properties such as antitumor and
antibacterial activities.[1,2] Naphthapyranes are important biologically active heterocyclic compounds, which possess analgesic, anti-inflammatory, antifungal, antiviral,
cytotoxic, anti-oxidative, and 5-lipoxygenase inhibitory activities.[3-7]
Ultrasonic-assisted organic synthesis (UAOS) as a green synthetic approach is a powerful technique that is being used more accelerates organic reactions.[8] UAOS can be
highly effective and it is applicable to a wide range of practical reactions. In order to
expand the application of ultrasound in the synthesis of heterocyclic compound, we
wish to report a general, rapid, productive and environment-friendly method for the
synthesis of naphthapyranes.
Triflates are effective and recoverable homogeneous catalysts for the modern synthesis.
Recently, rare earth metal triflates, a new type of Lewis acid, are broadly used in
organic reactions due to their low toxicity, high stability, ease of handling, water
tolerance, and recoverability from water. To the best of our knowledge, this study
reports a new procedure for the synthesis of naphthapyranes using Cu(OTf)2 as a
green catalyst under ultrasound irradiation.
[1]
S. Claessens, B. Kesteleyn, T. Nguyen Van, N. De Kimpe, Tetrahedron 2006, 62 (35), 8419.
V. Rukachaisirikul, K. Tadpetch, A. Watthanaphanit, N. Saengsanae, S. Phongpaichit, Journal
of Natural Products 2005, 68 (8), 1218.
[3]
L. Q. Wu, W. L. Li, F. L. Yan, Journal of Heterocyclic Chemistry 2010, 47 (5), 1246.
[4]
L.-Q. Wu, L.-M. Yang, X. Wang, F.-L. Yan, Journal of the Chinese Chemical Society 2010,
57, 738.
[5]
G. C. Nandi, S. Samai, R. Kumar, M. S. Singh, Tetrahedron 2009, 65 (34), 7129.
[6]
A. K. Bhattacharya, K. C. Rana, M. Mujahid, I. Sehar, A. K. Saxena, Bioorganic & Medicinal
Chemistry Letters 2009, 19 (19), 5590.
[7]
A. Kumar, S. Sharma, R. A. Maurya, J. Sarkar, Journal of Combinatorial Chemistry 2009,
12 (1), 20.
[8]
G. H. Mahdavinia, S. Rostamizadeh, A. M. Amani, Z. Emdadi, Ultrasonic Sonochemistry
2009, 16 (1), 7.
[2]
This study was financially supported by YILDIZ TECHNICAL UNIVERSITY, Coordination
of Scientific Research Projects with the project number of 2012-01-02-GEP01.
108
Thursday 17:40 - 20:10
Poster 051
Electroreduction of aliphatic chlorides at silver cathodes in
water, acetonitryle and mixed water-acetonitryle
Agnieszka Brzózka ∗ , Anna Brudzisz† , Grzegorz Sulka†
Faculty of Non-Ferrous Metals – AGH University of Science and Technology –
30 Mickiewicza Av. – Krakow – POL
†
Ingardena 3 – Krakow – POL
∗
[email protected]
As a result of widespread use in industry and in various household products and
poor biodegradability chlorinated aliphatic hydrocarbons are frequently found in soils,
drinking waters and gaseous emissions at levels that, in water sediments, can be as
high as 150 ppb. Contamination of drinking water by chlorinated aliphatic hydrocarbons is particularly dangerous in view of their toxicity or even carcinogenic nature and
hence efficient remediation technologies are highly desired. Indeed, the development
of degradation technologies for water pollutants is an active area of research, and
various methods are already known for the abatement of halogenated compounds.[1]
The electrocatalytic reductive dehalogenation of organic halides has been extensively
investigated as a technology for the detoxification and disposal of halogenated hydrocarbons in industrial effluents. In comparison to other reductive pathways such
as chemical, catalytic, and photochemical dehalogenation this method appears as
a very promising approach being intrinsically milder, more selective, and easier to
run. However, the reduction of organic halides at the most commonly used cathodes
occurs at very negative potentials, where a concomitant reduction of water might
take place. Experimental evidence is presented that Ag exhibits a powerful electrocatalytic activity for the dehalogenation of polyhalogenated hydrocarbons to less, or
non-halogenated hydrocarbons with positive shifts of the peak potentials as compared
to glassy carbon.[2]
The process of reduction C2 H4 Cl2 was investigated by cyclic voltammetry at glassy
carbon and silver electrodes (bulk and nanowires in the form of nanobrushes) in H2 O,
acetonitryle (ACN) and mixed H2 O/ACN with LiClO4 , tetraethylammonium perchlorate and tetrabutylammonium fluoride as a supporting electrolyte. Silver nanowire
array have been successfully fabricated using anodic alumina oxide templates by a
direct-current electrodeposition from a commercially available plating solution. The
porous anodic alumina membranes were prepared by a two-step anodizing process.
The morphology of samples was studied using a field emission scanning electron microscope (FE-SEM). To confirm the chemical composition of obtained Ag nanowires,
the EDAX analysis was performed. In order to test the long-term stability of the
silver nanowires, cyclic voltamperometry experiments were repeatedly carried out on
the Ag-nanowire electrode, without renewal of Ag nanowires.
Acknowledgement:
This research was partially supported by the National Science Centre (Grant No
2011/01/N/ST5/02510). The research was partially carried out with the equipment
purchased thanks to the financial support of the European Regional Development
Fund in the framework of the Polish Innovation Economy Operational Program (contract no. POIG.02.01.00-12-023/08).
[1]
G. Fiori, S. Rondinini, G. Sello, A. Vertova, M. Cirja, L. Conti, J. Appl. Electrochem. 2005,
35, 363-68.
[2]
S. Ardizzone, G. Cappelletti, P. R. Mussini, S. Rondinini, L. M. Doubova, J. Electroanal.
Chem. 2002, 532, 285-293.
Poster 052
Thursday 17:40 - 20:10
109
Charge Transfer Kinetics of SnS-Nanoparticle Monolayers
Susann Kittler , Jan Poppe, Stephen G. Hickey, Alexander Eychmüller
Physikalische Chemie und Elektrochemie – TU Dresden – Bergstraße 66b – Dresden –
GER
[email protected]
Scarcity of fossil fuels, a rising demand for power and a growing ecological sensitivity
are only three of the reasons as to why renewable energy sources are of great interest.
Photovoltaic devices have a huge potential but the level of efficiency is presently only
about 25 % for epitaxial solar cells.
In 1991 O’Regan and Grätzel published a new solar cell construction called a dye
sensitized solar cell (DSSC).[1] As the role of the dye is as the light harvesting component, semiconductor nanoparticles can be used in their stead giving rise to a quantum
dot sensitised solar cell (QDSSC). Primarily compound semiconductors nanoparticles
such as CdS, CdSe and PbS have been well investigated as possible sensitizer materials.
Tin(II) sulfide (SnS) as a IV-VI semiconductor represents a material with high potential for photovoltaic applications, because of its good chemical stability under normal
working conditions, high absorption coefficient (α > 104 cm-1) and position of a direct and indirect bandgap (1.09 and 1.3 eV respectively) in the wavelength range of
interest for solar harvesters.[2]
In this work SnS particles have been deposited onto a transparent conducting glass
substrate (indium tin oxide, ITO) through the use of bifunctional organic compounds.
The SnS-layers were then characterisized by scanning electron microscopy (SEM), absorption spectroscopy and different voltammetric and amperometric methods under
square wave modulated illumination.
SEM-picure of a SnS-NP monolayer
[1]
B. O’Regan, M. Grätzel, Nature 1991, 353, 737.
[2]
S. G. Hickey, C. Waurisch, B. Rellinghaus, A. Eychmüller, Journal of the American Chemical
Society 2008, 130, 14978.
110
Thursday 17:40 - 20:10
Poster 053
NMR Spectroscopy in Nuclear Safety Research
Jérôme Kretzschmar ∗ , Astrid Barkleit∗ , Vinzenz Brendler∗ , Eike Brunner†
Institut für Ressourcenökologie – Helmholtz-Zentrum Dresden-Rossendorf –
Bautzner Landstr. 400 – Dresden – GER
†
Bioanalytische Chemie – Technische Universität Dresden – Bergstr. 66 –
Dresden – GER
∗
[email protected]
Radioactive elements can be emitted to the environment for several reasons. There
are natural uranium and thorium compounds (and their decay products) in rock
formations, which can be released by geologic alteration or mining processes. As
a consequence of energy production in nuclear power plants over the last decades,
huge amounts of nuclear waste were produced. If this waste is not stored adequately,
radionuclides can enter the geo- or biosphere. Studying the transport behaviour of
these radioactive elements and their fission products is the key aspect of our research.
Here, rocks and natural mineral phases as well as organic molecules as potential
binding sites are objects of investigation.
Both, NMR spectroscopic structure elucidation of environmentally relevant complexes
of lanthanides, actinides and selenium as well as the verification of results obtained
by other techniques in former studies, are the aims of this work.
The study of large biomolecules such as proteins or humic acids is rather complicated.
Therefore, compounds which are themselves potential complexing agents or at least
possess structural similarities to larger molecules, are used as model substances, for
instance glutathione (a tripeptide) or citrate.
Different one- and two-dimensional solution and solid state NMR methods will be
applied to dedicated systems, supplied by TRLFS, ATR FT-IR and EXAFS. Where
possible, the radionuclides are supposed to be replaced by inactive analogues or isotopes. In the case of selenium[1] , the spin–1/2 nucleus of Se-77 is well suited to be
directly observed by NMR spectroscopy.
[1]
in cooperation with Erica Brendler, Institut für Analytische Chemie, Technische Universität
Bergakademie Freiberg
Poster 054
Thursday 17:40 - 20:10
111
Catalytic dehydrogenation of liquid organic hydrogen
carriers for a decentralized energy storage application
Katharina Obesser , A. Bösmann, P. Wasserscheid
Institute of Chemical Reaction Engineering – University Erlangen-Nuremberg –
Egerlandstr. 3 – Erlangen – GER
[email protected]
Liquid organic hydrogen carriers (LOHC) provide an efficient and convenient way
for hydrogen storage and transportation.[1,2] LOHC compounds like N-ethylcarbazole
(NEC) can be loaded with hydrogen by catalytic hydrogenation of unsaturated bonds.[3]
The originating energy-rich Dodecahydro-N-ethylcarbazole (H12-NEC) is liquid at
ambient conditions and can be handled very similar to diesel fuel. When energy is
demanded, the stored hydrogen is released in a catalytic dehydrogenation reaction
while the energy-lean compound is regenerated (Figure 1).
This LOHC approach is a promising technology for long-term storing local and temporary energy overproduction from regenerative sources. Within the context of the
Bavarian Hydrogen Center the construction of a pilot plant for domestic energy supply is planned in order to demonstrate the functionality and potential of the hydrogen
storage system. For the near-term realization of the project the usage of catalysts
which are commercially available in large quantities is crucial. The screening of various commercial catalysts for efficient dehydrogenation of H12-NEC under relatively
mild conditions is presented.
Figure 1 The LOHC system N-ethylcarbazole / Dodecahydro-N-ethylcarbazole: typical
parameters for the reversible hydrogenation and dehydrogenation process.[1]
[1]
D. Teichmann, K. Stark, K. Müller, G. Zöttl, P. Wasserscheid, W. Arlt, Energy Environ. Sci.
2012, 5, 9044-9054.
[2]
D. Teichmann, W. Arlt, P. Wasserscheid, , Freymann, Energy Environ. Sci. 2011, 4, 27672773.
[3]
F. Sotoodeh, K. J. Smith, Ind. Eng. Chem. Res. 2010, 49, 1018-1026.
112
Thursday 17:40 - 20:10
Poster 055
Synthesis and Structural Analysis of Some New
Hexahomotrioxacalix[3]arene Derivatives Based on
Terpyridine Units
Claudia Lar ∗ , Anamaria Terec∗ , Ion Neda† , Ion Grosu∗
∗
Department of Organic Chemistry –
Faculty of Chemistry and Chemical Engineering, Babes Bolyai University –
Arany Janos 11 – Cluj Napoca – ROU
†
Institut fur Anorganische und Analytische Chemie –
Technische Universitat Braunschweig – Hagenring 30 – Braunschweig – GER
[email protected]
Anion recognition, complexation and transport were recognised recently as a very important part of supramolecular chemistry.[1] In order to develop more specific function
or recognition, supramolecular chemists have widely used calixarene derivatives as a
platform and have selectively introduced a variety of groups into the upper and lower
rims. Calix[n]arenes are known as building blocks[2] in supramolecular chemistry and
can be used as molecular scaffolds for the synthesis of more elaborated structures. In
this work, the synthesis and structural aspects of some hexahomotrioxacalix[3]arene
derivatives[3] based on terpyridine units (Scheme 1) are discussed.
This work was possible with the financial support of the Sectoral Operational Programme for Human Resources Development 2007-2013, co-financed by the European
Social Fund, under the project number POSDRU 89/1.5/S/60189 with the title “Postdoctoral Programs for Sustainable Development in a Knowledge Based Society”.
Scheme 1
[1]
(a) “Supramolecular Chemistry of Anions” A. Bianchi, K. Bowman-James, E. Garcia-Espana,
Eds., Wiley-VCH: New York, 1997; (b) “Supramolecular Chemistry-Concepts and Perspectives”
J. M. Lehn, VCH: Weinheim, 1995.
[2]
(a) “Calixarenes 2001” Z. Asfari, V. Bohmer, J. Harrowfield, J. Vicens, Eds., Kluwer Academic: Dordrecht, 2001; (b) “Calixarenes: A Versatile Class of Macrocyclic Compounds” J. Vicens,
V.Bohmer, Eds., Kluwer Academic; Dordrecht, 1991.
[3]
(a) J. Kang, N. Cheong, Bull. Korean Chem. Soc. 2002, 23, 995-997; (b) M. Dudic, P.
Lhotak, I. Stibor, H. Dvorakova, K. Lang, Tetrahedron 2002, 58, 5475-5482; (c) P. Zlatuskova, I.
Stibor, M. Tkadlecova, P. Lhotak, Tetrahedron 2004, 60, 11383-11390.
Poster 056
Thursday 17:40 - 20:10
113
Reevaluation of Fulvene Based Self Replicating Diels-Alder
System
Ilhan Sevim, Gunter von Kiedrowski
Chair of Organic Chemistry I. Bioorganic Chemistry – Ruhr-Universität Bochum –
NC 2/172 Universitätsstrasse 150 – Bochum – GER
[email protected]
Chemical systems which have the ability of catalayzing their own formations by the
product templates are defined as chemical self replicating systems. Effective self
replicating systems without the aid of enzymes or external cofactors have attracted
the scientists‘ attention both for their potentials of synthetic applications and understanding of the origin of life. To understand these systems several artificial ones
have been demonstrated over the last two decades. The aims of these studies were to
understand the efficiency of the systems and structural information transfer which are
created during the reaction. With these concerns, fulvene and maleimide based self
replicating Diels-Alder system mediated by the hydrogen bonding has been investigated with the help of kinetic NMR measurements. The high efficiency of the system
has brought us to investigate the asymmetric version of the system. Different substituted maleimides have been used with this aim. The diastereomeric distribution of
these reactions have showed some imbalances compared with the main reaction and
this has brought us to reevaluate the main reaction. This study contains the reevaluation of fulvene and maleimide based self replicating Diels-Alder system with much
more detailed NMR and HPLC analysis. The efficiency of the different diastereomers
and their autocatalytic and cross-catalytic properties are still under investigation.
114
Thursday 17:40 - 20:10
Poster 057
The influence of water molecule coordination to a metal ion
on water hydrogen bonds
Majda Misini ∗ , Jelena Andrić† , Dragan Ninković† , Milan Milovanović∗ , Snežana Zarić
∗
Department of Chemistry – University of Belgrade – Studentski trg 12-16 – Belgrade –
SRB
†
Innovation center, Department of Chemistry – University of Belgrade –
Studentski trg 12-16 – Belgrade – SRB
‡
ICTM – University of Belgrade – Njegoševa 12 – Belgrade – SRB
Department of Chemistry – Texas A and M University – P.O. Box 23874 –
Doha – QAT
[email protected]
Interactions of water molecules with ions, molecules and interfaces, have been intensively studied.[1] Pure liquid water has a very complex hydrogen bond network nature
and this is still in the process of being clarified using spectroscopic techniques and
computational methods.[2]
In this work the influence of cation on water hydrogen bonds was studied by analyzing crystal structures from Cambridge Structural Database and by high level ab
initio calculations.[3] The hydrogen bonds of the water molecules in the first hydration
shell of the cation were compared with the hydrogen bonds of free water molecules.
To the best of our knowledge this is the first work reporting on the strength of the
hydrogen bonds of the first hydration shell of metal cations based on the data in the
crystal structures from the CSD. The results of statistical analysis of data from CSD,
show that the MLOH/O interactions have a larger tendency towards shorter H. . . O
distances and linear orientations, which is typical of stronger hydrogen bonds. The
results of calculation show that water coordination to a metal ion has a remarkable
influence on hydrogen bonds. Positively charged complexes form quite strong hydrogen bonds, the hydrogen bond energy of [Zn(H2O)6]2+ complex with water molecule
([Zn(H2O)6]2+ ...OH2) is -21.89 kcal/mol, which is several times stronger than the
hydrogen bond of non-coordinated water, -4.77 kcal/mol (HOH...OH2).
Moreover, the hydrogen bond of the aqua ligand has a strong influence on the stability
and coordination number of a complex. These results can be important for all the
systems where a water molecule is in contact with metal cations, from biomolecules
to materials.
[1]
G. R. Desiraju, Angew. Chem., Int. Ed. 2010, 49, 2.
R. Bukowski, K. Szalewicz, G. C. Groenenboom, A. van der Avoird, Science 2007, 315.
[3]
J. M. Andrić, G. V. Janjić, D. B. Ninković, S.D. Zarić, Physical Chemistry Chemical Physics
2012, 14, 10896.
[2]
Poster 058
Thursday 17:40 - 20:10
115
Multicomponent organogelator liquid system based
organogels: A tough competition between gelation and
crystallization
Eva-Maria Schön ∗ , Iti Kapoor∗ , Jürgen Bachl∗ , Dennis Kühbeck∗ , Carlos Cativiela† ,
Subhadeep Saha‡ , Rahul Banerjee‡ , Stefano Roelens , José Juan Marrero-Tellado# ,
David Díaz Díaz∗,†
∗
Institut für Organische Chemie – Universität Regensburg – Universitätsstraße 31 –
Regensburg – GER
†
Departamento de Química Orgánica, ISQCH – Universidad de Zaragoza - CSIC – Pedro
Cerbuna 12 – Zaragoza – ESP
‡
Physical/Materials Chemistry Division – National Chemical Laboratory – Dr. Homi
Bhabha Road – Pune – IND
Istituto di Metodologie Chimiche, Consiglio Nazionale della Ricerche, Dipart. di
Chimica – Universitá di Firenze – Via della Lastruccia 13 – Firenze – ITA
#
Instituto Universitario de Bio-Orgánica “Antonio González” – Universidad de La
Laguna – Astrofísico Francisco Sánchez 2 – La Laguna, Tenerife – ESP
[email protected]
As physical gels have attracted much attention in the last years[1] we present here
new organogels derived from methanolic solution of (1R,2R)-1,2-diaminocyclohexane
L-tartrate.[2]
In comparison with other organogelators, the system presented here (Figure 1 A) has
several feautures which makes it unique: 1) Simple, small and commercially available
chiral building blocks are the base of the multicomponent gelator system; 2) each
single component of the multicomponent solution and its stoichiometry is crucial for
the formation of the organogels and their stability; 3) contrarily to usual way where
the gelation phenomenon takes place during cooling-down from high temperatures,
here the gels are resulting from warming up the isotropic solution from low temperatures; 4) although the organogels are composed of low molecular weight components
and consequently hold together by non-covalent interactions, they are not thermoreversible.
This system exemplifies the delicate equilibrium between solution and crystallization
that defines the gel phase (Figure 1 B).
Figure 1:A) Components of the new gelator liquid system. B) Ilustration of the
competition between gelation and crystallization.
[1]
R. G. Weiß, P. Terech, “Molecular Gels: Materials with Self-Assembled Fibrillar Networks”,
Springer: NY 2006.
[2]
I. Kapoor, E.-M. Schoen, J. Bachl, D. Kühbeck, C. Cativiela, S. Saha, R. Banerjee, S. Roelens,
J. J. Marrero-Tellado, D. Díaz Díaz, Soft Matter 2012, 8, 3446-3456.
116
Thursday 17:40 - 20:10
Poster 059
Host-guest properties of some cage molecules
Adrian Woiczechowski-Pop ∗ , Anamaria Terec∗ , Christine Baudequin† ,
Yvan Ramondenc† , Ion Grosu∗
∗
Depart. of Organic Chem., Centre of Supramol. Organic and Organometallic Chem. –
Babes-Bolyai University – Arany Janos 11 – Cluj-Napoca – ROU
†
Institut de Recherche en Chimie Organique Fine de Rouen – Université de Rouen –
Rue Tesniére 76130 – Rouen - Mont Saint Aignan – FRA
[email protected]
Development of synthetic host compounds, combined with the numerous studies in
host-guest chemistry, led to the conclusion that the three-dimensional cage molecules
can be involved in specifically directed complexing, molecular recognition, and ion
transport through membranes.[1] Recently, coordination cage molecules have found
applications as nanoreactors[2] or transport vehicles for cytotoxic compounds[3] and
for the stabilization of reactive molecules[4] respectively. The size and the symmetry
of these cages may also display fascinating host-guest chemistry.
In this work, theoretical and experimental studies (NMR, UV-Vis, fluorescence) concerning the supramolecular host-guest properties of type I cage molecules have been
performed (Scheme 1). Different organic molecules have been used as guests for
1,3,5-tris(phenyl)benzene 1,3,5-tris(biphenyl)benzene and 2,4,6-tris(phenyl)-1,3,5-triazine based macrocycles.
This work was possible with the financial support of the Sectoral Operational Programme for Human Resources Development 2007-2013, co-financed by the European
Social Fund, under the project number POSDRU 89/1.5/S/60189 with the title “Postdoctoral Programs for Sustainable Development In a Knowledge Based Society”
Scheme 1.
[1]
(a) C. J. Pedersen, Angew. Chem. Int. Ed. 1988, 27, 1021; (b) F. Ebmeyer, F. Vögtle,
Angew. Chem. Int. Ed. 1989, 28, 79; (c) C. Seel, F. Vögtle, Angew. Chem. Int. Ed. 1991,
30, 442.
[2]
(a) M. Yoshizawa, J. K. Klosterman, M. Fujita, Angew. Chem. Int. Ed. 2009, 48, 3418; (b)
T. S. Koblenz, J. Wassenaar, J. N. H. Reek, Chem. Soc. Rev. 2008, 37, 247.
[3]
(a) O. Zava, J. Mattsson, B. Therrien, P. J. Dyson, Chem. Eur. J. 2010, 16, 1428; (b) B.
Therrien, G. Süss-Fink, P. Govindaswamy, A. K. Renfrew, P. J. Dyson, Angew. Chem. Int. Ed.
2008, 47, 3773.
[4]
M. Kawano, Y. Kobayashi, T. Ozeki, M. Fujita, J. Am. Chem. Soc. 2006, 128, 6558.
Poster 060
Thursday 17:40 - 20:10
117
Synthesis, structural aspects and ion transport investigation
of several new [1+1] condensed cyclophane ether
∗
Zafer Söyler ∗ , M. D. Amir† , Naz Mohammed Aghatabay†
Chemistry – Yıldız Technical University – Davutpaşa – İstanbul – TUR
†
Chemistry – Fatih University – Büyükçekmece – İstanbul – TUR
[email protected]
Six novel [1 + 1] condensed 14 membered cyclophane ethers were synthesized via
simple procedure affording high yields. The o-dibromoxylene and m-dibromoxylene
were incorporated to form macrocyclic units by coupling with the sodium salts of
the diols (3a, 3b, 3c).[1-3] They were characterized by elemental analyses, mass, FTIR, 1 H, and 13 C NMR spectral data. Ion transportation and permeability of the
compounds against Na+ , K+ hard ions and Ag+ soft ion were also investigated.[4]
Scheme a: KOH/EtOH, 60o C, 3h, 90%; b: MeOH/NaBH4 , 12h, 85%; c: Na/THF 75%.
[1]
P. Rajakumar, V. Murali, Tetrahedron 2004, 60, 2351-2360.
P. Rajakumar, R. Kanagalatha, Tetrahedron 2006, 62, 9735-9741.
[3]
A. H. M. Elwahy, A. A. Abbas, Tetrahedron 2000, 56, 885-895.
[4]
P. Rajakumar, A.M. Abdul-Rasheed, Tetrahedron 2005, 61, 5351-5362.
[2]
118
Thursday 17:40 - 20:10
Poster 061
Conductometry as a tool in research of β-cyclodextrin
inclusion complex
Katarzyna Abramczyk , Adam Bald
Physical Chemistry of Solutions – University of Lódź – Pomorska 163, 90-236 Lódź –
Łódź – POL
[email protected]
Over the last few years, cyclodextrins have become very popular. These macromolecules belong to the sugar class compounds. They consist of 6-, 7- or 8- units of
α-D(+) glucopyranoses which are connected by α-1,4-glycosidic bonds in such a way
that they form a truncated cone shape. The interior of the molecule is hydrophobic
while the exterior has a hydrophilic character. Depending on the number of sugar
particles, they are denoted α-, β-, γ-cyclodextrin.[1]
In literature there are many papers about wide application of cyclodextrins. The extraordinary properties of these compounds, relative non-toxicity and low price give rise
to great opportunities for using cyclodextrins in chemistry and numerous industries.[3]
A special attention shouold be paid to their ability to form inclusion complexes. In
our team, we focused on the determination of the binding constants and the basic
thermodynamic functions of inclusion complexes of β-CD with the sodium salts of
carboxylic acids using conductivity method.
Toroidal and chemical structure of cyclodextrin[2]
[1]
G. Gattuso, S. A. Nepogodiev, J. Fraser Stoddart, Chem. Rev. 1998, 98, 1919-1958.
A. A. Rafati, N. Hamnabard, E. Ghasemian, Z. B. Nojini, Materials Science and Engineering
C 2009, 29, 791–795.
[3]
M. V. Rekharsky, Y. Inoue, Chem. Rev. 1998, 98, 1875-1917.
[2]
Poster 062
Thursday 17:40 - 20:10
119
Phenanthroline derivatives and DNA
Philipp Scharf , Jens Müller
Institut für Anorganische und Analytische Chemie –
Westfälische Wilhelms-Universität Münster – Corrensstraße 28/30 – Münster – GER
[email protected]
Functionalization of the nucleic acids DNA and GNA by introduction of artificial
nucleobases is a growing field with relevance in several chemical disciplines (GNA
= glycol nucleic acid). In particular, the use of ligands as nucleobases resulting
in the formation of metal-mediated base pairs offers the opportunity to modify the
properties of these supramolecular assemblies. This is expected to lead to interesting
applications in nanotechnology, e. g. in the areas of conductivity or magnetism.[1-4]
1,10-Phenanthroline and its derivatives are versatile ligands for a variety of transition
metals.[5] Due to its planarity and aromaticity the use of this ligand in metal-mediated
base pairs appears to be feasible.
We report the synthesis of a novel building block of the ligand 1H-imidazo[4,5-f][1,10]phenanthroline and its integration into a DNA oligonucleotide. Thereafter we refer
to the interaction of this oligonucleotide with several metal ions especially regarding
the thermal stability of the formed metal-mediated base pairs.
[1]
L. Zhang, A. E. Peritz, P. J. Carroll, E. Meggers, Synthesis 2006, 645-653.
M. K. Schlegel, L. Zhang, N. Pagano, E. Meggers, Org. Biomol. Chem. 2009, 7, 476-482.
[3]
K. Seubert, C. F. Guerra, F. M. Bickelhaupt, J. Müller, Chem. Comm. 2011, 47, 11041-11043.
[4]
P. Scharf, J. Müller, ChemPlusChem 2013, 78, 1, 20-34.
[5]
A. Bencini, V. Lippolis, Coord. Chem. Rev. 2010, 254, 2096-2180.
[2]
120
Thursday 17:40 - 20:10
Poster 063
Cholesterol-Modified Nucleosides as Precursors for
Microtubes Self-Assembly
Anca Petran ∗ , Nicolai Brodersen† , Paula Pescador† , Holger Scheidt‡ , Louisa Losensky ,
Martin Loew , Andreas Herrmann , Daniel Huster‡ , Anna Arbuzova , Jürgen Liebscher†
∗
Phyisics of Nanostructural Systems –
National Institute for Research and Development of Isotopic and Molecular Technologies –
Donath, nr. 65-103 400293 Cluj-Napoca – Cluj-Napoca – ROU
†
Organic Chemistry – Institute of Chemistry, Humboldt-University Berlin –
Brook-Taylor-Str. 2 – Berlin – GER
‡
Institute of Medical Physics and Biophysics –
Institute of Medical Physics and Biophysics – Haertelstr. 16-18 – Leipzig – GER
Institute of Biology/Biophysics –
Institute of Biology/Biophysics, Humboldt-University Berlin – Invalidenstr. 42 –
Berlin – GER
[email protected]
Molecular self-assembly is the basis of supramolecular chemistry and can lead to a
variety of structural motifs, e. g. to molecular membranes such as in phospholipid
double layers. Under certain circumstances such membranes can form nanotubular structures. Nanotube formation requires highly ordered molecular packing and
anisotropic intermolecular interactions.
In our group a new lipophilic nucleoside 1 (figure 1, a) was synthesized which selfassembled in microtubes after mixing with a simple phospholipid.[1] The SEM image
of such a microtubule reveals a straight structure with an almost uniform outer diameter of about 300 nm (figure 1, b). The tubes posses open ends and thus are
interesting as potential carriers, e. g. for drugs.
Our target was to synthesize new cholesteryl-nucleoside and nucleobase derivatives
analogous to structure 1. In these compounds we varied chain length of the linker,
point of attachment of cholesterol and additional derivatisation of hydroxyl groups.
These variations give us the ability to study the effect of structural motifs on the
ability to form microtubes by mixing with phospholipids.
[1]
P. Pescador, N. Brodersen, H. A. Scheidt, M. Loew, G. Holland, N. Bannert, J. Liebscher, A.
Herrmann, D. Huster, A. Arbuzova, Chem. Commun. 2010, 46, 5358.
Poster 064
Thursday 17:40 - 20:10
121
Parallel Interactions at Large Horizontal Displacement in
Pyridine-Pyridine and Benzene-Pyridine Dimers
Jelena Andric ∗ , Dragan Ninkovic∗ , Snežana Zarić‡
Innovation center, Department of Chemistry – University of Belgrade –
Studentski trg 12-16 – Belgrade – SRB
‡
Department of Chemistry – Texas A and M University – P.O. Box 23874 – Doha – QAT
∗
[email protected]
Although aromatic–aromatic interactions have been extensively studied, interactions
at a large horizontal displacement (offset) have only been recently reported.[1] The
results indicated the importance of stacking interactions of benzene molecules at
large horizontal displacements and prompted us to study pyridine–pyridine and pyridine–benzene parallel interactions.
Herein, we present the results on the interactions of pyridine–pyridine and pyridine–benzene molecules in the parallel orientation. We analyzed crystal structures
from the Cambridge Structural Database (CSD) and performed DFT calculations. A
study of crystal structures from the CSD and DFT calculations revealed that parallel pyridine–pyridine interactions at large horizontal displacements (offsets) were
preferred,[2] similar to parallel benzene–benzene interactions.[1]
At large horizontal displacements (4.0-5.0 A) interaction energies in the benzenebenzene, pyridine–pyridine and pyridine–benzene dimers are similar; about 2 kcal
mol-1 .
[1]
D. B. Ninković, G. V. Janjić, D.Ž . Veljković, D. N. Sredojević, S. D. Zarić, ChemPhysChem
2011, 12, 1-4.
[2]
D. B. Ninković, G. V. Janjić, S. D. Zarić, Cryst. Growth Des. 2012, 12, 1060-1063.
122
Thursday 17:40 - 20:10
Poster 065
Improved Synthesis of Ozazoline-Based Chiral Ligands and
Their Application in Heteroleptic Transition-Metal
Complexes
Swantje Wiebalck , Gisa Meißner, Cindy Glor, Silke Plachetta, Patrick Kuhrt,
C. Christoph Tzschucke
Chemie und Biochemie – Freie Universität Berlin – Takustr. 3 – Berlin –
[email protected]
Oxazoline based structures provide a versatile design principle for the construction of ligand collections, since they can be derived from the chiral pool of natural
amino acids. Protocols for the synthesis of bisoxazolines (box), pyridinoxazolines (pyrox), and their derivatives 6-methylpyrininroxazoline (mepyrox) and quinolinoxazolin
(quinox) were established.After amide formation, the crucial ring closure was induced
by a strong base in methanol as polar solvent. The reaction protocol offers reliable
access to a variety of different substitution patterns.[1]
The box-type ligands were used for the preparation of new heteroleptic ruthenium or
iridium complexes. The complexes were characterized with respect to their structural
and spectroscopic properties. Initial results regarding the reactivity of the ruthenium
and iridium complexes will be presented. [2]
[1]
a) I. Butula, G. Karlovic, Liebigs Ann. Chem 1976, 1455; b) D. Sirbu, G. Consiglio, B.
Milani, P. G. A. Kumar, P. S. Pregosin, S. Gischig, J. Organomet. Chem. 2005, 690, 2254 2262;
c) R. I. McDonald, P. B. White, A. B. Weinstein, C. P. Tam, S. S. Stahl, Org. Lett. 2011, 13,
2830.
[2]
G. Mestroni, A., Camus, G. Zassinovich, J. Organomet. Chem. 1974, 73, 119.
Poster 066
Thursday 17:40 - 20:10
123
Direct synthesis of dimethyl carbonate from methanol and
carbon dioxide over surface functionalized Cex Zr1−x O2
catalysts
Patrick Kollmorgen, Iuliia Prymak, Narayana Kalevaru, Andreas Martin,
Sebastian Wohlrab
Leibniz-Institut für Katalyse e.V. – Albert-Einstein-Strasse 29a – 18059 Rostock – GER
[email protected]
Dimethyl carbonate (DMC) is a non-toxic, biodegradable solvent and can be used as
alkylation-/acylation agent, phosgene substitute, fuel additive/antiknock agent, intermediate in polymer synthesis, electrolyte in lithium-ion-batteries and in pharmacy.[1]
In an industrial scale DMC is mainly produced via oxidative carbonylation of methanol
using copper containing species. An interesting alternative sustainable route to linear carbonates is the direct carboxylation of alcohols which is topic of our current
research. The reaction itself uses CO2 as renewable zero cost feedstock and possess
high atom efficiency. A second aspect of CO2 utilization is the capture of CO2 as
greenhouse gas. Nevertheless for this reaction elementary problems have to be solved.
Due to the thermodynamic stability of the CO2 molecule the activation of the C-Obond is quite difficult and complex. In addition the reaction is thermodynamically
unfavoured (G=+26 KJ/mol) and consequently the position of the equilibrium leads
to low DMC yields. This work focuses on the Cex Zr1−x O2 system which has both
acidic and basic sites.[2] These sites play the dominant role on the catalytic performance. Our aim is the modification of those acidic and basic properties via changing
the Ce/Zr ratios or surface functionalization of the Cex Zr1−x O2 to enhance DMC
yield. In comparison to the monometallic archetypes mixed metal oxides show better
stabilities and higher catalytic activities. Cex Zr1−x O2 catalysts with varying molar metal ratios with x from 0 to 1 were prepared via an oxalate-gel-method.[3] All
synthesized catalysts were catalytically tested in a 25 ml autoclave. Reactions were
carried out for 1 h at 443 K, 65 bar of CO2 and typically 10 ml of methanol and 50 mg
of catalyst were used. DMC concentration was determined by gas chromatography.
Catalysts where x is 0.6 and 0.8 showed the highest catalytic activity and were further surface functionalized by different species. The catalysts were characterized by
BET-surface analysis and X-ray diffraction. BET surface areas range between 30 and
90 m2 /g and XRD-pattern showed that CeO2 exists in cubic phase and the ZrO2 exists in monoclinic and tetragonal phase. Our synthesized Cex Zr1−x O2 solid catalysts
showed comparable activities known from literature.[3] Acid Base surface modifications on Cex Zr1−x O2 led to changed catalytic performances. In this context DMC
yield could be increased from 0.4 to 1.1 mol% for Ce0.6 Zr0.4 O2 and from 0.3 to 1.7
mol% for Ce0.8 Zr0.2 O2 . Results reveal that the Ce content as well as the surface
modification has a significant effect on acid base properties and plays an important
role on the catalytic performance.
[1]
M. Aresta, A. Dibenedetto, C. Pastore, C. Cuocci, B. Aresta, S. Cometa, E. De Giglio, Catalysis
Today 2008, 137, 125-131.
[2]
W. Khaodee, B. Jongsomjit, S. Assabumrungrat, P. Praserthdam, S. Goto, Catalysis Communications 2007, 8, 548-556.
[3]
H. J. Hofmann, A. Brandner, P. Claus, Chemie Ingenieur Technik 2011, 83, 1711-1719.
124
Thursday 17:40 - 20:10
Poster 067
Photochemically Generated Singlet Oxygen as Mechanistic
Probe for the Interaction of Bisanthracenes
Matthias Klaper , Torsten Linker
Institut für Chemie – Universität Potsdam – Karl-Liebknecht-Str. 24-25 –
14467 Potsdam OT Golm – GER
[email protected]
The understanding of the interaction of Bisanthracenes via π-π interaction is important for applications in semiconductor techniques.[1] Accordingly, investigations
on the correlation between π-π stacking ability and photovoltaic performance were
made.[2] Furthermore, it is known that strong interaction will lead preferably to a
high degree of excitonic self quenching or other radiationless deactivation processes
resulting in poor quantum yields.[3] In literature there is nothing known about endoperoxides interactions with anthracenes yet.
Here we report about our investigation on photochemically generated singlet oxygen
as a probe for the interaction of α,ω-dianthrylalkanes and their monoendoperoxides.
Therefore, a number of linked anthracenes were synthesized by various procedures,
varying the chain-length from zero to eight.
With these distanced bisanthracenes in hand, the k 1 and k 2 values of the two photooxidation steps to the corresponding mono- and bisendoperoxides were detected.
Interestingly, the k 2 value does not simply rise with prolonged distance, due to less
steric hindrance like k 1 , but instead reaches a maximum at a certain chain length.
This can be ascribed to the strongest interaction of the anthracene – monoendoperoxid
at this particular distance. This is also assured by experiments of the photoinduced
intramolecular [4+4]-cycloaddition at 366 nm, which is only observed for C1 - up to
C4 -chaines and also by UV and fluorescence spectroscopy. Our findings allow concluding the formation of a ferrocene-like anthracen - singlet oxygen - anthracen sandwich
complex at this particular distance.
[1]
L. R. MacGillivray et al., J. Am. Chem. Soc. 2006, 128, 2806.
H. Hoppe et al., Macromolecules 2010, 43, 126.
[3]
a) D. A. M. Egbe et al., Macromolecules 2010, 43, 306; b) P. Günther et al., J. Phys. Chem.
1996, 100, 18931.
[2]
Poster 068
Thursday 17:40 - 20:10
125
Development of novel bifunctional chiral thiourea derivative
as organocathalyst
Ana Escamilla, Ana C. Cuñat, Juan F. Sanz
Department of Organic Chemistry – University of Valencia –
c/ Doctor Moliner No 50 46100 – Valencia – ESP
[email protected]
In this communication, we are describing the design of chiral bifunctional thioureas
bearing an imidazoline ring in expectation of their dual activation of both electrophiles
and nucleophiles to promote a wide range of nucleophilic addition reactions. We have
modified the ring A substitution in order to enhance the acidity of NH protons, thus
increasing the substrate’s nucleophilicity (see scheme below).
The most important moiety of this structure is the imidazoline ring, which is synthesized from a chiral diamine and an aldehyde. Diamine 2 was obtained through
amidation and reduction of phenyglycine methyl esther. In order to prepare the desired organocathalyst, a thiourea functionality was introduced by means of reaction
between an isothiocyanate and a primary amine.
The new organocathalysts will be tested in several transformations, such as Henry or
aza-Henry[1] , Michael[2] and Mannich[3] additions.
[1]
X. Xu, T. Furukawa, T. Okino, H. Miyabe, Y. Takemoto, Chem. Eur.J. 2005, 12, 466-476.
C. Chun-Li, Y. Meng-Chun, S. Xiu-Li, T. Yong Org. Lett. 2006, 8, 2901-2904.
[3]
Z.Hui, C. Yongming, L. Zhengyu, P. Yungui Adv. Synth. Catal. 2009, 351, 2288-2294.
[2]
126
Thursday 17:40 - 20:10
Poster 069
Asymmetric Total Synthesis of Smyrindiol Employing an
Organocatalytic Aldol Key Step
Jeanne Fronert, Tom Bisschops, Florian Boeck, Dieter Enders
Institute of Organic Chemistry – Landoltweg 1 – Aachen – GER
[email protected]
The natural product smyrindiol, also called (+)-(2’S,3’R)-3-hydroxymarmesin, is a
linear dihydrofurocoumarin which was isolated from the roots of Smyrniopsis aucheri
by Dzhafarov et al. in 1992 and from the roots of Brosimum gaudichaudii by Vilegas
et al. in 1993.[1] Smyrindiol has shown antifungal and antibacterial activity and can
be used to cure Vitiligo, a skin disease, or as a vasodilator.[1a,2]
The first organocatalytic asymmetric synthesis of smyrindiol using a (S )-proline catalyzed 5-enolexo aldol reaction as key step is described. The diastereo- and enantioselectivity is virtually complete (de 99%, ee 99%) and the title compound was
obtained in 15 steps in an overall yield of 6.3%.[3]
In addition to the aldol reaction the total synthesis also includes a new type of
coumarin assembly via a Sonogashira reaction to a propiolic acid derivative, followed
by a Lindlar reduction / lactonization sequence, which opens a new efficient and
flexible entry to the coumarin core of other natural products.
[1]
a) Z. R. Dzhafarov, Z. A. Kuliev, A. D. Vdovin, A. A. Kuliev, V. M. Malikov, N. M. Ismailov,
Chem. Nat. Compd. 1992, 28, 27; b) W. Vilegas, G. L. Pozetti, J. Harumi Yariwake Vilegas, J.
Nat. Prod. 1993, 56, 416.
[2]
B. Ngameni, V. Kuete, I. K. Simo, A. T. Mbaveng, P. K. Awoussong, R. Patnam, R. Roy, B.
T. Ngadjui, S. Afr. J. Bot. 2009, 75, 256.
[3]
D. Enders, J. Fronert, T. Bisschops, F. Boeck, Beilstein J. Org. Chem. 2012, 8, 1112.
Poster 070
Thursday 17:40 - 20:10
127
Investigation of organocatalytic reaction mechnisms using
ESI-MS
Martin Schmidt, Marianne Engeser
Kekule-Institut für Organische Chemie und Biochemie – Universität Bonn –
Gerhard-Domagk-Str. 1 – Bonn – GER
[email protected]
SOMO catalysis has obtained large interest as a new and powerful version of enantioselective organocatalysis which includes radical steps initiated by a one-electron
oxidation.[1] The key intermediate enamine radical cation has been postulated but
had not been observed directly until it we could detect it by ESI mass spectrometry
combined with an online microreactor technique.[2] This Combination has proven to
be an excellent tool to investigate reaction mechanisms in solution as it allows the
detection of short-lived, reactive molecules such as radical species.
We have identified enamine radical cation species in the case of four commonly used
imidazolidin-4-one organocatalysts so far. Subsequent reactions of the enamine radicals with e.g. styrene (Fig.1) could be observed in our experiments as well.[2] Currently, the project is extended towards establishing electrochemical oxidation online
coupled to the MS to replace the chemical oxidant.
A second project aims on mechanism elucidation of enamine mediated, proline catalysed reactions which has been a strongly investigated field of organocatalysis in the
last years. Therefore a charge labeled, proline based organocatalysts was synthesized.
The catalyst carries a fixed charge far away from the catalytic center which enables
us to detect intermediate species in low concentrations via MS without influencing
the properties of the catalytic center.
Figure 1. In situ formation of an intermediate enamine radical (red) cation and following
reaction with styrene under SOMO catalysis conditions.
[1]
T. D. Beeson, A. Mastracchio, J. Hong, K. Ashton, D. W. C. MacMillan, Science, 2007, 316,
582. [2] R. Beel, S. Kobialka, M.L. Schmidt, M. Engeser, Chem.Comm. 2011, 47, 3293.
128
Thursday 17:40 - 20:10
Poster 071
The influence of calcination parameters on Cu catalysts
derived from mixed Cu,Zn hydroxy-carbonate precursors
Julia Schumann, Andrey Tarasov, Nygil Thomas, Robert Schlögl, Malte Behrens
Department of Inorganic Chemistry – Fritz-Haber-Institut der Max-Planck-Gesellschaft –
[email protected]
Methanol is one of the most important bulk chemicals. Its synthesis is performed
over Cu/ZnO/Al2 O3 catalysts. The well-established catalyst preparation by coprecipitation leads to a precursor system with a complex phase mixture[1] , containing
different hydroxy-carbonates. Thermogravimetric (TG) measurements show, that the
decomposition of Cu,Zn hydroxy-carbonates during calcination proceeds in two main
steps: After the desorption of surface water, firstly, H2 O and CO2 are released simultaneously and in a second step only CO2 is released. The intermediate is therefore
termed “high temperature carbonate” (HT-CO3 ).[2] According to the TG data, the
typical calcination temperatures around 350 ◦ C would favor the formation of HTCO3 , but its role for the catalytic activity is unclear. The aim of this study is to
investigate the influence of the calcination parameters on the properties and catalytic
performance of catalysts derived from zincian malachite and aurichalcite precursors.
We prepared two series of catalysts by variation of the calcination conditions. The
first series starts from a phase pure aurichalcite, (Zn,Cu)5 (CO3 )2 (OH)6 , with a molar metal ratio Cu/Zn of 40:60. The second series starts from a zincian malachite,
(Cu,Zn)(CO3 )(OH)2 (Cu/Zn 80:20) precursor. All samples were calcined in a rotating furnace at 330 ◦ C for 3 h with a flow of 100 ml/min. The heating rates were varied
between 0.1 and 2 K/min. The resulting catalysts have been characterized in depth
by XRD, TG analysis and IR spectroscopy and the catalytic activities in methanol
synthesis have been tested.
TG investigations of the calcined sample series revealed, that catalysts heated with
different heating rates contain different amounts of HT-CO3 after calcination. By increasing the heating rate, more water accumulates in the atmosphere above the sample
and cannot be purged out fast enough. The amount of water in the atmosphere during
calcination crucially influences the decomposition kinetics of the hydroxy-carbonate
by promoting the decomposition of the HT-CO3 and the crystallization of the metal
oxides CuO and ZnO.[3] This is confimed by XRD measurements. The samples with
the highest heating rates are most crystalline in both series, the samples of the exaurichalcite series with lower heating rates are nearly amorphous, with some weak
features that cannot be ascribed to either ZnO or CuO. IR spectra of the calcined
samples show bands in the carbonate region, similar to the ones in the precursors.
Here again, the samples with the highest heating rate differ from the other samples by
showing weaker and much broader features. Copper metal surface areas varied in a
range of 19-25 m2 /g and 13-19 m2 /g for the ex-aurichalcite and ex-zincian malachite
series, respectively. Activity in methanol synthesis was measured, but only differences
smaller 10 % were found. There is an apparent trend in the activity data (normalized
per weighed portion), but this trend is reversed when normalizing the activity to the
actual reduced mass of catalyst. Therefore, no beneficial effect of a large amount of
HT-CO3 for the catalytic activity in methanol synthesis was observed.
[1]
C. Baltes, S. Vukojevic, F. Schüth, J. Catal. 2008, 258, 334.
M. Behrens, F. Girgsdies, A. Trunschke, R. Schlögl, Eur. J. Inorg. Chem. 2009, 1347.
[3]
S. Fujita, S. Moribe, Y. Kanamori, R. Takezawa, React. Kinet. Catal. Lett. 2000, 11.
[2]
Poster 072
Thursday 17:40 - 20:10
129
Gold-catalyzed Cycloisomerization of Fluorinated Allenes:
Application in BODIPY-Synthesis
∗
Linda Lempke ∗ , Norbert Krause∗ , Tobias Fischer† , Knut Rurack†
Organic Chemistry – TU Dortmund – Otto-Hahn-Straße 6 – 44227 Dortmund – GER
†
Bundesanstalt für Materialforschung und -prüfung – Fachbereich 1.9 –
Richard-Willstätter-Straße 11 – 12489 Berlin – GER
[email protected]
The gold-catalyzed cycloisomerization of α-functionalized allenes is a well-known
reaction.[1] Using this selective formation to prepare functionalized cycloisomerization products is of particular value for different applications or the total synthesis of
natural products and their derivatives.
In this project, the gold-catalyzed cycloisomerization of fluorinated α-aminoallenes is
applied for the synthesis of new BODIPY (boron-dipyrromethene) fluorescent dyes.[2]
Furthermore the use of ionic liquids as reaction medium for gold-catalyzed cyclisation
reactions[3] offers the possibility of recycling the catalyst, thus enhancing sustainability and industrial practicability.
BODIPY’s have particular spectroscopic properties like small stoke shifts and high
quantum yields which open new avenues for their application. The high fluorine content facilitates XPS-measurements beside the possibility of conventional fluorescent
detection.
Abb.1. Au-catalyzed cycloisomerisation as a key-step in BODOPY synthesis.
[1]
C. Winter, N. Krause, Chem. Rev. 2011, 111, 1994-2009.
G. Ulrich, R. Ziessel, A. Harriman, Angew. Chem. Int. Ed. 2008, 47, 1184-1201.
[3]
Ö. Aksın, N. Krause, Adv. Synth. Catal. 2008, 350, 1106-1112.
[2]
130
Thursday 17:40 - 20:10
Poster 073
One-pot organocatalytic asymmetric synthesis of
nitrogenated tricyclic compounds
David Sadaba ∗ , Ignacio Delso† , Tomas Tejero∗ , Pedro Merino∗
∗
Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) – C/ Pedro Cerbuna, 12 –
Zaragoza – ESP
†
Servicio de Resonancia Magnética Nuclear –
Centro de Química y Materiales de Aragón (CEQMA) – C/ Pedro Cerbuna, 12 –
Zaragoza – ESP
[email protected]
Five-membered cyclic nitrones have been demonstrated to be interesting heterocycles
and attractive building blocks for the synthesis of a variety of nitrogenated compounds
containing a pyrrolidine ring in their structure, many of them of biological interest.
Most of the reported syntheses of enantiomerically pure five-membered cyclic nitrones
employ natural sugars as starting materials. A different approach was carried out
in order to prepare other cyclic nitrones with different substituents, using common
reactants such as nitrostyrene.
In this work, a new three-step one-pot methodology was developed. The first step
is a Michael addition reaction of an aldehyde (1) to a nitroalkene (2). This is an
organocatalytic reaction mediated by a prolinol chiral derivative.[1] This reaction generates two chiral carbons in a γ-nitroaldehyde compound. In the following step, the
reduction of the nitro group to hydroxylamine group was done and, in situ, the condensation of the latter one with the aldehyde to yield the nitrone (3) took place. The
treatment of the reaction mixture provided alkenyl nitrones (3d) gave spontaneously
an intramolecular 1,3-dipolar cycloaddition leading to tricyclic derivatives 4.[2]
Figure 1
Acknowledgements:
D. S. thanks the Spanish Council for Scientific Research (CSIC) for his JAE-predoctoral grant.
References:
[1]
For a review see: D. Roca-Lopez, D. Sadaba, I. Delso, R. P. Herrera, T. Tejero, P. Merino,
Tetrahedron: Asymmetry 2010, 21, 2561-2601.
[2]
D.Sadaba, I. Delso, T. Tejero, P. Merino, Tetrahedron: Lett 2011, 52, 5976-5979.
Poster 074
Thursday 17:40 - 20:10
131
The effect of tertiary amines on the structure and selectivity
of dialkylallium alkoxides in the polymerization of rac-LA
Anna Maria Dabrowska, Anna Litwinska, Pawel Horeglad
Chemistry – University of Warsaw – Zwirki i Wigury 101 – Warsaw – POL
[email protected]
Polylactide (PLA), called a “nature’s polyethylene” [1] , is well known for its good
mechanical properties, biodegradability, and biocompatibility. Moreover, it can be
synthesized from renewable resources. These make PLA environmentally friendly
polymer of many potential applications. The latter results from the properties of
polylactide (PLA), which depend significantly on its tacticity. Therefore it is essential to synthesize PLA in the controlled and stereoselective way. One of the most
promising methods for the synthesis of PLA is the ring-opening polymerization (ROP)
of racemic lactide (rac-LA) using metal alkoxides as initiators.
Dialkylgallium alkoxides are very interesting catalysts as they can polymerize rac-LA
in controlled and stereoselective manner.[2] We showed that heterotactically enriched
polylactide can be obtained in the presence of dialkylgallium alkoxides modified with
Lewis bases, while the heteroselectivity was found to be strongly related to the coordination efficiency of a Lewis base to Ga center (Scheme 1).[2] Noteworthy is the
fact that dialkylgallium enabled for the first time the facile switch of stereoselectivity during the process of polymerization as the use of strong Lewis bases, such
as N-heterocyclic carbenes, for the complexation of dialkylgallium alkoxides led to
isoselective gallium catalysts.[3]
It is therefore important to examine in details the effect of various Lewis bases on
the activity and stereoselectivity of obtained dialkylgallium catalysts. I am going to
present the results of our studies on the effect of tertiary amines on the structure and
selectivity of dialkylgallium alkoxides, and the structure of obtained polylactide.
Scheme 1
[1] D.J. Cole-Hamilton, Angewandte Chemie 2010, 49, 8564-8566.
[2] P. Horeglad, P. Kruk, J. Pecaut, Organometallics 2010, 29, 3729-3734.
[3] P. Horeglad, G. Szczepaniak, M. Dranka, J. Zachara, Chemical Communications 2012, 48,
1171-1173.
132
Thursday 17:40 - 20:10
Poster 075
Supported MoV-Mixed Metal Oxide Catalyst for Selective
Oxidation of Propane
Pia Kjaer Nielsen, Kazuhiko Amakawa, Annette Trunschke, Robert Schlögl
Anorganische Chemie – Fritz-Haber-Institut der Max-Planck-Gesellschaft –
Faradayweg 4-6 – 14195 Berlin – GER
[email protected]
Introduction
MoV-mixed metal oxides are frequently applied as catalysts for selective oxidation,
in bulk phases as well as supported systems.[1] Supporting the metal oxide phases
on a high surface area, mesoporous, and inert SiO2 material, allows the possibility
to study the model catalyst surface isolated from bulk properties. In this study we
report a systematic investigation of the effects of the V:Mo metal oxide ratio of such
supported model systems.
Experimental
Supported MoV-mixed metal oxides were prepared by anchoring (NH4 )6 Mo7 O24
and NH4 VO3 to the surface of functionalized SBA-15 by applying an ion exchange
methodology.[2] Upon calcination the metal oxide precursors decomposed to disperse
metal oxide species on the surface of the support. A series of samples of varying
V:Mo ratio with constant total metal loading was obtained. Materials were characterized by N2 -physisorption, XRD, XRF, SEM/EDX along with in situ Raman and
UV-vis spectroscopy, before their catalytic performance in oxidative dehydrogenation
of propane (ODP) was investigated.
Results
The mesoporous structure of SBA-15 is maintained, while the metal oxide species are
distributed homogeneously throughout the final catalyst materials. Due to the variation in ratios, the interaction between the V and Mo oxides differs. The interaction
has been analyzed using in situ UV-vis and Raman spectroscopy. A consequence of
this variation is difference in the catalytic behavior in ODP.
[1]
[2]
H. Dai et al. Journal of Catalysis 2004, 221, 491-499.
Hess et al. J. Phys. Chem. B 2004, 108 (28), 9703-9709.
Poster 076
Thursday 17:40 - 20:10
133
Group 4 Sugar Complexes and Their Application in Catalysis
Anne Sachs, Jürgen Heck
Chemistry – Hamburg – Martin-Luther-King-Platz 6 – Hamburg – GER
[email protected]
In the last decade, we were successful to synthesise various organometallic complexes
of early transition metals with monosaccharide ligands. The obtained structures are
anionic or neutral dinuclear complexes which are bridged via one or two pyranosidato
ligands.[1-3]
Our first complex of this class of compounds was achieved by reaction of CpZrCl3 (thf)2
with methyl-4,6-O-benzylidene-β-D-glucopyranoside in presence of triethylamine.[1]
Thereby, the complex containing benzylidene protected glucopyranosidato ligands
forms a U-shaped chiral cavity with C 2 -symmetry. The anionic zirconate complex 1
incorporates a triethylammmonium cation forming a host-guest couple. Adding other
amines the incorporated cation is substituted. By using a racemic mixture the chiral
cavity is able to discriminate between R- and S -enantiomers.[4]
We obtained a similar complex containing two titanium centres by using Cp* instead
of Cp. Molecule 2 contains only two chlorido ligands and for this reason it is neutral
and cannot incorporate other anions. 2 is used as precatalyst for hydroamination
reactions.[5]
Next to dinuclear compounds we are also trying to synthesise mononuclear titanium
and zirconium sugar complexes to use them also as catalysts in different reactions.
Figure Dinuclear anionic zirconate complex 1 and neutral titanium complex 2
[1]
L. Jessen, E. T. K. Haupt, J. Heck, Chem. Eur. J. 2001, 7, 3791-3797.
C. Bolm, F. E. Hahn, Activating Unreactive Substrates, Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim, 2009, 147-164.
[3]
S. Tschersich, M. Böge, D. Schwidom, J. Heck, Rev. Inorg. Chem. 2011, 31, 27-55.
[4]
P. Kitaev, Dissertation, University of Hamburg, 2009.
[5]
D. Küntzer, L. Jessen, J. Heck, Chem. Commun. 2005, 5653-5655.
[2]
134
Thursday 17:40 - 20:10
Poster 077
Structure and reactivity of supported VOx and MoOx
selective oxidation catalysts
Juliane Scholz , Thorsten Ressler
Institut für Chemie – Technische Universität Berlin –
Sekr. C2 / Straße des 17. Juni 135 – 10623 Berlin – GER
[email protected]
Heterogeneous catalysis is an important tool to convert resources to valuable chemicals. One of the most important reactions to generate functionalized hydrocarbons
is selective oxidation of alkanes and alkenes with molybdenum and vanadium based
oxide catalysts. Industrially used catalysts exhibit a highly complex chemical composition. To understand principle reaction processes in catalytic oxidation it is essential
to study model systems under simplified conditions. Nanostructured oxide materials
are often used as support, to create suitable model systems for detailed simultaneous
investigations of catalysts structure and performance. The structure of the surface oxide catalysts is significantly affected by the properties of the support material. Thus,
it is possible to generate a variety of molecular model catalyst structures.
Here, we investigated the influence of MgO-coated SBA-15 (MgO/SBA-15 ) with alkaline surface properties on the structure of vanadium and molybdenum oxide catalysts.
To gain deeper insight into structure activity correlation, we used a combination of
spectroscopic techniques and simultaneous determination of catalytic activity under selective propene oxidizing conditions. The alkaline character of the MgO-based
support led to the formation of highly simplified catalysts units. X-ray absorption
spectroscopy (XAS) and diffuse reflectance UV-Vis (DR-UV-Vis) spectroscopy measurements showed that a similar structural motif was obtained for VOx and MoOx
supported on MgO/SBA-15 with a tetrahedral arrangement of oxygen atoms around
the metal centers. In situ XAS investigations under propene oxidizing conditions
revealed a correlation between structural changes and the onset of catalytic activity.
Selectivity towards the selective oxidation of propene to acrolein was directly correlated to the number of bridging M–O–M bonds (Fig. 1). Thus, the presence of
nucleophilic oxygen in the M–O–M bond proved to be crucial for selective oxidation.
Fig. 1: Selectivity towards acrolein of supported vanadium oxides at different V loadings
compared to a supported molybdenum oxide under propene oxidizing conditions.
We acknowledge HASYLAB, Hamburg and the Deutsche Forschungsgemeinschaft (DFG) for providing beamtime and financial support, respectively.
Poster 078
Thursday 17:40 - 20:10
135
New method for assessment of the photocatalytic
degradation of VOCs based on FTIR technique
Patrycja Lyczkowska, Małgorzata Cieślak, Grzegorz Celichowski
Pomorska 163 – Lodz – POL
[email protected]
These studies were carried out in cooperation with Scientific Department of Unconventional Technologies and Textiles, Textile Research Institute, Brzezinska 5/15, 92-103
Lodz, Poland (Head of work: PhD Eng. Małgorzata Cieślak)
Indoor air quality (IAQ) is one of the most significant factors affecting the health and
well-being of people who spend a lot of time in their lives indoors. Volatile organic
compounds (VOCs) include a variety of chemicals, which adversely affect on human
health. Among the different treatment methods developed for the degradation of
VOCs, photocatalytic oxidation process with using titanium dioxide as photocatalyst
can be considered as an innovative and promising solution. Currently, research is
carried out on the modification of textile materials with titanium dioxide. The evaluation of the photocatalytic activity of different forms of titanium dioxide and textile
materials modified by them requires searching a suitable techniques.
The aim of this study was the development of a new measurement method for the
photocatalytic effectiveness assessment based on Fourier Transform Infrared Spectroscopy (FTIR) technique. FTIR Spectrometer Bruker Vertex 70 equipped with the
gas cuvette was used and the specially photoreactor (with quartz cover) connected to
FTIR was built. The Xenon lamp Optel (150 W) to the photocatalytic process was
used. The photocatalytic activity of titanium oxide (IV) (TiO2) and titanium oxide
(IV) modified by silver (TiO2/Ag) was tested. As a model of VOCs the toluene was
selected.
It was found that, the assessment of the photocatalytic activity of titanium dioxide
towards VOCs using developed method based on FTIR spectroscopy technique is
possible.
136
Thursday 17:40 - 20:10
Poster 079
Mechanistic Investigations of the Palladium-Catalysed
Arylation of Pyridine N-Oxides
Emma Svensson, Sasa Duric, Sina Zucker, C. Christoph Tzschucke
Chemie und Biochemie – Freie Universität Berlin – Takustr. 3 – Berlin – GER
[email protected]
Direct arylation of pyridine N-oxides via palladium-catalysed C-H-activation has
shown to be a convenient synthesis of substituted bipyridine N-oxides.[1,2] The limitation of the coupling reaction lies within the electronic properties of the pyridine Noxide. Direct arylation of electron-deficient substrates such as 4-ethoxycarbonylpyridine
N-oxide gives product in good yields (eq. 1).[1] On the contrary, arylation of unsubstituted pyridine N-oxides is highly dependent on the nature of aryl halide. Reaction
with 4-bromotoluene gives the product in high yields (eq. 2),[2] whereas arylation
with 2-bromopyridine is limited and gives bipyridine N-oxide in low yields (eq. 3).
Initial kinetic measurements indicate that the rate-limiting step for pyridine N-oxides
with electron-withdrawing groups is the C-H-activation, regardless of aryl halide.
Preliminary data of the coupling of electron-rich pyridine N-oxides with bromobenzene
displays a linear consumption of aryl halide, whereas decay of bromopyridine does
not show the same linearity. However, kinetic measurements of bromopyridine are
hindered due to a decomposition pathway where nucleophilic attack of pyridine Noxide on bromopyridine forms the N-(2-pyridyl)-2-pyridone product.
Herein, we present kinetic measurements of the direct arylation of electron-deficient
and electron-rich substrates. Further mechanistic investigations with different electrophiles will be performed to elucidate the influence of aryl halide in the coupling
reaction.
[1]
[2]
S. Duric, C. C. Tzschucke, Org. Lett. 2011, 13, 2310.
L. C. Campeau, S. Rousseaux, K. Fagnou, J. Am. Chem. Soc. 2005, 127, 18020.
Poster 080
Thursday 17:40 - 20:10
137
Catalyst degradation in direct methanol fuel cells
Alexander Schökel ∗ , Claudia Brieger† , Christina Roth†
Materials Science – TU Darmstadt – Petersenstr. 23 – Darmstadt – GER
†
Institute of Chemistry and Biochemistry – FU Berlin – Takustr. 3 – Berlin – GER
∗
[email protected]
Introduction
One of the major degradation mechanisms in direct methanol fuel cells utilizing a
carbon-supported platinum-ruthenium alloy catalyst (PtRu/C) (see [1] ) is the dissolution of ruthenium from the anode catalyst and consecutive migration and deposition
of Ru species onto the cathode catalyst and other parts of the fuel cell. While there
are various reports about Ru dissolution from unsupported (e.g. [2] ) and supported
catalysts (e.g. [3] ), none of these focusses on elucidating the mechanisms involved on
an early timescale of operation (0 − 100 h).
Experimental
Two different techniques (wet spraying and hot pressing) for preparation of the
membrane-electrode assemblies (MEA) were chosen to study the influence of the electrode preparation process. MEAs from both preparation routes were subjected to
specific operation conditions in a methanol fuel cell. This way, a set of samples with
different histories (i.e. cell potential, runtime, fuel) was created and analyzed using different techniques. While the particle size was determined by X-ray diffraction
(XRD), the Ru content was measured by quantitative synchrotron X-ray fluorescence
spectroscopy (synXRF) and cyclic voltammetry (CV). X-ray absorption spectroscopy
(XAS) was used as a fingerprint technique to identify the chemical nature of the
ruthenium by comparison of the near edge features. The most important drawback is
the low concentration of Ru species, which is high enough to severly impact the performance, but almost too low to be detected by standard characterization techniques.
Results
It is observed that already during preparation of the MEA a crossover of ruthenium
from the anode to the cathode occurs. As there is no cell potential involved, this has
to be attributed to soluble Ru species permeating through the membrane. A process
that most definitely continues during further operation of the fuel cell.
It was possible to obtain XAS spectra of catalyst samples containing ruthenium in
the 10 - 100 ppm range. The quality of the cathode samples’ spectra is good enough
to compare the absorption edge shape to known ruthenium references and identify
the ruthenium’s oxidation state.
Taking into account the different histories of the samples, we see the expected correlation between runtime and amount of Ru migration (i.e. longer runtime means more
Ru being transferred). The correlation between cell potential and Ru migration on
the other hand is not that obvious and will be discussed in further detail.
Acknowledgements
The authors gratefully acknowledge the financial support from the Federal Ministry
of Economics and Technology, Germany (Grant no. 0327853-C).
[1]
E. J. Antolini, Solid State Electrochem. 2011, 15, 455.
P. Piela, C. Eickes, E. Brosha, F. Garzon, P. J. Zelenay Electrochem. Soc. 2004, 151, A2053.
[3]
FZ Juelich, IEF-3 Report 2007
[2]
138
Thursday 17:40 - 20:10
Poster 081
Sulfoximines as Ligands in Copper-Catalysed Asymmetric
Friedel -Crafts Reactions
Anne-Dorothee Steinkamp, Marcus Frings, Carsten Bolm
Institut für Organische Chemie – RWTH Aachen University – Landoltweg 1 –
52074 Aachen – GER
[email protected]
Indole-containing compounds are ubiquitous, and many of them exhibit interesting
biological activity. One strategy commonly employed to further functionalise indoles is
a Friedel-Crafts reaction, one of the most important methods to form bonds between
two carbon atoms. Since Jørgensen published the metal-catalysed enantioselective
alkylation of indoles in 2001,[1] additional research projects have been accomplished
in this field.[2]
Sulfoximines have been verified as powerful ligands in asymmetric metal catalysis.
C2 -symmetric bissulfoximines, for example, have been sucessfully employed in allylic
alkylations[3] and (hetero)-Diels-Alder reactions.[4]
Here, we present our preliminary results of an asymmetric Friedel-Crafts reaction between indole (1) and diethyl-2-benzylidenemalonate (2) catalysed by a chiral sulfoximinecopper-complex to achieve the desired product 3 in high enantioselectivity.
[1]
a) W. Zhuang, T. Hansen, K. A. Jørgensen, Chem. Commun. 2001, 347-348; b) K. B. Jensen,
J. Thorhauge, R. G. Hazell, K. A. Jørgensen, Angew. Chem. 2001, 113, 164-167; Angew. Chem.
Int. Ed. 2001, 40, 160-163.
[2]
For selected examples, see: a) J. Zhou, Y. Tang, J. Am. Chem. Soc. 2002, 124, 9030-9031;
b) G. Huang, H. Sun, X. Qiu, Y. Shen, J. Jiang, L. Wang, J. Org. Chem. 2011, 696, 2949-2957;
c) H. J. Lee, D. Y. Kim, Synlett 2012, 23, 1629-1632.
[3]
C. Bolm, O. Simić, M. Martin, Synlett 2001, 1878-1880.
[4] a) C. Bolm, O. Simić, J. Am. Chem. Soc. 2001, 123, 3830-3831; b) C. Bolm, M. Martin, O.
Simić, M. Verrucci, Org. Lett. 2003, 5, 427-429.
Poster 082
Thursday 17:40 - 20:10
139
A simple model of a copolymer chain: the influence of the
confinement on the structure
Tomasz Piskorz , Andrzej Sikorski
[email protected]
A coarse-grained model of polymer chains on a three-dimensional lattice was built.
The chains were represented by sequences if beads a [310] hybrid lattice. The linear
and star-branched chains were under consideration. The Monte Carlo simulations
employing the algorithm with micromodifications of chain’s conformation was performed. The size, structure and ordering in model macromolecules were investigated.
[1]
I. Carmesin, K. Kremer, Macromolecules 1988, 21 (9), 2819-2823
140
Thursday 17:40 - 20:10
Poster 083
Stereoselective Intramolecular Cyclopropanation through
Catalytic Olefin Activation
Sebastian Klimczyk ∗ , Xueliang Huang∗ , Luis F. Veiros† , Nuno Maulide∗
∗
Max-Planck-Institut für Kohlenforschung – Kaiser-Wilhelm-Platz 1 –
45470 Mülheim an der Ruhr – GER
†
Departamento de Engenharia Química – Universidade Técnica de Lisboa –
Av. Rovisco Pais – 1049-001 Lisboa – POR
[email protected]
The direct cyclopropanation of olefins is an important and valuable transformation
in organic synthesis from a laboratory scale all the way to industrial production, as
cyclopropanes are common structural features of both naturally occuring and nonnatural bioactive substances.[1] Olefin cyclopropanation is dominated by the powerful chemistry of diazo compounds, which can be decomposed by specific transition
metals (commonly rhodium, ruthenium, palladium, iridium or copper) to produce
metallocarbene complexes in situ.[2] These metallocarbenes are mild and selective
cyclopropanating agents and perform best with electron-rich or -neutral olefinic partners.
During our recent studies on the gold-catalysed rearrangement of sulfonium ylides
bearing an allyloxycarbonyl moiety,[3] we serendipitously discovered a direct intramolecular cyclopropanation of sulfonium ylides onto olefins. In this presentation, we shall
report on the development of a gold-catalysed intramolecular cyclopropanation of
electron-neutral alkenes by stabilised sulfonium ylides, mechanistic and computational
investigations into this process and preliminary results on an asymmetric version.[4]
Gold-catalysed intramolecular cyclopropanation of sulfonium ylides.
[1]
a) Brackmann, F.; de Meijere, A. Chem. Rev. 2007, 107, 4493; (b) Brackmann, F.; de Meijere,
A. Chem. Rev. 2007, 107, 4538.
a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis
with Diazo compounds; Wiley Interscience: New York, 1998; b) Lebel, H.; Marcoux, J.-F.;
Molinaro, C.; Charette, A. B. Chem. Rev. 2003, 103, 977; c) Reissig, H.-U.; Zimmer, R. Chem.
Rev. 2003, 103, 1151; d) Maas, G. Chem. Soc. Rev. 2004, 33, 183.
[3]
Huang, X.; Peng, B.; Luparia, M.; Gomes, L. F. R.; Veiros, L. F.; Maulide, N. Angew. Chem.
Int. Ed. 2012, 51, 8886.
[4]
Huang X.; Klimczyk, S.; Veiros, L. S.; Maulide, N. Chem. Sci. 2013 doi: 10.1039/C2SC21914J.
[2]
Poster 084
Thursday 17:40 - 20:10
141
Influence of calcination conditions on supported Cu particles
as a catalyst for methanol steam reforming
Lena Schmidt, Gregor Koch, Thorsten Ressler
Institut für Anorganische und Analytische Chemie – Technische Universität Berlin –
Straße des 17. Juni 135 – 10623 Berlin – GER
[email protected]
Hydrogen is frequently discussed as energy carrier of the future. Complications in
handling due to its gaseous aggregate state can be avoided by chemically binding hydrogen, e.g. as methanol. Methanol synthesis and its reverse reaction (i.e. methanol
steam reforming to release hydrogen) are industrially catalyzed by a Cu/ZnO/Al2
O3 catalyst.[1,2] For a more efficient use of valuable resources catalysts need to be
improved in both activity and selectivity. reliable structure-activity relations are required. In order to exclude contributions from other components, here Cu particles
in the size range of few nm and stabilized on a nanostructured silica support were
investigated as model systems.
Four samples of Cu particles on a SBA-15 support were prepared by incipient wetness with Cu-citrate solutions with different concentrations. Afterwards samples of
varying layer thickness and concentration were calcined under controlled conditions.
Reducibility of the prepared CuO particles and activity of the resulting Cu phase
were studied by temperature programmed reduction (TPR) and catalytic measurements (Fig. 1), respectively. It was shown, that activity in methanol steam reforming
and structure of the active Cu phase were influenced by the calcination conditions.
Corresponding structure activity correlations are presented.
Fig. 1: Comparison of the relative H2 ion currents under methanol steam reforming
conditions of Cu particles supported on SBA-15 calcined under different conditions and
with varying Cu loadings.
[1]
[2]
S. Sá, H. Silva, Applied Catalysis B 2010, 99, 43.
M. M. Günter, T. Ressler, Catalysis Letters 2001, 71, 37.
142
Thursday 17:40 - 20:10
Poster 085
Continuous-flow photoreactor packed with magnesium(II)
2,3-bis(1-adamantylsulfanyl)phthalocyanine immobilized on
silica
Michal Kryjewski ∗ , Michal Nowak† , Tomasz Goslinski† , Jadwiga Mielcarek∗
∗
†
[email protected]
(1 O
Singlet oxygen
2 ) constitutes a versatile reagent in many synthetic approaches,
able to oxidize substrates that are unaffected by oxygen in its normal, triplet state. Organic chemists have found utility of 1 O2 as synthetic reagent, characterized its versatility, availability, low costs, and negligible environmental impact. 1 O2 reacts rapidly
with unsaturated carbon-carbon bonds in ene reactions, [4+2] and [2+2] cycloadditions, heteroatom oxidations.[1] Phthalocyanines (Pcs) are synthetic aza-analogues of
porphyrins, which upon illumination with light of an appropriate wavelength generate
1O .
2
We synthesized magnesium(II) 2,3-bis(1-adamantylsulfanyl)phthalocyanine and reported its photochemical properties.[2] This new macrocycle exhibited high singlet
oxygen quantum yield value Φ∆ = 0.49 in both dimethylformamide and dimethylsulfoxide. Therefore, it was chosen as an active agent in design of continuous-flow
photoreactor for singlet oxygen generation. The phthalocyanine was deposited on
silica gel and next used to pack glass chromatography column. LED array emitting
light of wavelength λ = 690 nm, corresponding to the absorbance maximum of the
compound, was used.
1,3-Diphenylisobenzfuran (DPBF) is a chemical quencher of singlet oxygen which was
used in a hexane solution passing via column during the measurements. Illumination
of silica gel modified with Pc resulted immediately in decrease of DPBF concentration
in eluate, while silica gel without immobilized Pc showed no 1 O2 production.
Fig. 1 Scheme of the photoreactor, change of absorbance at λ = 411 nm during constant
flow of DPBF solution in dark and light conditions.
[1]
[2]
M. C. DeRosa et al., Coord. Chem. Rev. 2002, 233-234, 351-371.
M. Kryjewski et al., Inorg Chem Commun 2013, 27, 56-59.
This study was supported by grant from the Polish Ministry of Science and Higher Education –
National Science Centre (N N404 069440).
Poster 086
Thursday 17:40 - 20:10
143
Stable ruthenium indenylidene complexes with a sterically
reduced NHC ligand
Adam Zielinski, Grzegorz Szczepaniak, Karol Grela
[email protected]
Over the past decade olefin metathesis became a powerful tool in organic synthesis.[1]
New ruthenium complexes that combine high catalytic activity with excellent tolerance to multiplicitous functional groups have been developed.[2] Despite the fact that
many modifications of olefin metathesis catalysts have been introduced during the
past years, obtaining a new complex that allows good yields with demanding partners is still a challenge.
Since the introduction of the ‘first generation’ Ru-based catalysts the basic structure
has been modified leading to different catalyst families[3] , including the most prominent mixed N-heterocyclic carbine (NHC)–phosphine metathesis catalysts, described
as ‘second generation’. The replacement of one labile phosphine ligand with a nonlabile NHC led to an increased longevity of the active species and therefore better
catalyst performance.
A new indenylidene complex containing o-tolyl NHC ligand has been synthetized.[4]
The catalytic activity of the complex was investigated in model reactions. Notably,
for the RCM of sterically demanding olefins it is one of the most efficient catalysts
reported so far.
Fig. 1. New o-tolyl Ru catalyst
[1]
T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18-29.
K. Grela, S. Harutyunyan, A. Michrowska, Angew. Chem., Int. Ed. 2002, 41, 4038.
G. C. Vougioukalakis, R. H. Grubbs, Chem. Rev. 2010, 110, 1746.
[4]
C. Torborg, G. Szczepaniak, A. Zieliński, M. Malińska, K. Woźniak, K. Grela, “Stable Ruthenium Indenylidene Complexes with a Sterically Reduced NHC Ligand” Chem. Commun. 2013,
in press
[2]
[3]
144
Thursday 17:40 - 20:10
Poster 087
New Sustainable Decarboxylative Allylations of Benzoic acid
Derivatives
Kai Pfister , Lukas J. Gooßen
FB Organische Chemie – Technische Universität Kaiserslautern –
Erwin-Schrödinger-Straße Building 54 – Kaiserslautern – GER
[email protected]
Within recent years, the field of decarboxylative allylation reactions has undergone
tremendous development.[1] However, most of the known catalytic protocols are versions of the Carroll rearrangement and extend only to allyl esters of carboxylic acids
that – upon extrusion of CO2 – form stabilized carbanions.[1] Even fewer methods
for the decarboxylative allylation of benzoic acids have been developed and they still
suffer from limited substrate scope, for example the restriction to electron-rich benzoic acids.[2] Furthermore the requirement of an excess of silver(I) salts and toxic allyl
halides makes this approach less attractive.
We have recently overcome these drawbacks by developing a waste free method for the
decarboxylative allylation of benzoic acid derivatives without the need of stoichiometric amount of additives. The developed method gives the corresponding allylbenzenes
in good to excellent yields, proceeds at moderate temperatures and produces only CO2
as byproduct.
The new catalyst also allows the conversion of benzoic esters that are generated in
situ. For example, benzoic acids can be allylated with diallyl carbonate and directly
be converted to the corresponding allylarenes. In this process, CO2 and allyl alcohol
remain the only side products.
Decarboxylative Allylations
[1]
[2]
J. D. Weaver, A. Recio, A. J. Grenning, J. A. Tunge, Chem. Rev. 2011, 111, 1846–1913.
J. Wang, Z. Cui, Y. Zhang, H. Li, L.-M. Wu, Z. Liu, Org. Biomol. Chem. 2011, 9, 663–666.
Poster 088
Thursday 17:40 - 20:10
145
Development new convenient palladium-catalyzed
trifluorovinylations of arene halides
Sina P. Zucker , Sasa Duric, Bernd M. Schmidt, Nina M. Ninnemann, Dieter Lentz,
C. Christoph Tzschucke
Institut für Chemie und Biochemie – Freie Universität Berlin – Takustraße 3 –
[email protected]
Trifluorostyrenes are interesting and important compounds in material sciences and
drug development, yet, only few convenient reactions for their preparation have
been reported.[1] Most of them require the formation of highly reactive and unstable, organometallic intermediates or are multistep sequences. Recently we developed the synthesis of trifluorostyrenes by coupling of aryl bromides with stable
trimethoxy(trifluorovinyl)borate 1 derived from the bulk compound HFC-134a.[2] To
further simplify the procedure and to broaden the substrate scope, we are developing a
one-step/one-pot procedure for a convenient palladium-catalyzed coupling reaction of
aryl halides with in situ generated trifluorovinylanion synthons. This method requires
highly active catalysts, which operate at very low temperatures as well as a better
understanding of the elemental steps involved. The synthesis of differnt precatalysts
and preliminary results of coupling reactions will be discussed.
[1]
R. Anilkumar, D. J. Burton, Tetrahedron Letters 2002, 43, 2731-2733; A. Raghavanpillai, D.
J. Burton, J. Org. Chem. 2004, 69, 7083-7091; M. Ohashi, T. Kambara, T. Hatanaka, H. Saijo,
R. Doi, S. Ogoshi, J. Am. Chem. Soc. 2011, 133, 3256-3259; M. Ohashi, H. Saijo, M. Shibata,
S. Ogoshi, Eur. J. Org. Chem. 2012, 3454-5457; Eur. J. Org. Chem. 2013, 3, 443-447; T.
Yamamoto, T. Yamakawa, Org. Lett. 2012, 14, 3454-3457; C. Xu, S. Chen, L. Lu, Q. Shen, J.
Org. Chem. 2012, 77, 10314-10320.
[2]
S. Duric, B. M. Schmidt, N. M. Ninnemann, D. Lentz, C. C. Tzschucke, Chem. Eur. J. 2012,
18, 437-441.
146
Thursday 17:40 - 20:10
Poster 089
Searching for the Transmetalation Intermediate in
Copper-Catalyzed 1,4-Addition Reactions via NMR
Spectroscopy
Felicitas von Rekowski, Katrin Schober, Ruth M. Gschwind
Department of Organic Chemistry – University of Regensburg – Universitätsstr. 31 –
Regensburg – GER
[email protected]
For the formation of C-C bonds, with a new chiral center, one of the most powerful methods is the enantioselective catalytic 1,4-addition reaction to α,β-unsaturated
systems. With a catalytic system consisting of chiral phosphoramidite ligands and
copper(I) salts it is possible to reach high chemo- and regioselectivity and quantitative yields. A further advantage are the relatively low costs compared to other
applied catalytic systems.[1−4] In order to elucidate the structure of the formed Cu(I)
complexes as well as their temperature dependent geometry we combine experimental as well as simulated 31 P NMR spectra and 1 H diffusion experiments of various
mixtures. For this purpose the Cu(I) source, the ligand to salt ratio and the solvent
were varied. With these data we were able to identify a binuclear precatalytic complex structure with a mixed trigonal/tetrahedral coordination on copper.[5−8] This
complex structure provides a free coordination site for the transmetalation reagent.
The transmetalation of the organic moiety from the organometallic reagent to the
precatalytic copper complex represents the first step in the proposed mechanism.
However, up to now no experimental proof for such a transmetalated species was
found. Thus we elucidate several systems combining the precatalytic copper complex
with diaryl/dialky zinc or trialkyl aluminum reagents by various NMR spectroscopic
techniques. Recently we were able to detect for the first time a transmetalation intermediate by 1 H31 P HMBC experiments, but the structure of the transmetalated
species is until now not completely elucidated.
Schematic presentation of the 1,4-addition of a trialkylaluminum reagent with the
investigated precatalytic copper complex.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
A. Alexakis et al., Chem. Rev. 2008, 108, 2796.
T. Jerphagnon et al., Chem. Soc. Rev. 2009, 38, 1039.
N. Krause et al., Synthesis 2001, 2, 171.
J. F. Teichert et al., Angew. Chem. Int. Ed. 2010, 41, 2486.
H. Zhang et al., Angew. Chem. Int. Ed. 2006, 45, 6391.
H. Zhang et al., Chem. Eur. J. 2007, 13, 6691.
K. Schober et al., J. Am. Chem. Soc. 2008, 130, 12310.
K. Schober et al., Angew. Chem. Int. Ed. 2010, 49, 2794.
Poster 090
Thursday 17:40 - 20:10
147
Secondary Phospine Oxides: A Stable Approach for Gold
Catalysis
∗
Felix Schröder ∗ , Jean Philippe Goddard† , Virginie Mansuy† , Louis Fensterbank†
Chemistry Department – Technische Universität Berlin – Straße des 17. Juni 115 –
Berlin – GER
†
Chimie Organique de Synthèse – Université Pierre et Marie Curie Paris 6 –
4 Place Jussieu – Paris – FRA
[email protected]
The use of Secondary Phosphine Oxide Gold(I) Complexes (SPO-Au) in enyne cycloisomerizations was examined. The SPO-Au complex is affordable and easy to synthesize, and it is not as instable under no protecting atmospheric conditions as other
transition metal-ligand complexes are. A large variety of different enynes (Scheme
1) were synthesized in order to determine the activity and selectivity of the catalytic
system. The main focus was put on 1,6-enynes with a tosyl or ortho-tosyl protected
nitrogen linker in position four on the enyne with a varying substitution pattern at
the triple and double bond. Other enynes bearing malonic acid dimethyl ester in position four or an acetyl group in position three also gave very interesting results. The
catalytic conversion mostly followed the general procedure given in the literature.[1,2]
Three different main product classes could be identified. Two of them are formal
metatheses products bearing highly substituted 1,3-dienes and the third is an interesting class of cyclopropane derivatives (Scheme 2). The class of enynes bearing an
acetyl group showed furthermore a 1,2-migration of the acetyl which was presented
earlier by Fensterbank et al.[3] The chiral background of the SPO-Au complex was
also used for enantioselective cycloisomerizations of 1,6-enynes. The enantiomeric
excess could be raised in the beginning from 0% to 11% by changing the reaction
conditions. It was shown that the used SPO-Au complex has the potential for substituting other more expensive and fragile catalytic systems and our results encourage
further investigation.
[1]
L. Zhang, J Sun, S. A. Kozmin, Adv. Synth. Catal. 2006, 348, 2271-2296.
C. H. M. Amijs, V. López-Carrillo, M. Raducan, P. Pérez-Galán, C. Ferrer, A. M. Echevarren,
J. Org. Chem. 2008, 73, 7721-7730.
[3]
X. Moreau, J.-P. Goddard, Matthieu Bernard, G. Lemière, J. M. López-Romero, E. Mainetti,
N. Marion, V. Mouriès, S. Thorimbert, L. Fensterbank, M. Malacria, Adv. Synth. Catal. 2008,
350, 43-48.
[2]
148
Thursday 17:40 - 20:10
Poster 091
Synthesis of biphenolic natural products through
Suzuki-Miyaura-reaction using Pd/C in water
Martin Riemer ∗ , Bernd Schmidt†
Institut für Chemie – Universität Potsdam –
Karl Liebknechtstraße 24-25 Haus 25 D1.12 – Golm – GER
†
Institut für Chemie – Universität Potsdam –
Karl Liebknechtstraße 24-25 Haus 25 D1.16 – Golm – GER
∗
[email protected]
Biphenols and their derivatives are lead structures in many natural products, drugs
(e.g. vancomycin) and precursor of many ligands.[1] Biphenyls are phytoalexins of
Pyrinae (apples, pears) and therefore economically attractive.[2]
A good method to synthesise biaryls is the Pd-mediated SUZUKI-MIYAURA-reaction.
The reaction is hampered by the phenolic structure of these phytoalexins, because
electron-rich arylhalides are less reactive. It is challenging to avoid the protecting/deprotecting steps and actually only a few examples of a direct coupling are
known.[3]
We report an efficient method for the synthesis of biphenols and the total synthesis
of biphenolic phytoalexins which features a ligandless SUZUKI-MIYAURA-reaction
using simple Pd on charcoal (heterogenous, easy to remove) in water.[4]
[1]
G. Bringmann, T. Gulder, T. A. M. Gulder, M. Breuning, Chem. Rev. 2011, 111, 563.
C. Chizzali, L. Beerhues, Beilstein J. Org. Chem. 2012, 613.
[3]
J. S. Freundlich, H. E. Landis, Tetrahedron Lett. 2006, 47, 4275.
[4]
T. Hirao, H. Sakurai, J. Org. Chem. 2002, 67, 2721.
[2]
Poster 092
Thursday 17:40 - 20:10
149
Synthesis and characterization of long-term sintering-stable
Ni catalysts for dry reforming of CO2
Katharina Mette ∗ , Stefanie Kühl∗ , Robert Schlögl∗ , Malte Behrens∗ , Hendrik Düdder† ,
Kevin Kähler† , Martin Muhler†
∗
Abteilung Anorganische Chemie – Fritz-Haber-Institut der Max-Planck-Gesellschaft –
Faradayweg 4-6 – 14195 Berlin – GER
†
Laboratory of Industrial Chemistry – Ruhr-University Bochum – Universitätsstr. 150 –
44801 Bochum – GER
[email protected]
Fossil power generations emit large amounts of the greenhouse gas CO2 . Thus, the
efficient conversion of CO2 into useful chemical intermediates is an important component for prospective resource-saving and sustainable energy economics.
This work mainly focuses on the use of CO2 and methane as raw materials to obtain
syngas by dry reforming (DRM: CO2 + CH4 −→ 2CO + 2H2 ). Since dry reforming is a highly endothermic reaction, several carbon producing side reactions can
occur leading to deactivation of the catalysts.[1] To suppress side reactions, high reaction temperatures are needed. For the catalyst development the main challenge is the
preparation of a noble metal-free material, which prevents coking and is stable at high
temperatures. Here, we show that Ni/MgAlOx catalysts derived from hydrotalcitelike (htl) precursors fulfill these requirements.
Ni/MgAl2 O4 catalysts have been prepared from hydrotalcite-like (htl) compounds as
precursors by a constant pH co-precipitation method. The precursors and catalysts
were extensively characterized in their calcined and reduced states as well as after
DRM, using a variety of methods.
XANES spectroscopy reveals the presence of two different Ni oxide species in the
mostly amorphous calcined materials; NiO and NiAl2 O4 . The reduced catalysts exhibit a homogeneous metal distribution with high BET and specific Ni surface areas
(up to 40 m2 /gN i ) and small Ni particles (∼10 nm), which are embedded in an
MgAlOx matrix (Fig. 1). The ex-htl catalysts show high activities and outstanding
stabilities in DRM at 900◦ C over 100 hours. The specific activities are found to correlate linearly with the specific metal surface area. TEM analysis of the spent catalysts
reveals a good stability of the microstructure and only minor carbon deposition. In
summary, we developed a noble metal free Ni/MgAlOx catalyst, which is stable at
high temperatures even with high Ni loadings. With these materials coking during
DRM can be suppressed to a certain extent by an increase of the reaction temperature
allowing stable operation over 100 hours.
Fig. 1: TEM micrographs of the Ni/MgAlOx catalysts reduced at 1000◦ C; 50 mol%
(left), 25 mol% (center) and 5 mol% Ni (right).
[1]
S. Wang, G. Q. (Max) Lu, Energy & Fuels 1996, 10, 896-904.
150
Thursday 17:40 - 20:10
Poster 093
Postsynthesis, Characterization, and Catalytic Properties in
Alkene Epoxidation of Hydrothermally Stable Mesoporous
Ti-SBA-15
Edyta Makuch, Agnieszka Wróblewska
Department of Chemical Organic Technology –
Institute of Organic Chemical Technology, West Pomeranian University of Technology Szczecin –
Pulaskiego 10 – Poland – POL
[email protected]
The microporous TS-1 catalyst (with the structure of MFI type) used in the process
of allylic compounds epoxidation was obtained in 1983 by Taramasso at al.[1] A few
years later, in 1990, the microporous titanium-silicalite catalyst TS-2 with the MEL
structure was obtained by Reddy at al.[2] Despite of the differences in the structures
of TS-1 and TS-2, these catalysts have close and small pore size (0.5 nm) and a similar
catalytic activity. Because of small pore size these materials can be used only for the
epoxidation of unsaturated compounds with the small molecules.
In 1992 Camblor at al.[3] obtained the titanium silicalite catalyst Ti-Beta (with pore
size of 0.8 nm) having the structure of BEA. Ti-Beta due to the incorporation of
aluminum in the crystal lattice, is considered as a catalyst showing oxidizing and
acidic properties. This properties of the Ti-Beta catalyst cause that epoxides formed
duning the epoxidation of allylic compounds can easily undergo hydration. The research published by Mobil R & D Corporation in 1992 confirmed the discovery of
mesoporous materials of M41S type. These materials are characterized by narrow
distribution of pores (from 2 to 30 nm) and large specific surface (from 800 to 1600
m2/g).[4] The literature data show that all titanium silicalite catalysts (TS-1, TS-2,
Ti-Beta, Ti-MCM-41, Ti-MCM-48) undergo deactivation in the process of allyl alcohol epoxidation. One of the reasons is the leaching of titanium from the structure of
the catalyst. In the case of mesoporous titanium silicalite catalysts (Ti-MCM-41, TiMCM-48) deactivation is also connected with the instability of the structure in water
solution. Much greater thermal stability (compared to the other titanium silicalite
catalysts) and high arrangement of the structure has the mesoporous Ti-SBA-15 catalyst. This material, which belong to newest titanium silicalite catalysts, is obtained
with the use of a biodegradable polymer Pluronic P123 as a structure-directing agent.
[1]
M. Taramasso, G. Perygo, B. Notari, “Preparation of porous crystalline synthetic material
comprised of silicon and titanium oxides”, Pat. USA 4 410 501, 1983.
J. S. Reddy, R. Kumar, P. Ratnasam, “Titanium silicalite-2: synthesis, characterization and
catalytic properties”, Appl. Catal. A: General 1990, 58, L1-L4.
[3]
M. A. Camblor, A. Corma, J. Perez-Pariente, “Zeolites, A new highly efficient method for the
synthesis of Ti-Beta zeolite oxidation catalyst”, Appl. Catal. A: General 1995, 133, L185-L189.
[4]
G. Oye, J. Stocker, “Sythesis, characterization and potential applications of new marerials in
the mesoporous range”, Adv. Colloid Interfac. 2001, 89-90, 439-466.
[2]
Poster 094
Thursday 17:40 - 20:10
151
Synthesis and immobilisation of Pd-bipyridine catalysts for
aerobic alcohol oxidation
Anja Sokolowski, C. Christoph Tzschucke
Chemie und Biochemie – Freie Universität Berlin – Takustraße 3 – Berlin – GER
[email protected]
Palladium-catalysed oxidations typically require a stoichiometric secondary oxidant
such as benzoquinone or CuCl2 . This increases the complexity of the reaction and
complicates product isolation and reduces the atom efficiency.[1] A major interest in
palladium-catalysed reactions is the stabilisation of the catalyst and the reoxidation of
the Pd(0) intermediate to prevent Pd-black formation. To address these limitations,
recent developments utilise coordinating solvents or ligands to stabilise the Pd(0)
intermediates and molecular oxygen as stochiometric oxidant.[2,3]
Our work investigates the viability of immobilisation of Pd bipyridine-complexes on
gold electrode. This methodology could both provide fast reoxidation of Pd(0) on the
electrode surface and prevent Pd black formation. A variety of substituted bipyridines
were synthesized and attached to a sulfur functionalised linker that can be immobilised
on gold surfaces. The synthesis of the functionalized linkers and characterisation of
the immobilized complexes will be presented.
[1]
B. A. Steinhoff, I. A. Guzei, S. S. Stahl, J. Am. Chem. Soc. 2004, 126, 11268-11278.
D. M. Pearson, N. R. Conley, R. M. Waymouth, Organometallics 2011, 30, 1445-1453.
[3]
G.-J. ten Brink, I. W. C. E. Arends, M. Hoogenraad, G. Verspui, R. A. Sheldon, Adv. Synth.
Catal. 2003, 345, 1341-1352.
[2]
152
Thursday 17:40 - 20:10
Poster 095
Ultrasound-Assisted Rapid Synthesis of Ferrocene
Containing Beta-Amino Ketone with Direct-Type Catalytic
Mannich Reaction ans Investigating its Physical Properties
∗
Bahadir Keskin ∗ , S. Arda Ozturkcan∗ , Ahmet Altindal‡
Chemistry – Yildiz Technical University – 34210 – Istanbul – TUR
‡
Physics – Yildiz Technical University – 34210 – Istanbul – TUR
[email protected]
The scientific endeavor on the investigation of ferrocene containing molecules keeps
increasing although 60 years has passed over its discovery by Pauson and Kealy.[1] An
important carbon–carbon bond forming reaction in organic synthesis for the preparation of beta-amino carbonyl compounds[2] is Mannich reaction. Water is one of
the eco-friendly, ease of access, inexpensive solvent and can certainly be considered
as the cleanest solvent available for chemists.[3] Sonochemistry as a green innovation
powerful technique can be extremely efficient and is applicable to a wide variety of
practical syntheses has increasing interest in accelerate organic reactions.[4] The concept of green innovations in synthetic chemistry have emerged as a major solution
for the development of cleaner and more benign chemical processes.[5] As part of
this green concept, “water” and “ultrasound” have become so popular and received
substantial interest.
A green innovative, quite rapid, powerful novel and efficient method was developed
to synthesize various beta-aminoketone derivative (4) from cyclohexanone (3), substituted 4-aminobenzyl cyanide (2) and, ferrocenecarboxaldehyde (1) via ultrasoundassisted direct-type catalytic Mannich reaction using bismuth (III) triflate in water.
Good yields of the desired product (4) were obtained from available substrates, such
as beta-aminoketones, at room temperature in 2 hours by ultrasound. The prominent
advantages of the proposed method are simple conditions, easy work-up, low toxicity,
shorter reaction time, anti-selectivity and higher yields over to traditional methods.
The product clarified by spectroscopic methods (FTIR, 1 H NMR, UV-Vis, MS) after
the purification processes and investigated its physical properties.
Scheme 1. Synthesis of beta-aminoketone using Mannich reaction.
[1]
D. A. Boyd, R.J. Crutchley, P.E. Fanwick, T. Ren, Inorg. Chem. 2009, 49, 1322-1324.
S. Kobayashi, H. Ishitani, Chem. Rev. 1999, 99, 1069-1094.
J. Noei, A. R Khosropour, Ultras. Sonochem. 2009, 16, 711-717.
[4]
Y. Q. Liu, L. H. Li, L. Yang, H. Y. Li, Chemical Papers 2010, 64, 533-536.
[5]
S. K. Hota, A. Chatterjee, P. K. Bhattacharya, P. Chattopadhyay, Green Chem. 2009, 11,
169-176.
[2]
[3]
Poster 096
Thursday 17:40 - 20:10
153
Synthesis of complex Phosphonates via Fe-catalyzed Allylic
Substitution
Susanne Rommel, André P. Dieskau, Bernd Plietker
Institut für Organische Chemie – Universität Stuttgart – Pfaffenwaldring 55 –
70569 Stuttgart – GER
[email protected]
Organo-phosphonates are useful building blocks in organic synthesis. They are used
in a broad spectrum of reactions, e.g. the Horner-Wadsworth-Emmons-reaction. So
far the access to complex organo-phosphonates is mostly limited to high temperature
procedures. Even more challenging are phosphonates with two adjacent quaternary
carbon centers due to unfavorable steric interactions.
Previously, our group succeeded in developing a Fe-catalyzed regioselective alkoxyallylation of activated double bonds. Here we present the extension of this method to
the snythesis of diversely functionalised organo-phosphonates via a tandem phosphaMichael-addition-allylic substitution-reaction.
[1]
S. Rommel, A. P. Dieskau, B. Plietker, Eur. J. Org. Chem., accepted.
A.P. Dieskau, M.S. Holzwarth, B. Plietker, Chem. Eur. J. 2012, 18, 2423.
[3]
W.S. Wadsworth, W.D. Emmons, J. Am. Chem. Soc., 1961, 83, 1733.
[2]
154
Thursday 17:40 - 20:10
Poster 097
Small molecules adsorbed on fuel cell catalysts studied by a
combined XAS/in-situ DRIFTS approach
Claudia Brieger ∗ , Alexander Schökel∗ , André Wolz∗ , Christina Roth∗
Institute of Chemistry and Biochemistry – FU Berlin – Takustr. 3 – Berlin – GER
†
Institute of Material Science – TU Darmstadt – Petersenstr. 23 – Darmstadt – GER
∗
[email protected]
One problem in fuel cell technology is the Pt-catalyzed carbon corrosion at the cathode, leading to a severe degradation of the performance in long-term operation. Consequently, new support concepts are required. One approach is to replace the carbon
support by electron conducting (doped) oxides. But while oxide supports are very
common in heterogeneous catalysis, only little is known about their structure, working principles, degradation behavior and their application in electrocatalysis. Thus
to follow structural changes of the novel catalyst systems, and in particular changes
of the novel oxide support materials, will be of great importance in the future.
Here we report on our approach to combine XAS (in particular delta µ XANES)
and in-situ DRIFTS for future investigation of the interaction between the support
material and the adsorption of small molecules relevant to fuel cell catalysis. In-situ
measurements shall be used to differentiate between reactive intermediates and “spectator” adsorbates and account for metal-support-interactions. Due to the catalysts’
small particle size and low metal loadings, XAS is the optimum choice for our studies,
since it provides information on structure (EXAFS) and adsorbates (delta µ XANES)
at the same time. In particular, EXAFS yields results about cluster size and morphology whereas delta µ XANES gives additional information about binding sites
and adsorbate coverage. With in-situ DRIFTS interactions between the adsorbates
and the oxide support can be studied. A combination of both techniques, for instance
XAS-IR, has been shown by Newton.[1] To further establish the novel delta µ XANES
technique, in-situ DRIFTS measurements will be carried out simultaneously to complement the delta µ XANES information. Therefore, CO oxidation has been picked as
a model reaction to analyze the metal-support interactions of oxide-supported Pt-M
catalysts, since numerous studies for comparison can be found in the literature. Additionally, it exhibits a good spectral signature, which allows for comparison between
delta µ XANES and DRIFTS.
For the planned experiments, we will examine the adsorption of CO on Pt-M (M=Pt,
Ru) on different support materials (carbon, oxides) as a model system which is relevant to fuel cell catalysis. Using a temperature controlled, combined reactor cell, delta
µ XANES and in-situ DRIFTS measurements will be done simultaneously. This cell
is constructed right now and based on a DRIFTS cell design by Drochner.[2] Different
requirements have to be taken into account, such as implementation of X-ray windows and minimization of the dead volume. This design allows for the first time to
take XAS and in-situ DRIFTS spectra of the sample and the reference in one single
cell, thus under the same conditions. The new insight will be used to develop tailormade and more stable catalysts, whose structure will be adapted to the prevailing
conditions in order to reduce costs, which is of particular interest for commercial applications. Furthermore, new information will be gained about reaction and poisoning
mechanisms of catalysts in fuel cells.
[1]
[2]
M. A. Newton, A. J. Dent, S. G. Fiddy, B. Jyoti, J. Evans Catalysis Today 2007, 126, 64-72.
S. Kohl, A. Drochner, H. Vogel Catalysis Today 2010, 150, 67-70.
Poster 098
Thursday 17:40 - 20:10
155
Regio- and Enantioselective Cyclobutene Allylations
Supaporn Niyomchon, Davide Audisio, Marco Luparia, Nuno Maulide
Max-Planck-Institut für Kohlenforschung – Kaiser-Wilhelm-Platz 1 –
45470 Mülheim an der Ruhr – GER
[email protected]
Palladium catalysed asymmetric allylic alkylation (AAA) is a powerful synthetic
method for the preparation of optically active compounds.[1] Recently, our laboratory
has focused on the palladium-catalysed reactions of bicyclic lactone 1 with stabilized
(“soft”) nucleophiles to generate highly functionalised cyclobutenes with impressive
diastero- and enantioselectivities.[2,3]
We have now investigated the behaviour of this system in the presence of nonstabilized (“hard”) nucleophiles. In this presentation, we report our preliminary results
on the catalytic, asymmetric regioselective allylation of lactone 1 with allyl boronates
2 as well as exploratory mechanistic studies.[4]
[1]
B. M. Trost, M. L. Crawley, Chem. Rev. 2003, 103, 2921-2943.
a) F. Frébault, M. Luparia, M. T. Oliveira, R. Goddard, N. Maulide, Angew.Chem. Int. Ed.
2010, 49, 5672-5676; b) M. Luparia, D. Audisio, N. Maulide, Synlett. 2011, 735-740.
[3]
a) M. Luparia, M. T. Oliveira, D. Audisio, F. Frébault, R. Goddard, N. Maulide, Angew.
Chem. Int. Ed. 2011, 50, 12631-12635; b) D. Audisio, M. Luparia, M. T. Oliveira, D. Klütt, N.
Maulide, Angew. Chem. Int. Ed. 2012, 51, 7314-7317.
[4]
S. Niyomchon, M. Luparia, D. Audisio, submitted.
[2]
156
Thursday 17:40 - 20:10
Poster 099
Effect of the preparation conditions on the photoactivity of
TiO2 prepared by hydrolysis of titanium isopropoxide
Magdalena Grześkowiak , Jacek Przepiórski, Antoni W. Morawski
Institute of Chemical and Environmental Engineering –
West Pomeranian University of Technology – Pułaskiego 10 – Szczecin – POL
[email protected]
Titanium dioxide also called as titania is very well-known photocatalyst.[1]
Received TiO2 powders were obtained through the hydrolysis of precursor solution
consisting of a mixture of organometallic compound, titanium isopropoxide (TTIP),
and 2-propanol in a volume ratio of 1:3. Subsequently, precursor solution was dissolved by slowly adding into water under magnetic stirring at ambient temperature
in various pH. Obtained a colloidal white suspension was dried overnight at 110o C.
Finally, portions of the hydrated amorphous titanium dioxide was calcined at 500o C
for various times in an argon atmosphere.
The aim of the present work is to focus on the influence of the water volume used
to hydrolysis process and calcination time on the chamical and physical properties
of obtained TiO2 photocatalysts. Moreover, titanias obtained through hydrolysis
process carried out in 250 ml of water in an environment of both acidic and alkaline
conditions were compared.
The obtained powders were characterized by N2 adsorption-desorption (BET) and
X-ray powder diffraction. Also the photocatalytic activity of obtained TiO2 powders
and its photodecomposition of azo-dye as a model compound (New Coccine) was
investigated (Fig. 1).
Figure 1. Concentration changes of New Coccine during the photodecomposition process
under UV irradation using test materials obtained by: a) hydrolysis in various water
volume and calcined at 500o C for 180 min, b) hydrolysis in 250 ml of water and calcined
at 500o C for various times
[1]
D. P. Macwan, P. N. Dave, S. Chaturvedi, “A review on nano-TiO2 sol-gel type synthesis and
its applications”, The Journal of Materials Science 2011, 46, 3669-3686.
Poster 100
Thursday 17:40 - 20:10
157
Microwave Assisted Synthesis of Chitosan & Protein
Conjugates
Zafer Omer Ozdemir
Chemistry – Kırklareli University – Kirklareli – TUR
[email protected]
Chitosan is a biodegradable natural polyelectrolyte bearing -NH2 groups.
characteristics of chitosan make it convenient for conjugation reactions.[1-3]
These
Microwave assisted synthesis of varying ratios of conjugates of chitosan with proteins (BSA and HSA) and polyacrylic acid using various activators (carbodiimide
and HBTU/HOBt) and characterization of these molecules are aimed in this project.
In addition, chitosan will be modified with bromoacetic acid to make it water-soluble.
Microwave usage in conjugation reactions is a new approach and usage of microwave
energy in chemical reactions is rapidly increasing.
Synthesized bioconjugates will be characterized with various chromatographic and
spectroscopic methods and interpreted. The bioconjugates synthesized in the project
will have usage potential in many fields (enhancing immunogenicity, drug delivery,
molecular imaging, gene transfer, artificial tissues, etc.) by modifying them with
various methods.
[1]
[2]
[3]
H. Zhang, R. Li, W. Liu, International Journal of Molecular Sciences 2011, 12, 917-934.
I. Aranaz, R. Haris, A. Heras, Current Organic Chemistry, 14, 308-330, 2010.
S. C. Yadav, A. Kumari, R. Yadav, Peptides, 32, 173-187, 2011.
This work was supported by Yildiz Technical University Project No 29-07-04-GEP01
158
Thursday 17:40 - 20:10
Poster 101
Efficiently Quenched Fluorescent NIR Probe for Detection of
Enzyme Activity
Jagoda Sloniec, Ute Resch-Genger, Andreas Hennig
Analytical Chemistry; Reference Materials –
Federal Institute for Materials Research and Testing – Richard-Willstätter-Straße 11 –
Berlin – GER
[email protected]
Fluorescence technologies are powerful research tools in the detection of enzyme
activity.[1] The use of activatable optical probes, which are targeted against diseaserelated enzymes, allows imaging of enzymatic activity, monitoring of enzyme reaction
and determination of kinetic properties of an enzyme.[2] Herein we introduce an efficiently quenched fluorescent probe for activity detection of a model enzyme (PGA).
Owing to positioning dye and quencher at the same side of the enzyme recognition
moiety we secure a close spatial proximity and thereby an optimal dye-quencher interaction in our fluorescent probe. Hence, our approach ensures efficient fluorescence
quenching for NIR dyes by exploiting contact-based quenching mechanisms. The enzymatic cleavage of our fluorescent probe leads to a fragmentation into individual
molecular building blocks via a well-established quinone-methide elimination and to
a release of previously quenched dyes. We report the successful multistep synthesis,
a dye screening with a set of NIR dyes, relative quantum yields of synthesized fluorescent probes, fluorescence quenching mechanism and enzyme kinetic parameters.
Fig.1. Design principle of our efficient quenched fluorescent probe.
[1]
a) A. Hennig, D. Roth, T. Enderle et al., ChemBioChem 2006, 7, 733; b) H. Sahoo, A. Hennig,
M. Florea et al., J. Am. Chem. Soc. 2007, 129, 15927; c) A. Hennig, H. Bakirci, W. M. Nau,
Nat. Meth. 2007, 4, 629; d) A. Hennig, M. Florea, D. Roth et al., Anal. Biochem. 2007, 360,
255; e) R. N. Dsouza, A. Hennig, W. M. Nau, Chem. Eur. J. 2012, 18, 3444.
[2]
W. Pham, Y. Choi, R. Weissleder et al., Bioconjugate Chem. 2004, 15, 1403.
Poster 102
Thursday 17:40 - 20:10
159
Fluorescent Lipids as FRET-Probes
– Shining Light on Sphingolipid Metabolism –
Thomas Pinkert, Christoph Arenz
[email protected]
Lipid signaling processes have been shown to be related to major cellular events
e.g. proliferation, cell death (apoptosis, necroptosis), autoimmune and inflammatory processes.[1] Related diseases comprise acute lung injury, diabetes and cancer[2]
as well as bacterial infections (e.g. Neisseria gonorrhoea).[3] Therefore, the realtime-visualization and in-situ-quantification of these processes in living tissues are
of key importance in lipid chemistry. Recently, this was accomplished for the acid
ceramidase[4] and different phospholipases[5] by the synthesis of doubly labeled fluorescent lipid analogues which allow the determination of enzyme activity within the
living cell by means of Förster resonance energy transfer (FRET).
These biochemical tools could not only supersede laborious and expensive radioactive
assays, but could also shine light on transport kinetics and topology, essential information that is still elusive since established analytical methods (mass spectrometry
of purified fragments) fail in this regard.
Having synthesized a probe for the acid ceramidase[4] we now aim at establishing
probes for the sphingomyelin-synthase and acid sphingomyelinase (aSMase). The latter enzyme is responsible for the degradation of membrane constituent sphingomyelin
and involved cell cycle regulation and development of Niemann-Pick lysosomal storage
disease.[3] In order to design a FRET-probe for the aSMase we want to synthesize a
fluorescently labeled artificial substrate, which upon action of the enzyme shows different photospectral properties. This should allow the determination of the enzyme
activity in situ.
Structure and mode of operation of the envisioned aSMase-FRET-probe.
[1]
R. W. Jenkins, D. Canals, Y. A. Hannun, Cell Signal 2009, 21, 836-846.
E. L. Smith, E. H. Schuchman, FASEB J 2008, 22, 3419-3431.
[3]
T. Kolter, K. Sandhoff, Angew. Chem. Int. Ed. 1999, 38, 1532-1568.
[4]
K. P. Bhabak, A. Hauser, S. Redmer, S. Banhart, D. Heuer, C. Arenz, 2013, in revision.
[5]
O. Wichmann, J. Wittbrodt, C. Schultz, Angew. Chem. Int. Ed. 2006, 45, 508-512.
[2]
160
Thursday 17:40 - 20:10
Poster 103
LC-MS of intact proteins - a tool for fast venom mass
profiling. Application to death adder (Acanthophis laevis)
venom.
Daniel Petras ∗ , Stefan H. Hüttenhain† , Roderich D. Süssmuth∗ , Juan J. Calvete‡
∗
Institut für Chemie – TU Berlin – GER
†
Fachbereich Chemie- und Biotechnologie – Hochschule Darmstadt – GER
‡
Laboratorio de Venómica y Proteinómica Estructural –
Instituto de Biomedicina de Valencia, CSIC – ESP
[email protected]
Snake venoms are complex mixtures of bioactive polypeptides. A deep understanding
of the composition of venoms is of applied importance not only for exploring their
enormous potential as sources of pharmacological novelty, but also to fight the dire
consequences of snakebite envenomings.[1] Unraveling complex molecular venom phenotypes is now within the reach of “omic” tecnologies. In particular, the last decade
has witnessed the development of bottom-up proteomic strategies to explore venom
proteomes.[2] Proteomics-based protocols to quantify the extent of cross-reaction of
IgG or (Fab’)2 antivenoms against homologous and heterologous venoms, have been
also recently introduced.[3-5] Drawbacks of bottom up venomics include the co-elution
(HPLC), low mass resolution (SDS-PAGE), or impaired quantification ability (2DE),
of the venom components. In addition, HPLC peak identification is restricted to the
detection limit (LOD) of UV detectors, which is up to 100 times higher than LODs
of mass analysers.[6] Further, off-line mass determination is time-consuming and not
amenable for high-throughput screening. To overcome these difficulties, LC-MS can
be applied for the rapid venom analysis.[7] In this work, we applied a LC-MS method
using high resolution mass spectrometry for the rapid mass profiling of death adder,
Acanthophis laevis, venoms from three different geographic regions of Papua-New
Guinea. Quantification of detected masses was achieved by combining UV chromatographic areas and the summed extracted ion chromatogram signals. Our results show
that A. laevis venom consists of PLA2 s (50-75%), 3FTxs (10-35%), Kunitz-type inhibitors (2-15 %), peptides (< 1%), and non-assigned m/z < 2000 (5-7 %) and >23
kDa (∼4%) components. These data provide a valuable insight into A. laevis venom
composition and geographic variability, and found the scaffold for the further venomic
characterization of this medically relevant snake.
[1]
R. J. McCleary , R. M. Kini, Toxicon 2013, 62, 56-74.
J. J. Calvete, Expert Rev. Proteomics 2011, 8, 39-58.
B. Lomonte, J. Escolano, J. Fernández, L. Sanz, Y. Angulo, J. M. Gutiérrez, J. J. Calvete, J.
Proteome Res. 2008, 7, 2445-2457.
[4]
D. Petras, L. Sanz, A. Segura, M. Herrera, M. Villalta, D. Solano, M. Vargas, G. León, D. A.
Warrell, R. D. Theakston, R. A. Harrison, N. Durfa, A. Nasidi, J. M. Gutiérrez, J. J. Calvete, J.
Proteome Res. 2011, 10, 1266-1280.
[5]
D. Pla, J. M. Gutiérrez, J. J. Calvete, Toxicon 2012, 15, 688-699.
[6]
R. J. Hein, Proquest, Umi Dissertation Publishing 2011.
[7]
B. G. Fry, J. C. Wickramaratna, W. C. Hodgson, P. F. Alewood, R. M. Kini, H. Ho, W. Wüster,
Rapid Commun Mass Spectrom. 2002, 1, 600-608.
[2]
[3]
Poster 104
Thursday 17:40 - 20:10
161
Mutual Lewis Acid–Base Interactions of Cations and Anions
in Ionic Liquids
Markus Holzweber ∗ , Ralf Lungwitz† , Denise Doerfler‡ , Stefan Spange† , Mihkel Koel ,
Herbert Hutter‡ , Wolfgang Linert‡
∗
Division 6.8 - Surface Analysis and Interfacial Chemistry –
BAM - Federal Institute for Material Science and Testing – Unter den Eichen 44 –
Berlin – GER
†
Institute of Chemistry – Chemnitz University of Technology – Strasse der Nationen 62 –
Chemnitz – GER
‡
Institute of Applied Synthetic Chemistry – Vienna University Of Technology –
Getreidemarkt 9/ – Vienna – AUT
Institute of Chemistry – Tallinn Technical University – Akadeemia Tee 15 –
Tallinn – EST
[email protected]
Solute properties are known to be strongly influenced by solvent molecules due to
solvation. This is due to mutual interaction as both the properties of the solute
and of the solvent strongly depend on each other. The presented work is based
on the idea that ionic liquids are cations solvated by anions and anions solvated
by cations. To show this (in this system strongly pronounced) interaction the long
time established donor–acceptor concept for solvents and ions in solution by Viktor
Gutmann is extended to ionic liquids. A number of solvent parameters, such as the
Kamlet–Abboud–Taft and the Dimroth–Reichardt ET scale for ionic liquids neglect
this mutual influence, which, however, seems to be in fact necessary to get a proper
description of ionic liquid properties. It is shown how strong such parameters vary
when the influence of the counter ion is taken into account. Furthermore, acceptor
and donor numbers for ionic liquids are presented.
162
Thursday 17:40 - 20:10
Poster 105
Synthesis and study of antioxidant properties of fullerene C60
derivatives.
Robert Czochara, Michał Symonowicz, Grzegorz Litwinienko
[email protected]
Oxidative damage of organic materials is caused by free radicals and Reactive Oxygen Species (ROS). Antioxidants can inhibit oxidation reaction by removal of free
radicals. Activity of antioxidants depends on structure and chemical nature, thus,
nanoparticles are new promising objects for free radical research. Fullerenes[1] can
find many potential applications in science, industry and medicine.[2,3] Carbon core
makes fullerene an interesting initial structure in the development of novel radicalscavenging compounds with specific functionalities. Recently, it has been shown that
fullerenes and their derivatives can trap several radicals per molecule[4] and can potentially be used as a protective substance against ROS.
The aim of our studies is to synthesize[5] organic derivatives of fullerene C60 (X)n
(where X= C10 Hqq N O2 ; (N HC6 H4 OH)6 ; C9 H9 N O). The structures are shown in
Figure 1.
By means of the differential scanning calorimetry (DSC) and Clark electrode[6,7] we
also carried out the investigations on the potential antioxidant properties during the
oxidation of stearic (ST) and linolenic (LNA) acids as models of oxidizable organic
materials. Our results showed that at high temperature in bulk lipid phase the C60
and its derivatives are stable and can break radical oxidation chains. This feature
is useful because new derivatives can be applied as antioxidants working in extreme
conditions.
This work was supported by Faculty of Chemistry, University of Warsaw, grant BST
501/86-DSM-102400.
Figure 1. Obtained fullerene C60 derivatives.
[1]
H. W. Kroto, J. R. Heath, S. C. O’Brien, R. F. Curl, R. E. Smalley, Nature 1985, 318, 162.
B.C. Yadav, R. Kumar, International Journal of Nanotechnology and Applications 2008,
2, 15.
[3]
R. Bakry, R. Vallant, International Journal of Nanomedicine 2007, 2, 639.
[4]
S. S. Huang, S. K. Tsai, C.L. Chih, L.Y. Chiang, Free Radical Biol. Med. 2001, 30, 643.
[5]
M. Prato, M. Maggini, Acc. Chem. Res. 1998, 31, 519.
[6]
P. Ziaja, K. Jodko-Piorecka, R. Kuzmicz, G. Litwinienko, Polym. Chem. 2012, 3, 93.
[7]
R. Czochara, P. Ziaja, P. Piotrowski, R. Pokrop, G. Litwinienko, Carbon 2012, 50, 3943.
[2]
Poster 106
Thursday 17:40 - 20:10
163
Homogeneous immunoassay based on bioluminescence
resonance energy transfer from Luciola mingrelica luciferase
Daria V. Smirnova, Janna V. Samsonova, Alexander P. Osipov, Natalia N. Ugarova
Chemistry Department – M.V. Lomonosov Moscow State University –
Leninskiye Gory 1-3 – Moscow – RUS
[email protected]
Homogeneous immunoassay is one of the perspective, but insufficiently explored direction of bioluminescence resonance energy transfer (BRET) applications. Here we
propose a rapid and potentially sensitive homogeneous immunoassay of low molecular
weight antigen based on the BRET. In this work we studied possibility of luciferase L.
mingrelica application in homogeneous immunoassay for determination of low molecular weight antigens. Progesterone was chosen as a model antigen. System includes
thermostable mutant form of luciferase (4TS), conjugated with progesterone (donor)
and fluoro-labeled antibody (acceptor of bioluminescence). As an acceptor we used
Alexa fluor 610-x dye, because it has an optimal spectral overlap of the luminescent
and dye excitation spectra and a larger quantum yield as compared with Cy3 or Cy3.5,
described at [1] . The method could find a wide range of applications by exchanging
antigens and corresponding antibodies.
In this work, we optimized conditions of synthesis of luciferase-progesterone conjugates. Via heterogeneous ELISA we demonstrated, ability of progesterone-luciferase
conjugate form a complex with antibody. The strict dependence of Bioluminescent
activity on the ratio luciferase/progesterone in reaction mixture was observed: increased from 12 to 63 percent, while this ratio was reduced from 1: 50 to 1: 5. We
obtained conjugates of dye-labeled antibody (BRET-acceptor), with an F/P ratio of
3 to 10, and tested them for the luminescence energy transfer measurement.
Then bioluminescent progesterone-tagged luciferase spectra in absence and presence
of fluoro-labeled antibody were registrated at different concentrations of components.
In absence of fluoro-labeled antibody only one maximum (590 nm), correspond to
the luciferase emission was obserwed. When fluoro-labeled antibody was added, a
reduction in the light emission at around 590 nm, and increase around 630 nm were
observed, suggesting a transfer of energy from the progesterone-tagged luciferase to
the fluoro-labeled anti-progesterone antibody.
BRET-indices were taken as the ratios of the light emissions at 630 and 590 nm.
Linear relationship was observed between BRET indices and the amount of dye incorporated into a protein. Then the relationships between the BRET indices and labeled
antibodies concentration were plotted. A reduction of BRET index in presence of progesterone was observed. This show possibility of application Luc4TS conjugate for
the determination of low molecular weight antigen via homogeneous ELISA in short
time.
[1]
Y. Yamakawa, H. Veda et al., Journal of Bioscience and Bioengineering, 2002, 93, 537-542.
164
Thursday 17:40 - 20:10
Poster 107
Wheat Bran as Anti-Urolithiasis Crystallization
Khaled Sekkoum ∗ , Nasser Beleboukhari∗ , Abdelkrim Cheriti† , Safia Taleb‡
Biomolecules & Chiral Separation Laboratory – University of Bechar – POBox 417 –
Bechar – ALG
†
Phytochemistry & Organic Syntheesis Laboratory – University of Bechar –
POBox 417 – Bechar – ALG
‡
Material & Catalysis Laboratory – Djilali Liabes University – Sidi Bel Abess – ALG
∗
[email protected]
Urolithiasis can lead to the loss of renal function in some cases. In this study, we
tested the inhibiting effect of wheat bran (Triticum aestivum L) extract on calcium
oxalate crystallization in a turbidimetric model, by FTIR spectroscopy, and polarized
microscopy. The results show that this plant extract has a major inhibitory effect on
calcium oxalate crystallization.
Poster 108
Thursday 17:40 - 20:10
165
Preparation of zinc phthalocyanine catalysts by cotton fabric
dyeing
Ahmet Lütfi Uğur ∗ , Ali Erdoğmuş† , M. Arif Kaya†
Chemistry – Canakkale 18 March University – Canakkale – TUR
†
Chemistry Department – Yildiz Technical University – Istanbul – TUR
∗
[email protected]
Among tetrapyrrole compounds, phthalocyanines (Pc) which are full-aromatic planar
molecules due to their 18-π electron structure can be substituted with a great deal of
functional groups. In addition to their extensive use as pigments and dyes, this versatility gives rise to many applications, such as catalysts, liquid crystals, electrochromic
and photochromic substances, data storage systems, photodynamic cancer therapy
agents, photoactive units, chemical sensors, and nonlinear optical devices.[1-3] Catalytic activities of metallo-phthalocyanines derived from their structural similarity to
metallo-porphyrin complexes have been widely studied because of their rather cheap
and facile preparation in a large scale and of their chemical and thermal stability.[4]
In this study, a novel phthalonitrile derivative was prepared from a single step reaction. By using phthalonitrile derivative, metallo-phthalocyanines carrying acidic substituents on the periphery were synthesized. Spectral results such as FT-IR, UV–Vis,
EI-MS and 1H-NMR for the newly synthesized compounds are in good agreement
with the proposed structures. Last part of this work dealt with the cotton fabric
which was modified with a cationic auxiliary and converted to cationic cotton fabric
for dyeing process.
[1]
N. B. McKeown, Phthalocyanine materials: synthesis, structure and function Cambridge
University Press, Cambridge, 1998.
[2]
F. H. Moser, A. L. Thomas, Properties The phthalocyanines, vol. 1CRC Press, Boca Raton,
FL, 1983.
[3]
C.C. Leznoff, A.B.P. Lever, Phthalocyanines properties and applications, VCH Publishers,
Weinheim, 1989.
[4]
M. Kimura, Y. Yamaguchi, T. Koyama, K. Hanabusa, H. Shirai, “Catalytic oxidation of 2mercaptoethanol by cationic water-soluble phthalocyaninatocobalt(II) complexes”, J. Porphyrin
Phthalocyanines 1997, 1 (4), 309-315
166
Thursday 17:40 - 20:10
Poster 109
The structure and biological activity of the fucoidans from
the brown alga Fucus evanescens
Ksenia Porshneva ∗ , Olesya S. Vishchuk † , Tatiana N. Zvyagintseva†
bioorganic chemistry and biotechnology – Far Eastern Federal University –
27, Oktabrskaya Street – Vladivostok – RUS
PIBOC FEB RAS – prospekt stoletiya Vladivostoka, 159 – Vladivostok – RUS
∗
†
[email protected]
Nowadays the search and isolation of biological active substances from algae are very
actual problems. Polysaccharides from brown algae of the Russian Far Eastern seas
possess unique structure and properties. Thus, brown algae of the Russian Far Eastern are of great interest because they are renewable and easily cultivated source of
this substances. Fucoidans are high sulfated homo- and heteropolysaccharides from
brown algae. The reason of high interest to these polysaccharides is wide spectrum
of biological activities, such as antineoplastic, immunomodulating, antibacterial, antiviral and antiphlogistic activity. Due to fucoidans are nontoxic for the body they
are widely tested on ability to prevent from development of different types of cancer.
The alga Fucus evanescens was found out to be the richest source of fucoidans. The
aim of this research was to obtain highly purified fucoidans from this species of algae
for further determination of the structural characteristics of isolated fucoidans. The
next stage of the investigation is to elucidate correlation between the structure of
fucoidans and their anticancer and antineoplastic activity.
Poster 110
Thursday 17:40 - 20:10
167
Analysis of the size distribution and the fluorence probe
encapsulation in water in oil macromeulsion used as cell
model systems
Maria Concetta Dipalo ∗ , Emiliano Altamura∗ , Pasquale Stano† , Fabio Mavelli∗
∗
Chemistry Department – University – Via Orabona 4 – Bari – ITA
†
Biology Department – University of Roma Tre – Viale Guglielmo Marconi 446 –
Roma – ITA
[email protected]
Emulsion droplets and lipid vesicles have been extensively used as compartmentalized
chemical systems to model cells in lab experiments[1] , since they have an aqueous core
enclosed by a lipid boundary. Their size can range from few nanometers to tens of
micron and they can encapsulate biomolecules, like proteins, DNA and RNA, in the
inner aqueous solution.[2] Recently, the phase transfer method has been presented as
a new method for giant vesicle preparation where the macroemulsion formation is the
initial step of the procedure. Moreover, the physics of the biomolecules encapsulation
during the lipid compartment preparation is highly relevant both in basic and applied
research. In origin of life studies, the entrapment of solutes inside liposomes might
explain the onset of metabolic pathways in primitive cells. Preliminary unexpected
observations[3] seem to indicate that the formation of liposomes acts as an attractor
for the solutes in solution, bringing about a very high local concentration in some of
them.
In this contribution, we present a study of macroemulsion droplets preparation and
fluorescence probes encapsulation. The ternary system studied is mineral oil/1palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine(POPC)/water. The influence of the
vortexing time on the droplets size distribution and on the probe encapsulation has
been studied by performing both a dimensional and a fluorescence intensity analysis
by confocal microscopy. We have also investigated the correlation between the yield
of encapsulation of various fluorophores and different physical-chemical properties, in
order to determine a law of distribution of their local concentration.
Water in Oil droplets containing 10 µM Calcein in
[1]
P. Walde, K. Cosentino, H. Engel,P. Stano, ChemBioChem 2010, 11, 848-865.
P. Stano, P. Carrara, Y. Kuruma, T. de Souza, P. L. Luisi, J. Mat. Chem. 2011, 21, 1888718902.
[3]
P. L. Luisi, M. Allegretti, T. de Souza, F. Steiniger, A. Fahr, P. Stano, ChemBioChem 2011,
11, 1989-1992.
[2]
168
Thursday 17:40 - 20:10
Poster 111
Thymine and 2,6-diaminopurine: a crystal architecture study
in the context of crystal engineering and nucleic acid base
pairing
Urszula Budniak , Katarzyna N. Jarzembska, Paulina M. Dominiak
[email protected]
Nucleobases, i.e. either purines or pyrimidines, constitute undoubtedly a crucial group
of compounds in the context of nucleic acids. The specific interactions between these
moieties are responsible for maintaining a proper structure of DNA, and thus are
essential for the correct transfer of the genetic information. Nucleobases may form
hydrogen bonding (in general, between the complementary pairs) but also may participate in π-stacking interactions (between the aromatic ring fragments).
Beside the natural nucleic acid bases (NABs), also their analogues are commonly
investigated. Some of such derivatives are encountered in organisms, while others
are obtained artificially. Nevertheless, the information gained from the studies of
unnatural compounds can contribute to our knowledge about nucleic acid properties
in general, and is extremely useful for drug design.
The presented project is focused on two nucleobases, i.e. thymine and 2,6- diaminopurine. The first one occurs naturally in biological systems, whereas the second is the
derivative of adenine. The two analysed moieties should bind together via triple hydrogen bonding, which is in contrast to a double Watson-Crick bonding characteristic
for a standard A-T pair. Within this project a lot of effort was dedicated to synthesising the component crystals and the co-crystal, and to characterise them. For that
purpose X-ray diffraction experiments were carried out. For good quality and well
diffracting crystals the experimental charge density analysis was performed, while for
the remaining cases the TAAM procedure (Transferable Aspherical Atom Model) was
applied.[1] Here, we present a comprehensive study of crystal packing and energetic
features of the analysed systems in the context of the related compounds deposited
in the Cambridge Structural Database (CSD) and our previous works dedicated to
the NAB derivatives.[2,3] The nature of intermolecular interactions, structural motifs
and crystal packing was analysed via Hirshfeld surfaces and fingerprint plots, charge
density distribution, and theoretical calculations (CRYSTAL, Gaussian, and PIXEL).
The solvent impact was also considered.
[1]
N. K. Hansen, P. Coppens, “Testing aspherical atom refinements on small-molecule data sets”,
Acta Cryst. 1978, A34, 909-921.
K.N. Jarzembska, M. Kubsik, R. Kamiński, K. Woźniak, P.M. Dominiak, “From a single molecule
to molecular crystal architectures - structural and energetic studies of selected uracil derivatives”,
Cryst. Growth Des. 2012, 12, 2508-2524.
[3]
K.N. Jarzembska, A.M. Goral, R. Gajda, P.M. Dominiak, “Hoogsteen-Watson-Crick 9-methyladenine:1-methylthymine complex: charge density study in the context of crystal engineering and
nucleic acid base pairing”, Cryst. Growth Des. 2012, 13, 239-254.
[2]
[4]
The authors acknowledge Polish Ministry of Science and Higher Education for financial support
within the “Diamond Grant” program.
Poster 112
Thursday 17:40 - 20:10
169
Synthesis and evaluation of polycations as inhibitors of
human coronavirus NL63
Justyna Ciejka ∗ , Aleksandra Milewska† , Kamil Kaminski∗ , Anna Karewicz∗ ,
Dorota Bielska∗ , Maria Nowakowska∗ , Jan Potempa† , Krzysztof Pyrc† ,
Krzysztof Szczubialka∗
∗
Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Krakow – POL
†
Faculty of Biochemistry Biophysics and Biotechnology – Jagiellonian University –
Gronostajowa 7 – Krakow – POL
[email protected]
Human coronavirus NL63 (HCoV NL63) is generally classified as a common cold virus
and it may cause severe upper and lower respiratory tract diseases. Thus, there is a
need to develop effective methods of preventing and treating these infections.
The aim of this study was to synthesise and explore anticoronaviral activity of polymerbased compounds. Four polycations, i.e. N(2 hydroxyl)propyl 3 trimethylammonium chitosan chloride (HTCC), hydrophobically modified HTCC (HM HTCC), O(2
hydroxypropyl) 3 trimethylammonium poly(vinyl alcohol) chloride (HTPVA) and
poly(allylamine hydrochloride) (PAH) were investigated. In order to evaluate the
inhibitory activity of the tested polymers in vitro study using LLC MK2 cells and
ex vivo study using human airway epithelium (HAE) cultures were performed. The
cytopathic effect (CPE) was correlated with a quantitative RT PCR based assay. The
cytotoxicity was examined by an XTT assay and a Neutral Red assay.
The results show that cationically modified polymers are effective inhibitors of HCoV
NL63 replication. A cationically modified chitosan derivative HTCC seems to be the
best inhibitor of replication of HCoV NL63 at nontoxic concentrations. Non modified
polymers (chitosan, polyvinyl alcohol) did not show any antiviral properties.
Acknowledgements
This work was supported by the grant from Foundation for Polish Science Team
Programme cofinanced by the EU European Regional Development Fund (PolyMed,
TEAM/2008 2/6), the Ministry of Scientific Research, Poland (0095/B/P01/2009/37
and N N204 151336), Iuventus Plus grant from the Ministry of Science and Higher
Education, Poland (IP 2010 033870) (KP) and Foundation for Polish Science within
the Homing Programme. The Faculty of Biochemistry, Biophysics and Biotechnology of the Jagiellonian University is a beneficiary of the structural funds from the
European Union (grant No: POIG.02.01.00 12 064/08 “Molecular biotechnology for
health”).
Structures of the polymers showing anticoronaviral properties
170
Thursday 17:40 - 20:10
Poster 113
Polymeric photosensitizer for use in antimicrobial
photodynamic therapy
Urszula Kwolek , Ewa Rząd, Mariusz Kępczyński, Maria Nowakowska
Ingardena 3 – Kraków – POL
[email protected]
A porphyrin-polycation conjugate, a polymeric photosensitizer was synthesized and
characterized. The conjugate (Fig. 1) was prepared by modification of the method
described previously[1] , based on covalent attachment of the protoporphyrin IX (Pp)
to the polycation chain of polyethyleneimine (PEI). Protoporphyrin was chosen due
to its good photosensiziting properties[2] , while PEI was previously shown to cross
through bacterial outer membranes.[3,4] Therefore, this conjugate is expected to be
promising for use in antibacterial photodynamic therapy (APDT).
The polymeric photosensitizer was characterized using spectroscopic methods (fluorescence, absorption and NMR spectra) and chromatographic analysis. The obtained
results indicate that Pp-PEI exhibits strongly aggregation in aqueous solution at physiological pH (pH=7.4), whereas absorption and fluorescence spectra of Pp-PEI dissolved in methanol were typical for monomeric form of porphyrins. Chromatographic
analysis (GPC) provided information that synthesized product is uncrosslinked.
The influence of Pp-PEI on lipid membranes was studied using liposomes as a model.
The kinetics of the incorporation of Pp-PEI into the liposomes, the binding constant
(Kb ) to the lipid membranes and fluorescence quenching of porphyrin were evaluated.
The results demonstrate that porphyrin chromophores bind to liposomes, but due to
the large size of the attached polymer, the binding constant is rather low. Incorporation of Pp-PEI into lipid membranes was confirmed using laser scanning confocal
microscopy.
Fig. 1. The structure of Pp-PEI.
[1]
L. Huang, T. Zhiyentayev, Y. Xuan, D. Azhibek, G. B. Kharkwal, M. R. Hamblin, Lasers in
Surgery and Medicine 2011, 43, 313-323.
[2]
F. Ricchelli, Journal of Photochemistry and Photobiology B: Biology 1995, 29, 109-118.
[3]
T. Dai, G. P. Tegos, T. Zhiyentayev, E. Mylonakis, M. R. Hamblin, Lasers in Surgery and
Medicine 2010, 42, 38-44.
[4]
I. M. Helander, K. Latva-Kala, K. Lounatmaa, Microbiology 1998, 144, 385-390.
Poster 114
Thursday 17:40 - 20:10
171
An Novel Acyclic Nucleic Acid Mimic: Preparation,
Properties and Prospection[1]
Meng Su
Fakultät für Chemie und Pharmazie – Ludwig-Maximilians-Universität München –
Butenandtstr. 5-13, Building F – 81377 Munich – GER
[email protected]
For decades, nucleic acid mimics have aroused continued interest to chemist as well as
biologist and shown impressive applications in molecular biology and pharmaceutical
sciences. Herein, a novel nucleic acid mimic based on 3-amino-1,2-propanediol was
designed and synthesized. The opened sugar ring allowed more flexibility. Amide
linkage was introduced to avoid nuclease hydrolysis, and the reserved phosphodiester
bond ensured the solubility. Finally, the distance between the base and sugar was
increased, which benefited the repulsion between strands.
After the four monomers were in hand, substituted single strands and thrombin binding aptamers (TBA) were synthesized with solid phase synthesizer, confirmed by
MADLI-TOF mass spectrometry. According to the melting temperatures, all the
15-mer oligomers, substituted at different positions, showed lower duplex stability
compared to dsDNA (-3.7 ∼ -9.0 K). However, when the acyclic monomer placed
in positions T3, T7 and T12, the aptamer showed higher thermodynamic stability
than unmodified one (+10.7K ), while substitution at other positions decreased the
stability (-16.4 ∼ -20.2 K). Besides, conformational difference was indicated by CD
spectra. Furthermore, for the single strand, the hydrolysis resistance were improved
50 fold in SVPDE and 32 fold in bovine serum, and for the quadruplex 3.6 fold and
1.7 fold respectively.
In short, the novel acyclic nucleic acid mimic offered greater protection towards exonucleases, specific substituted aptamers even showed improved thermodynamic stability.
This study provides valuable information regarding the optimal design of oligonucleotides. Study of further applications such as RNA interference and molecular
beacon are now underway.
Left: acyclic nucleic acid monomers in this study, R = P(OCH2 CH2 CN)Ni Pr2 ; middle:
melting temperatures (partially) of modified dsDNA and aptamers, letters in bold and
italic stand for modified monomers; right: PAGE showing the cleavage kinetics of ssDNA
and aptamers by SVPDE and bovine serum
[1]
This work was supported by the National Natural Science Foundation of China. The author
thanks Dr. Xinjing Tang at Peking University Health Science Center for helpful discussions.
172
Thursday 17:40 - 20:10
Poster 115
Characterization of a Cisplatin-DNA-Antibody and its
Corresponding Antibody-Antigen-Complexes by Mass
Spectrometry Under Native Conditions
Lena Ruhe ∗ , Johanna Hofmann† , Ulrike Hochkirch∗ , Jürgen Thomale‡ ,
Michael W. Linscheid∗
∗
Department of Chemistry – Humboldt-Universität zu Berlin – Brook-Taylor-Str. 2 –
Berlin – GER
†
Department of Molecual Physics – Fritz-Haber-Institute of Max-Planck-Society –
‡
Institute of Cell Biology – University Hospital Essen – Hufelandstraße 55 –
Essen – GER
[email protected]
Since antibodies have been increasingly used in the diagnostic and therapeutic medicine,
new analytical tools for their detection and characterization are getting more and
more important. In recent years, especially soft ionization techniques of mass spectrometry like electrospray ionization (ESI) were improved for the detection of high
masses. This allows the analysis of precise molecular masses of large native proteins
like antibodies without any fragmentation. In order to understand structural aspects
of native non-covalent complexes the analysis of a whole antibody-antigen-complex is
a big challenge and first results are presented in this work.
In this study we analyzed the monoclonal rat antibody R-C18 specific for Cisplatin
induced DNA adducts which was developed by Thomale et al.[1] The detection of
this antibody in its native state was successfully performed by a modified nano-ESI
time of flight mass spectrometer (ToF-MS).[2] The antibody was found to be 20 to
50 fold charged - extremely depending on the parameters used. The correct mass of
the unmodified antibody was determined to 144 kDa. As a model for the antigen
we used synthetic oligonucleotides with known base sequences to produce the specific
platinated DNA antigens. Oligomers contain 50 bases and were analyzed as single
and double strands. The sequences of these 50mers was chosen that only one of the
single strands contains two adjacent guanines to give the supposed binding pattern
G*G*-cisPt(NH3)2 after incubation with Cisplatin. As a result we could detect the
unmodified and the platinated DNA oligomers using mass spectrometry in positive
and negative mode. The whole antibody-antigen-complex using these synthetic platinated oligomers could be successfully measured in positive mode. Surprisingly, the
antibody binds not only to the platinated synthetic 50mer double strand but also to
each of the corresponding platinated single strands. That means that the binding
pattern of this special antibody might neither be restricted to DNA double strands,
nor to the until now assumed binding pattern of G*G* intrastrand Cisplatin adducts.
In conclusion we show the successful detection of antibodies and their antibodyantigen-complexes under native conditions via nano-ESI-High Mass-Q-ToF-MS. In
future it could be possible to determine the precise epitope-binding structure of DNA
antigens detected by diagnostic relevant antibodies.
[1]
[2]
Liedert et al., Nucl. Acids Res. 2006, 34 (6), e47.
van den Heuvel et al., Anal. Chem. 2006, 78, 7473-7483.
Poster 116
Thursday 17:40 - 20:10
173
Kinetic studies on the antiradical activity of sulforaphane.
Jakub Cędrowski, Grzegorz Litwinienko
[email protected]
Sulforaphane (1-isothiocyanato-4-(methylsulfinyl)butane, SFN, Figure 1) is a product of glucoraphanin hydrolysis, a compound naturally found in cruciferous vegetables
such as broccoli. SFN belongs to the group of isothiocyanates and it is considered as
a potential anticancer agent with antioxidant activity.[1]
The antiradical molecular mechanism of SFN has not been clearly recognized yet.
Yuan et al.[2] suggested that methylene sulfoxide group (CH3 -SO-CH2 -) is responsible for SFN activity and proposed a mechanism involving H-atom transfer from
methylene group (CH3 -SO-CH2 -) to an alkyl radical. This interpretation is surprising because of high BDE value (Bond Dissociation Energy) for C-H bond of methylene
sulfoxide group (eg. BDE for C-H bond in dimethyl sulfoxide is 94 kcal/mol).[3] It
is also suggested that isothiocyanate group of SFN (–N=C=S) is not essential for
antioxidant properties, because after reaction of benzyl isothiocyanate with hydroxyl
radical, the –N=C=S group is unchanged.[2]
The aim of this study was to answer which moiety is responsible for SFN antioxidant activity. In our work we studied SFN and its analogues (n-hexyl isothiocyanate
(HITC) and dibuthyl sulfoxide (DBSO)) with model DPPH radical in methanol. The
progress of the reaction was measured by stopped-flow measurements at 517nm.
Obtained bimolecular rate constants show that DBSO is almost inactive toward
DPPH radical. On the other hand HITC reacts with DPPH but much slower than
SFN. Equimolar mixture of DBSO with HITC does not change the rate of reaction
as compared to HITC used alone.
We have proved that isothiocyanate group (-NCS) slowly reacts with radicals and this
observation is in agreement with reports on kinetics of reactions of other compounds
with -NCS group and radicals.[4,5] We account that the presence of both the methylene sulfoxide group and isothiocyanate group in SFN is necessary for its antiradical
properties.
This work was supported by Faculty of Chemistry, University of Warsaw, grant BST
501/86-DSM-102400.
Figure 1. The structure of sulforaphane.
[1]
Zhang Y.S., Talalay P., Cancer Res.(Suppl.) 1994 54, 1976-1981. [2] Yuan H. et al.,
Chin.J.Chem.Eng. 2010 18, 312-321. [3] Luo Y.R., Handbook of bond dissociation energies in organic compounds, CRC Press LLC 2003. [4] Leardini R. et al., J.Org.Chem. 1997
62, 8394-8399. [5] Benati L. et al., J.Org.Chem. 2000 65, 8669-8674.
174
Thursday 17:40 - 20:10
Poster 117
Towards new fungal enzyme inhibitors via five and six
membered nitrones
Mattia Ghirardello, Fernando Gomollon-Bel, David Sadaba, Tomas Tejero, Pedro Merino
Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) –
Universidad de Zaragoza - CSIC - C/ Pedro Cerbuna 12 – Zaragoza – ESP
[email protected]
Even though they are not the most understood molecules in biology, it is well known
that glycans are a primary class of biomolecules, as important as DNA, RNA, proteins
or lipids.[1] For instance, carbohydrates decorate the surface of most cells directing
the interactions between them. Therefore, studying the enzymes that synthesize and
modify membrane-attached glycans may lead to the understanding of very important
biological pathways. Also, by preparing and studying modified sugars to inhibit this
enzymes we can achieve potencial antibiotics, fungicides or antitumoral agents.
In our laboratory, thanks to the vast experience we have in the chemistry of nitrones,[2]
we are developing several methods for the preparation of five and six membered nitrones that can be functionalized and then reduced to give pirrolidines and piperidines,
classic inhibitors of glycosidases and transglycosidades (Figure 1). The products
obtained are currently being tested in molecular docking, molecular dynamics and
inhibition assays.
Figure 1
Aknowledgements:
M. G. thanks the Spanish Ministry of Education, Culture and Sports for a FPU Predoctoral grant.
F. G.-B. and D. S. are grateful to the Spanish Council for Scientific Research (CSIC) for their JAE
Predoctoral grants.
References:
[1]
R. F. Service, Science 2012, 18, 321-323.
[2]
P. Merino, S. Franco, F. Merchán, T. Tejero, Synlett. 2000, 442-454; I. Delso, T. Tejero, A.
Goti, P. Merino, J. Org. Chem. 2011, 76, 4139-4143.
Poster 118
Thursday 17:40 - 20:10
175
A mechanistic study of the interaction between nitrite and
oxy myoglobin using ultra fast techniques
Gabriela Denisa Hathazi, Sonia Mahut, Radu Silaghi-Dumitrescu
Faculty of Chemistry and Chemical Engineering – Babes-Bolyai University –
Arany Janos Str. no. 11 RO-400028, Cluj Napoca – Cluj-Napoca – ROU
[email protected]
NO−
2
The nitrite anion
has recently received much biochemical attention as an endogenous source of nitric oxide that has the potential to be supplemented for therapeutic
effects[1] , as well as for its involvement in the Blue Baby Syndrome[2] , or its use as a
preservative in meat products.[3] Since the reaction can proceed in two directions due
to the equilibrium between the oxy and the deoxy form of the globins, we set out to
establish which is the route taken and which are the very first species formed at the
start of the process. This reaction is known to have complex autocatalytic kinetics,
mediated by protein free-radicals, starting with a slow (lag) phase, after which proceeds onto a fast autocatalytic phase, leading to the oxidation of the oxy form to the
met form, nitrite to nitrate; in the presence of a higher concentration of NO−
2 nitritemet adducts are formed.[4] UV-vis spectra were collected upon stopped-flow mixing
of globins with a supraphysiological excess of nitrite and various kinetic simulations
were performed, deconstructing the resulting spectra into individual components, we
have found a match, that suggests that the initial pathway involves the formation
of an iron(II)-peroxonitrate adduct which releases nitrate and the high-valent radical species, ferryl. This is the first study where a reaction intermediate is directly
detected in the oxy+nitrite reaction.
[1]
A. Keszler, B. Piknova, A. N. Schechter, N. Hogg “The reaction between nitrite and oxyhemoglobin: a mechanisti study”, J. Biol. Chem. 2008, 281(1), 9615-1922.
R. H. Steinhorn, “Therapeutic approaches using nitric oxide in infants and children”, Free
Radic. Biol. Med. 2011, 51(5), 1027-1034.
[3]
A. Dejam, C.J. Hunter, C. Tremonti, R. M. Pluta, Y. Y. Hon, G. Grimes, K. Partovi, M.M.
Pelletier, E. H. Oldfield, R. O. Cannon, A. N. Schechter, M. T. Gladwin, “Nitrite infusion in
humans and nonhumans primates: endocrine effects, pharmacokinetics and tolerance formation”,
Circulation 2007, 116(16), 1821-1831.
[4]
R. Grubina, Z. Huang, S. Shiva, M. S. Joshi, I. Azarov, S. Basu, L. A. Ringwood, A. Jiang,
N. Hogg, D. B. Kim-Shampiro, M. T. Gladwin, “Concerted nitric oxide formation and the release
from simultaneous reactions of nitrite with deoxy and oxy hemoglobin”, J. Biol. Chem. 2007,
282, 12916-12927.
[2]
176
Thursday 17:40 - 20:10
Poster 119
Structural modification of thiazolin-4-ones as potent
5-lipoxygenase inhibitors
Andreas Lill, Sebastian Barzen, Carmen B. Rödl, Dieter Steinhilber, Bettina Hofmann,
Holger Stark
Institute of Pharmaceutical Chemistry – Goethe University – Max-von-Laue-Straße 9 –
Frankfurt am Main – GER
[email protected]
Arachidonic acid released from cytoplasmic membrane upon external stimuli is the
source of one important group of inflammatory mediators: the leukotrienes (LTs). The
key enzyme of their biosynthesis is the iron-containing, heme-free 5-lipoxygenase (5LO). LTs play a pivotal role in inflammation, allergic disorders, asthma, cardiovascular
diseases and cancer. Up to now, only two LT-interfering drugs are marketed with
R and the iron
limited success: the LT-receptor antagonist Montelukast (Singulair)
R
chelating 5-LO inhibitor Zileuton (Zyflo).
The need to discover new active ligands
for anti-leukotriene therapy is still urgent.[1,2]
Based on early virtual screening[3] and medium-throughput screening we previously
identified the 5-arylidene-2-aryl-thiazolin-4-one as a lead structure (Fig. 1).[4]
Our previous studies on structure activity-relationships (SAR) pointed out that this
lead shows a continuous SAR for 5-LO.[4] Now we were focused on further evaluation, characterization and cytotoxicity of the thiazolinones. Therefore we designed
and synthesized novel 5-arylidene-2-aryl-thiazolin-4-one derivatives as direct 5-LO inhibitors, modifying lipophilicity, the exocyclic double bond and introducing bicylic or
mono aryl residues (part A to C). The compounds were prepared by one-pot domino
reaction of thioglycolic acid, the corresponding benzaldehyd and benzonitrile or in a
related two-step synthetic procedure.
With the results of 5-LO inhibitory assay using cell-free as well as whole-cell (PMNL
cells) [2][4] conditions we identified a naphthalene derivative with a ten-fold higher
inhibitory potency than Zileuton and gained further insights into the SAR of the
thiazolinone-based 5-LO inhibitors.[5]
Kindly supported by TRIP, OSF, NeFF, Anwendungsorientierte Arzneimittelforschung
(Fraunhofer IME) and EU COST Actions CM1103, BM1107, BM0806.
Figure 1: 5-Arylidene-2-aryl-thiazolinone core scaffold with structural variations
[1]
M. Peters-Golden and W. Henderson, N. Engl. J. Med. 2007, 357, 1841.
O. Werz, O and D. Steinhilber, Pharmacol. Ther. 2006, 112, 701.
[3]
G. Schneider et al., ChemMedChem 2008, 3, 1535.
[4]
B. Hofmann et al., J. Med. Chem. 2011, 54, 1943.
[5]
S. Barzen et al., Bioorg. Med. Chem. 2012, 20, 3575.
[2]
Poster 120
Thursday 17:40 - 20:10
177
Identification and Characterization Of Secondary
Metabolites Of Paenibacillus larvae
Sebastian Müller ∗ , Eva Garcia-Gonzalez† , Rainer Borriss‡ , Elke Genersch† ,
Roderich Süßmuth∗
∗
Department of Organic Chemistry, Biological Chemistry –
Technische Universität Berlin – Müller-Breslau Straße 10 – Berlin – GER
†
Bee Research Institute, Molecular Microbiology and Bee Diseases –
Humboldt-Universität Berlin – Friedrich-Engels-Str. 32 – Hohen Neuendorf – GER
‡
Bacterial Genetics – Humboldt-Universität Berlin – Chausseestr. 117 – Berlin – GER
[email protected]
American foulbrood (AFB) is considered the most contagious and destructive infectious disease in honeybees, caused by the Gram-positive, spore-forming bacterium
Paenibacillus larvae.[1] Recently, comparative genome analysis revealed that P. larvae
harbours giant gene clusters that code for polyketide synthases (PKS) and nonribosomal peptide synthetases (NRPS).[2] These enzymatic complexes are responsible for
the biosynthesis of natural products that are implicated in multiple functions such as
antibiotic, immunosuppressive, cytostatic and toxic activity. We hypothesized that
P. larvae requires these substances in order to successfully compete against bacterial
competitors present in the larvae, i.e. that the substances produced by these NRPS
serve as antibiotics. In P. larvae genome, we so far identified, extended, and assembled three putative NRPS/PKS clusters. Using bacterial growth inhibition assays
we were able to demonstrate that P. larvae strains indeed inhibited the growth of
different bacterial species suggesting that at least some of these NRPS/PKS clusters
are functional and lead to non-ribosomal antibiotic production. One of these clusters
expresses a tripeptide that is related to antibiotic activity of P. larvae supernatants.
The structure of the tripeptide D-Phe-D-Ala-L-Trp could be elucidated by means of
LC-ESI-MS and GC-CI-MS. A knock-out mutant for the trimodular NRPS cluster
showed a dramatic decrease in bacterial growth inhibition. The NRP itself showed
no antibiotic activity. Further experiments, both in vitro and in vivo, are planned to
prove the role of this substance in pathogenesis.
NRPS assembly line of tripeptide FAW (D-Phe-D-Ala-L-Trp)
[1]
E. Genersch, E. Forsgren, J. Pentikäinen, A. Ashiralieva, S. Rauch, J. Kilwinski, I. Fries. Int.
J. Syst. Evol. Microbiol. 2006, 56, 501-511.
[2]
A. Koumoutsi, X. H. Chen, A. Henne, H. Liesegang, G. Hitzeroth, P. Franke, J. Vater, R.
Borriss, JB. 2004, 186.4, 1084-1096.
178
Thursday 17:40 - 20:10
Poster 121
3,9,17,23-tetraiodo-phthalocyanine magnesium(II) for
applications in targeted photodynamic therapy of cancer
Małgorzata Cyza ∗ , Mariusz Kępczyński∗ , Grzegorz Szewczyk† , Arkadiusz Gut∗ ,
Łukasz Łapok∗ , Maria Nowakowska∗
∗
†
Department of Biophysics – Jagiellonian University – Gronostajowa 7 – Cracow – POL
[email protected]
Over the past years, metallophthalocyanines (MPc) have been recognized as a very
important compound in biomedical studies. MPc derivatives are aromatic macrocycles based on an 18 π electron system. These compounds are photoactive and tend to
generate singlet oxygen species. Due to this property they can be used as potential
photosensitizers in the photodynamic therapy (PDT) of tumors.[1]
Phthalocyanines are known to aggregate in aqueous solution.[2] It is expected that
aggregates will have an adverse effect on efficacy of the PDT. One way to overcome
the low solubility of MPc is their encapsulation in liposomal vesicles.[1]
3,9,17,23-tetraiodo-phthalocyanine magnesium(II) (PcI4 Mg), a MPc derivative, was
obtained in this study and its photochemistry was evaluated. The obtained compound
is characterized by low value of fluorescence quantum yield. The tendency to generate
singlet oxygen species was measured using phosphorescence detection. This method
indicated a high value of the singlet oxygen quantum yield. Unfortunately, it was observed a tendency for aggregation both in aqueous environments and methanol. The
aggregation constant in methanol was determined using physicochemical techniques
including UV-ViS and fluorescence. Next, the interaction between PcI4 Mg and liposomes, a model of biological membrane, was studied. So called binding constant to
liposomes was determined. Studies using the liposomes were carried out in a phosphate buffer solution (pH 7.4). Finally, photostability of the obtained phthalocyanine
in organic solvents was evaluated.
3,9,17,23-tetraiodo-phthalocyanine magnesium(II) (PcI4 Mg)
[1]
C. Gol, M. Durmus, Synthetic Metals 2012, 162, 605-613.
A. Ogunisipe, D. Maree, T. Nyokong, Journal of Molecular Structure 2003, 650, 131-140.
K. Nawalany, A. Rusin, M. Kępczyński, A. Mikhailov, G. Kramer-Marek, M. Śnietura, J. Połtowicz, Z. Krawczyk, M. Nowakowska, Journal of Photochemistry and Photobiology B: Biology
2009, 97, 8-17.
[2]
[3]
Poster 122
Thursday 17:40 - 20:10
179
Vibrational multiconfiguration self-consistent field theory
and a webinterface for providing potential energy surfaces
Florian Pfeiffer , Sandra Heislbetz, Guntram Rauhut
Institute of Theoretical Chemistry – University of Stuttgart – Pfaffenwaldring 55 –
Stuttgart – GER
[email protected]
The accurate determination of vibrational state energies based on variational approaches requires the inclusion of vibration correlation effects. However, based on
VSCF wavefunctions many states show very small leading VCI coefficients and show
thus multi-reference character. For that reason we have implemented vibrational multiconfiguration self-consistent field theory (VMCSCF).[1] With several improvements
we have been able to accelerate our program tremendously.[2] We will present the
theory of the current implementation and illustrate benchmark calculations. Based
on multi-level potential energy surfaces (PES) obtained from explicitly correlated
coupled-cluster theory, i.e. CCSD(T)-F12/VTZ-F12, mean absolute deviations with
respect to experimental data were found to be as low as 3.0 cm−1 .[3]
To provide these high-level multi-dimensional PES to the scientific community we have
set up a web interface (www.pes-database.theochem.uni-stuttgart.de) which allows to
download potential files free of charge.[4] These can be used for vibrational structure
calculations, molecular dynamics simulations and many other purposes, which require
very accurate representations of the PES. The functionality of the web interface allows
the users to search for certain molecules and even to upload potential files, which have
been generated by Molpro.
[1]
S.
S.
[3]
F.
[4]
F.
[2]
180
Heislbetz, G. Rauhut, J. Chem. Phys. 2010, 132, 124102.
Heislbetz, F. Pfeiffer, G. Rauhut, J. Chem. Phys. 2011, 134, 204108.
Pfeiffer, G. Rauhut, J. Phys. Chem. A 2011, 115, 11050.
Pfeiffer, M. Neff, G. Rauhut, to be submitted 2012.
Thursday 17:40 - 20:10
Poster 123
Three-dimensional, porous superstructures by self-assembly
of noble metal nanoparticles – investigation of structural
properties and their application in catalysis
Anne-Kristin Herrmann, Nikolai Gaponik, Alexander Eychmüller
Physical Chemistry/Electrochemistry – TU Dresden – Bergstraße 66b – Dresden – GER
[email protected]
New challenges in nanotechnology arise in the assembly of nanocrystals into threedimensional and complex superstructures which may carry synergistic properties and
opens up new kind of application fields. A new approach leading to highly porous,
non-ordered nanostructured solids makes use of a sol-gel process where noble metal
nanoparticles act as building blocks for nanowires which are interconnected and interpenetrating and therefore forming a self supporting network with macroscopic
dimensions.[1,2] In this case no linker systems or templates are used in order to realize
the network formation. Instead of this controlled destabilization of the colloidal solution act as key step for initialization of the process. Subsequent supercritical drying
in CO2 is used in order to remove the solvent from the pores and transfer the material
into so called aerogels. Details concerning the mechanism and the particle interaction
are still under investigation. In order to characterize the aerogels concerning their
composition and structure on the nano- and micro-scale different techniques are used
as for example optical spectroscopy (HR)TEM, SEM, XRD, EDX, N2 and H2 adsorption. It was shown that their primary structural units match the size range of
the initial nanoparticles (5-15 nm) and they provide a very high surface area, extreme
low density (1/1000 compared to the corresponding bulk metals) but also macroscopic dimensions whilst maintaining most of the nanoscale properties. Therefore
metallic aerogels provide promising candidates for many different application fields as
for example: heterogeneous- and electrocatalysis, energy harvesting systems, optical
sensors, surface enhanced Raman scattering (SERS) substrates, broad band optical
limiters, and conducting transparent substrates.[3] As an example of an application
in the field of catalysis the electrocatalytical activity towards the oxidation of ethanol
of a freestanding α-, β-, or γ- cyclodextrin modified palladium nanoparticle aerogel
with extremely high electrocatalytic current density and good durability was recently
reported.[4] Further possibilities and results for application in catalysis will be discussed within the presentation.
[1]
Bigall, Herrmann, Vogel, Rose, Simon, Carrillo-Cabrera, Dorfs, Kaskel, Gaponik, Eychmüller,
“Hydrogels and Aerogels from Noble Metal Nanoparticles”, Angew. Chem. Int. Ed. 2009, 48,
9731.
[2]
Herrmann, Bigall, Lu, Eychmüller, “Ordered and nonordered porous superstructures from metal
nanoparticles”, in: Complex-Shaped Metal Nanoparticles, ed. Sau, Rogach, Wiley-VCH, 2012.
[3]
Gaponik, Herrmann, Eychmüller, “Colloidal Nanocrystal-Based Gels and Aerogels: Material
Aspects and Application Perspectives”, J. Phys. Chem. Lett. 2012, 3, 8-17.
[4]
Liu, Herrmann, Geiger, Borchardt, Simon, Kaskel, Gaponik, Eychmüller, Angew. Chem. Int.
Ed. 2012, 51, 5743-5747.
Poster 124
Thursday 17:40 - 20:10
181
Towards large scale vibrational structure calculations
Dominik Oschetzki, Michael Neff, Guntram Rauhut
Institut für Theoretische Chemie – Universität Stuttgart – Pfaffenwaldring 55 –
D-70569 Stuttgart – GER
[email protected]
The calculation of accurate anharmonic frequencies for large molecules or clusters is
still very demanding. The reason for that are the calculation of high-level potential energy surfaces (PES) in combination with accurate vibrational correlation calculations
as provided by vibrational configuration interaction methods (VCI). For the efficient
calculation of the PES several techniques can be used for acceleration, like an automated iterative interpolation or a gridcomputing interface. The gridcomputing interface allows for the use of massive parallel architectures and distributed systems, like
the Cray XE6 at the HLRS in Stuttgart. Together with the SEGL Client the generation of the PES can be completely automated on these massive parallel architectures.
In addition to this bottleneck the subsequent VCI calculation becomes expensive,
since the configuration space grows rapidly with the system size. To reduce the computational demands of the VCI calculation, a configuration selection technique is used
to limit the calculation to those configurations, which have a large contribution to the
energy. The observation is that only a very small fraction of the configuration space
is needed to get wavenumber accuracy compared to the experiment. The selection
is based on a VPT2 like energy criterion. To reduce the computational demands of
the VCI calculations further, contractions in the calculation of matrix elements and a
more rigorous use of Slater-Condon analogous rules are used. We investigated a set of
lithium fluoride cluster (up to Li10 F10 ). The equilibrium structures and PES of these
clusters have been calculated at the DF-LCCSD(T)-F12a level of theory using a reasonable basis set. For these systems the LCCSD(T)-F12a method gives an accurate
discription of the electronic structure, while the PES calculation on several thousand
cores benefits from the DF implementation. As the bottleneck of the PES calculation
is reduced dramatically by using the Cray XE6 the subsequent VCI calculations get
more and more the bottleneck. Thereby improving the VCI calculations will be again
in focus.
182
Thursday 17:40 - 20:10
Poster 125
The application of X-rays fluorescence spectroscopy to
determination of fluorides in solid materials
Zuzanna Kowalkiewicz , Sylwia Lipiecka, Katarzyna Makowska, Włodzimierz Urbaniak
Faculty of Chemistry – Adam Mickiewicz University in Poznań –
Umultowska Street 89b – Poznań – POL
[email protected]
X-rays fluorescence spectroscopy is a method based on the fluorescence phenomenon.
Fluorescence is an emission of characteristic X-rays from sample after radiation of a
high energy (X-rays or Gamma rays). Fluorescent radiation of a certain ingredient is
result of the transition of electrons during release of absorbed energy. Characteristic
emitted radiation can be measure as wavelength of photons (wavelength dispersive
spectrometer- XRF WDS) or energy of photons (energy dispersive spectrometer- XRF
EDS). The majority of X-rays fluorescence spectrometers are limited to determination elements from sodium to uranium, therefore determination of fluorine by XRF
spectroscopy is impossible. Moreover, hydrofluoric acid reacts with silicon dioxide
(a component of glass), thus ICP-MS technique is not allowed to measure samples
consist of even small amounts of fluorides.
The aim of this study is to design the new method of determination of fluorides in
solid samples using X-rays fluorescence spectroscopy. This method includes two steps
of preparation of sample-lixiviation calcium compounds by acetic acid and sample
filtration. The residue on the filter constitutes the most insoluble in water fluoride
salt-calcium fluoride (CaF2 , fluorspar). Fluorides from a filtrate are determined by
ion-selective electrode measurement and simultaneously fluorides from a residue are
determined using XRF apparatus. Owning to mentioned reason fluorine could not be
directly measured by XRF spectroscopy. Hence, a concentration of the anions is calculated by measurement of a content of calcium in the residue. Thus, the concentration
of fluorides are computed by stoichiometric composition of CaF2 .
Poster 126
Thursday 17:40 - 20:10
183
A sesquiterpenes acids content of the sedative properties of
lavender flowers (Lavandula angustifolia)
Michalina Adaszyńska, Maria Swarcewicz, Małgorzata Śmist
Department of Organic Synthesis and Drug Technology –
West Pomeranian University of Technology, Szczecin – Piastow Avenue 42 – Szczecin –
POL
[email protected]
Lavender is a valuable resource for a wide therapeutic biological activity. In a series
of publications, new varieties of lavender are still generating interest in research,
resulting in the possibility of using this herb, such as an antibacterial agent, antifungal,
antioxidant, anti-inflammatory as well as acting as a natural antidiabetic medication
and sedative.[1-3] Counting a group of sedative drugs and sleep aids, almost completely
devoid of adverse side effects at normal dosages, preparations are made based on plant
extracts. The aim of this study was to determine the content of sesquiterpenes acids:
valeric and acetoxyvalerenic acids with flowers of different varieties of lavender.
The determination was performed by the method described in the European Pharmacopoeia.[4] Samples of lavender flowers were subjected by grinding. Extraction of
sesquiterpenes acid were made in methanol. The resulting extract was analyzed by
HPLC chromatography and chromatographic analysis were carried out in parallel with
the addition of the internal standard (1,8-dihydroxyantrahinone). Studies have shown
that different varieties of lavender sesquiterpenes acids content. Most valeric acid was
determined in the variety ’Ellegance Purple’ (1.52 mg/100 g), and the least in the
variety ’Blue River’ (0.75 mg/100 g). However, the flowers of ’Blue River’ contained
10-fold more acetoxyvalerenic acid (65.8 mg/100 g) than those of ’Ellegance Purple’
(6.5 mg/100 g).
[1]
L. Hui, L. He, L. Huxan, L. XiaoLan, Afri. J. Microbiol. Res., 2010, 4, 309-313.
A. Issa, M. Mohammad, M. Hudaib, K. Tawah, J. Med. Plants. Res. 2011, 5 (16), 3876-3882.
[3]
W. Soyowan, V. Siripornpanich, T. Piriyapunyaporn, J. Med. Assoc. Thai. 2012, 9 (4), 2-9.
[4]
European Pharmacopoeia 5.0.
[2]
184
Thursday 17:40 - 20:10
Poster 127
Gas chromatographic-mass spectrometric identification and
quantitation of volatile cognac spirit components
Peter Nalivayko
Analitycal Chemistry – Belarussian State University – ul. Leningradskaya 14 – Minsk –
BLR
[email protected]
Cognac is a heavy object of analysis because of the complexity of production technology that requires sophisticated analytical equipment, specialized methodological
materials, skilled labor and certain material costs. This fact combined with the lack
of funding and high cost of production generated a flow of counterfeit that occupied
significant market share. The purpose of this study is to develop a methodology of
finding of most common ways of cognac adulteration in Eastern Europe. The study
is based on an assessment of the organoleptic characteristics of cognac, and gas GCMS analysis that allows to define the composition and ratio of volatile cognac spirit
components as well as components of the decomposition of oak.
Poster 128
Thursday 17:40 - 20:10
185
A DFT Study on The Coordination of N,
N-dimethyl-N’-(2-chloro)benzoylthiourea with Ni2+ and
Co3+ Metal Ions
Celal Özpınar ∗ , Gül Altınbaş Özpınar† , Fatih Mehmet Emen‡ , Nevzat Külcü
Department of Chemistry – Kirklareli University – Kavakli – Kırklareli – TUR
†
Department of Chemistry – Bursa Technical University – Merinos – Bursa – TUR
‡
Department of Chemistry – Mehmet Akif Ersoy University – Burdur – TUR
Department of Chemistry – Mersin University – Mersin – TUR
∗
[email protected]
N,N-dialkyl-N’-benzoylthioureas are extensively used as ligands in coordination chemistry due to the fact that these structures including very strong donor groups such
as carbonyl and thioamide are able to coordinate to especially transition metal ions
as monoanionic bidentate ligands which are formed by deprotonation.[1,2] They have
recently attracted great attention as versatile ligands in numerous applications such
as in pharmaceutical and agrochemical industries for potential therapeutic agents.
In this study, we have performed theoretical investigation on the bis(N,N-dimethyl-N’(2-chloro)benzoylthioureato)nickel(II) and tris(N,N-dimethyl-N’-(2-chloro)benzoylthioureato)cobalt(III) complexes using density functional B3LYP, BLYP, OLYP,
PBEPBE, and wB97XD methods with cc-pVDZ basis set. Optimized geometries,
electronic and spectral properties of the complexes are compared with experimental
data.
Figure 1. Structures of Cu (left) and Ni (right) complexes
Bis(N,N-dimethyl-N’-(2-chloro)benzoylthioureato)nickel(II) (right) and
tris(N,N-dimethyl-N’-(2-chloro)benzoylthioureato)cobalt(III) (left) complexes
[1]
[1]
P. Muhl, K. Gloe, F. Dietze, E. Hoyer, L. Beyer, Z. Chem. 1986, 26, 81.
K. R. Koch, Coord. Chem. Rev. 2001, 473, 216-217.
186
Thursday 17:40 - 20:10
Poster 129
Method of finding of honey adulteration by means of
determination of 5-hydroxymethylfurfural presence
Irina Alshakova, Peter Nalivayko
Organic Chemistry – Belarussian State University – ul. Leningradskaya, 14 – Minsk –
BLR
[email protected]
Method of finding of honey adulteration by means of determination of 5-hydroxymethylfurfural presence was proposed in this article. Method includes synthesis of
standart of 5-HMF, sample preparation of honey samples and following chromatographic analysis by means of high performance liquid chromatography accordingly
to proposed conditions. The quality of synthesized standard was confirmed by gas
chromatography-mass-spectrometry. Comparative characteristics of classical methods of determination of 5-HMF in homey samples that was introduced in this article
confirm higher efficiency HPLC analysis as primary method of determination of adulteration of honey samples.
Poster 130
Thursday 17:40 - 20:10
187
Accurate anharmonic vibrational frequencies and
Franck-Condon factors for SeH2 /SeH+
2
Patrick Meier ∗ , Joonsuk Huh† , Robert Berger† , Guntram Rauhut∗
Institute of Theoretical Chemistry – University of Stuttgart – Pfaffenwaldring 55 –
Stuttgart – GER
†
Clemens-Schöpf-Institute – Technical University of Darmstadt – Petersenstr. 22 –
Darmstadt – GER
∗
[email protected]
Photoelectron spectra provide valuable insight into the vibronic structure of a molecule.
In many cases a reliable interpretation of such spectra requires the accurate simulation
based on ab initio calculations. If the relevant potential energy surfaces are expanded
in different coordinates, the Duschinsky rotation needs to be taken into account. This
rotation in combination with an accurate description of the vibrational wavefunctions
by a linear combination of distributed Gaussians leads to a computational bottleneck,
which is subject to current research. Such an approach was tested quite recently.[1]
A new program for the calculation of Franck-Condon factors making use of these
features has been developed within the Molpro suite of ab initio programs.
Here we present highly accurate calculations on the vibronic transitions of the
SeH2 / SeH+
2 system based on wavefunctions obtained from vibrational configuration
interaction calculations. The potential energy surface has been obtained from CCSDTQ calculations with basis sets up to quadruple-ζ quality. Moreover, relativistic and
core correlation effects were found to be important and were thus included within the
determination of the 3-dimensional potential energy surface. Vibrational structure
calculations make use of the full Watson Hamiltonian. Comparison with experimental data is provided.
[1]
J. Huh, M. Neff, G. Rauhut and R. Berger, Mol. Phys. 2009, 108, 409.
188
Saturday 9:00 - 11:30
Poster 131
GC/MS Analysis of Extract and Essential Oil Samples from
Wisteria sinensis
Justyna Sobczak , Elżbieta Huzar, Halina Kwiecień
West Pomeranian University of Technology, Szczecin – al. Piastów 42 – 71-065 Szczecin –
POL
[email protected]
Wisteria sinensis is a woody climbing vine of the family Leguminosae, that can reach
a height of 20 m, characterized by pendent racemes of light blue-violet, scented flowers. Originally from China, Japan and Southern USA, wisteria was brought into
Europe in the nineteenth century.
Several compounds isolated from different wisteria species have been reported to have
antioxidant, antibacterial and anticancer activities.[1,2] Wisteria sinensis flowers are
known for their pleasant, creamy sweet smell. A survey of the literature showed that
the key ingredients of the characteristic fragrance of Wisteria sinensis flowers are two
aromatic compounds: 7-hydroxy-6-methoxy-4H-1-benzopyran and 6,7-dimethoxy-4H1-benzopyran.[3]
We report our results on the analysis of solvent extracts and essential oils from Wisteria sinensis flowers. The essential oil was obtained by steam distillation of the
Wisteria sinensis flowers collected in Poland with use of the Deryng apparatus. The
extracts were prepared by maceration both fresh and dried flowers using methanol,
chloroform and n-hexane as solvents. Samples were analyzed with use gas chromatograph with a mass selective detector. The compounds were identified using a NIST
02 mass spectral library and the programmed temperature retention indexes were also
determined. A preliminary analysis by GC/MS lead to characterize the essential oil
and extracts of Wisteria sinensis flowers. Methyl or ethyl esters of fatty acids such
as 14-methylpentadecanoic, hexadecanoic, octadecanoic, 9,12,15-octadecatrienoic and
linoleic acid as well as 9-octadecenamide and aliphatic hydrocarbons such as heptacosane, eicosane were identified as the main components. Eugenol, 6,10,14-trimethyl2-pentadecanon and phytosterols were also detected.
Figure 1. Wisteria sinensis
[1]
T. Konoshima, M. Takasaki, M. Kozuka, H. Tokuda, H. Nishino, E. Matsuda, M. Ngai, Biol
Pharm Bull, 1997, 20(8), 865-868.
[2]
M.A. Mohamed, M.M. Hamed, A.M. Abdou, W.S. Ahmed , A.M. Saad, Molecules, 2011, 16(5),
4020-4030.
[3]
D. Joulain, R. Tabaccchi, Phytochemistry, 1994, 37(6), 1769-1770.
Poster 132
Saturday 9:00 - 11:30
189
SPE-HPLC Online Coupling for the Determination of
Zearalenone in Edible Oil: First Results
Drzymala Sarah ∗ , Marten Silvia† , Stefan Risch† , Matthias Koch∗
Department 1 – Federal Institute for Materials Research and Testing –
Richard-Willstätter-Str. 11 – Berlin – GER
†
Department "Applications and Columns" –
Wissenschaftlicher Gerätebau, Dr. Ing. Herbert Knauer GmbH – Hegauer Weg 38 –
Berlin – GER
∗
[email protected]
Zearalenone (ZEN) is a non-steroidal hyperestrogenic mycotoxin that contaminates
different crops worldwide. Due to its lipophilic nature it is often found in edible oil
derived from contaminated material. The dilemma of seperating an apolar analyte
from an apolar matrix either leads to a lack of specifity or very laborious, cost intensive
techniques. Thus, the extraction and clean-up of ZEN from edible oil has long been
termed problematic.
In 2010, Siegel et al.[1] proposed a highly specific one-pot sample preparation technique. Carbonyl compounds as ZEN can be covalently bound to hydrazine functionalized polymer particles. After the clean-up process ZEN is cleaved from the polymer
and quantified by HPLC with fluorescence detection.
The aim of this work was to find out if a covalent SPE approach is suitable for
online-coupling to HPLC.
Seven different resins, polymer and silica based, were tested for their suitability. One
silica and one polymer resin were found to have superior kinetic properties and were
chosen for SPE cartridge fillings. First results regarding the technical setup, recovery
and reusability rates are presented. This is the first work to explore whether a SPE
based on covalent interaction has the potential to be coupled to HPLC.
[1]
D. Siegel, K. Andrae, M. Proske, C. Kochan, M. Koch, M. Weber,I. Nehls, “Dynamic covalent
hydrazine chemistry as a selective extraction and cleanup technique for the quantification of the
Fusarium mycotoxin zearalenone in edible oils.” J.Chromatogr. A 2010, 1217 (15), 2206-2215.
190
Saturday 9:00 - 11:30
Poster 133
Synthesis, characterization and sensory property of
magnesium porphyrazine possessing
methyl(2-thienylmethyl)amino substituents in the periphery
Wojciech Szczolko ∗ , Jacek Kujawski† , Zbigniew Dutkiewicz∗ , Marek Bernard† ,
Tomasz Goslinski∗
∗
†
Department of Organic Chemistry – Poznan University of Medical Sciences –
Grunwaldzka 6 – Poznan – POL
[email protected]
INTRODUCTION Peripherally functionalized porphyrazines (Pzs) 1 are isoelectronic
with porphyrins, but in comparison possess substantially different electronic properties. The first possibility to modify Pz is to substitute the core with metal entities
(M), while the second one is connected with peripheral modifications (Figure). Pzs
substituted in the periphery have many potential applications as photosensitizers
in photodynamic therapy, sensors, molecular semiconductors and non-linear optical
materials.[1]
RESULTS Maleonitrile (3) was synthesized according to the two approaches (Figure). In the first approach double-reductive alkylation of diaminomaleonitrile (2)
was employed to yield 2,3-bis[(2-thienylmethyl)amino]-2(Z)-butene-1,4-dinitrile (3)
following a method elaborated by the Sheppard[2] and Barrett-Hoffman[3] teams. In
second approach maleonitrile 3 was synthesized in a one-step procedure using 5-ethyl2-methylpyridine borane complex and acetic acid in methanol.[1] Alkylation reaction
of 3 with dimethyl sulfate in THF led to the novel maleonitrile (4) which was subsequently used in Linstead macrocyclization reaction towards symmetrical porphyrazine
(5). Peripheral metallation study of Pz 5 with PdCl2 (PhCN)2 in the UV-Vis and
NMR are ongoing. Experimental results will be compared with the theoretical calculations (Gaussian G09 suite code). The structures of the different Pz 5 conformers with
PdCl2 have been optimized according to the density functional theory at B3LYP/631G(d,p) level, including PCM solvation model. Moreover, the related calculations
will be compared to the experimental NMR spectra and analyzed using (i) IGLOII
basis for H, C, N, O, S atoms, (ii) standard base cc-pVTZ for magnesium cation, and
(iii) LANL2DZ ECP for palladium salt.[5,6]
Figure
[1]
M. S. Rodriguez-Morgade, P. A. Stuzhin, J. Porphyr. Phthalocya. 2004, 8, 1129.
R. W. Begland, D. R. Hartter, F. N. Jones, D. J. Sam, W. A. Sheppard, O. W. Webster, F. J.
Weigert, J. Org. Chem. 1974, 39, 2341.
[3]
L. S. Beall, N. S. Mani, A. J. P. White, D. J. Williams, A. G. M. Barrett, B. M. Hoffman, J.
Org. Chem. 1998, 63, 5806.
[4]
E. R. Burkhardt, B. M. Coleridge, Tetrahedron Lett. 2008, 49, 5152.
[5]
J. Kujawski, M. Doskocz, H. Popielarska, A. Myka, J. Kruk, M. K. Bernard, Polyhedron 2013,
submitted.
[6]
P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270.
[2]
Wojciech Szczołko and Jacek Kujawski are scholarship holders within the project “Scholarship
support for PH.D. students specializing in majors strategic for Wielkopolska’s development”, Submeasure 8.2.2 Human Capital Operational Programme, co-financed by European Union under the
European Social Fund. The authors acknowledge financial support for the project from the Polish
Ministry of Science and Higher Education (N N405 356339).
Poster 134
Saturday 9:00 - 11:30
191
Synthesis of N-substituted
3,4-dihydropyrimidine-2(1H )-thiones via regioselective
additions of organolithiums to pyrimidine-2(1H )-thiones
Łukasz Struk , Jacek G. Sośnicki
Institute of Chemistry and Environmental Protection –
West Pomeranian University of Technology, Szczecin – Piastów Avenue 42 – Szczecin –
POL
[email protected]
In the last twenty years 3,4-dihydropyrimidine-2(1H )-thiones were recognized as valuable pharmacophores, which show a wide range of pharmalogical activity.[1] A large
majority of 3,4-dihydropyrimidine-2(1H )-thione derivatives were synthesized according to three-component protocol developed by Biginelli in 1893 (Scheme 1). To the
present, a number of improvements have been introduced in order to enhance the efficiency of this reaction.[2,3] As the result of the last attempts N-substituted derivatives
were obtained starting from N-substituted thiourea.[4] However, despite of the vast
derivatization opportunities, Biginelli reaction suffers from the lack of the attachment
of the optional substituent at C-5 and lead mainly to the derivatives with carbonyl
groups bonded to this carbon atom. Recently, we have demonstrated a new synthetic
approach to C-4 substituted, NH 3,4-dihydropyrimidine-2(1H )-thiones via addition of
organolithiums to commercially available NH pyrimidine 2(1H )-thione.[5] Following
this strategy we present now the preliminary results of the synthesis of 4-alkil(aryl),
5-(H)aryl N-substituted 3,4-dihydropyrimidine-2(1H )-thiones (2). The efficiency and
the regioselectivity of the addition of organolithium reagents are discussed. Besides,
the synthesis of new 5-aryl N-substituted pyrimidine 2(1H )-thiones (1) is presented.
Acknowledgment
Financial support by the National Science Center (N N204 219640) is gratefully
acknowledged
[1]
J.-P. Wan, Y. Pan, Mini-Rev. Med. Chem. 2012, 12, 337.
Suresh, J.S. Sandhu, ARKIVOC 2012, 1, 66.
C. O. Kappe, Acc. Chem. Res. 2000, 33, 879.
[4]
H. Comas, D.-A. Buisson, R. Najman, F. Kozielski, B. Rousseau, R. Lopez. Synlett 2009,
1737.
[5]
J.G. Sośnicki, Phosphorus, Sulfur, Silicon Relat. Elem. 2009, 184, 1946.
[2]
[3]
192
Saturday 9:00 - 11:30
Poster 135
Synthesis of Highly Luminescent Zinc Containing Indium
Phosphide Nanoparticles
Gordon M. Stachowski, Stephen G. Hickey, Alexander Eychmüller
Physikalische Chemie/ Elektrochemie – Technische Universität Dresden –
Bergstraße 66b – 01069 Dresden – GER
[email protected]
Progress in the field of semiconductor quantum dots has been driven mainly by research into cadmium chalcogenides. As a result these materials are presently among
the most investigated colloidal quantum dots and can be synthesized to possess high
emission quantum yields across the visible spectral region. Unfortunately, with regard
to bio-applications, the toxicity aspects argue against the use of cadmium containing quantum dots. However, the more biocompatible material indium phosphide can
be synthesized such that it covers almost the same spectral range as the cadmium
chalcogenides.
In this work we present the synthesis and characterization of highly emitting indium
phosphide quantum dots with a distinct amount of zinc. The emission color of the
as-formed material spans the visible spectrum from blue-green to red. A one-pot hot
injection dehalosilylation synthesis method has been combined with a well-controlled
temperature program to modify the reaction rate. The as-prepared quantum dots
possess high quantum yields without the further requirement for a passivating shell.
Furthermore the amount of zinc incorporated in the quantum dots has been investigated using ICP/OES and XPS. We have observed a relationship between the amount
of zinc and the higher quantum yields as well as a shift of the emission profile to higher
energies.
Poster 136
Saturday 9:00 - 11:30
193
Five-membered, N-heterocyclic Ligands in Organometallic
and Coordination Chemistry
Markus Kreye ∗ , Andreas Glöckner∗ , Constantin Daniliuc∗ , Matthias Freytag∗ ,
Peter G. Jones∗ , Matthias Tamm∗ , Marc D. Walter∗
∗
Chemie – Institut für Anorganische und Analytische Chemie, TU Braunschweig –
Hagenring 30 – 38106 Braunschweig – GER
†
Chemie – Organisch-Chemisches Institut, WWU Münster – Corrensstr. 40 –
48149 Münster – GER
[email protected]
In contrast to the well-developed chemistry of cyclopentadienyl ligands (Cp) and
their complexes, the coordination chemistry of the related N-heterocyclic ligands is
underdeveloped. First reported by Kuhn in 1991, the sterically demanding 2,5-ditert-butyl-pyrrolyl (PyrtBu2 ) was found to react as a Cp-analogue and to bind in a
eta5 -fashion forming diaza-metallocenes of Fe, Co, Ni, Sn and Pb.[1]
We have recently begun to explore the coordination and reaction chemistry of sterically demanding pyrrolyl and imidazolyl ligands with transition metals.[2] In this context the possibility to switch between different coordination modes was established
with Cr(II) and Mn(II) centers. These and other results will be presented.
[1]
a.) N. Kuhn, K. Jendral, R. Boese, D. Bläser, Chem. Ber. 1991, 124, 89-91; b.) N. Kuhn,
M. Köckerling, S. Stubenrauch, D. Bläser, R. Boese, J. Chem. Soc., Chem. Commun. 1991,
1368-1370; c.) N. Kuhn, G. Henkel, J. Kreutzberg, S. Stubenrauch, J. Organomet. Chem. 1993,
456, 97-106; d.) N. Kuhn, G. Henkel, S. Stubenrauch, J. Chem. Soc., Chem. Commun. 1992,
760; e.) N. Kuhn, G. Henkel, S. Stubenrauch, Angew. Chem. 1992, 104, 766-768.
[2]
M. Kreye, A. Glöckner, C. G. Daniliuc, M. Freytag, P. G. Jones, M. Tamm, M. D. Walter,
Dalton Trans. 2013, 42, DOI: 10.1039/c2dt32433d.
194
Saturday 9:00 - 11:30
Poster 137
SiO6 containing Silicophosphates - Syntheses at Room
Temperature
Sandra Jähnigen ∗ , Erica Brendler† , Uwe Böhme∗ , Edwin Kroke∗
Institut für Anorganische Chemie – TU Bergakademie Freiberg – Leipziger Straße 29 –
Freiberg – GER
†
Institut für Analytische Chemie – TU Bergakademie Freiberg – Leipziger Straße 29 –
Freiberg – GER
∗
[email protected]
In nature, only a few silicates are known where silicon is coordinated with six oxygen
atoms, e.g. stishovite.[1,2] Most of them are formed at high-pressure. Silicophosphates
also contain SiO6 octahedra but the main difference lies in their formation at normal
pressure. Examples for it are SiP2 O7 [3] and Si5 P6 O25 [4] phases. However, their
syntheses still require high temperatures or the addition of alkali or alkaline earth
halides.
Recently[5,6] we developed a novel synthesis of silicophosphates starting from anhydrous H3 PO4 . We also investigated one of the products by single crystal X-ray
structure analysis (Fig. 1). In addition to established but parameter dependend reactions at high temperatures or sol-gel-techniques, we were now able to synthesize
silicophosphates at room temperature and normal pressure.
Fig. 1 SiV I (PO4 )6 (SiIV O4 Et2 )6 -Ion5 with SiO6 located in the center of the
complex.
[1]
S.M. Stishov, S.V. Popova, Geokhimiya 1961, 837.
E.C.T. Chao, J.J. Fahey, J. Littler, J. Geophys. Res. 1962, 67, 419.
E. Tillmanns, W. Gebert, W.H. Baur, J. Solid State Chem. 1973, 7, 69.; G. Bissert, F.
Liebau, Acta Cryst. 1970, B26, 233.; F. Liebau, K.F. Hesse, Z.Kristallogr. 1971, 133, 213.
[4]
H. Mayer, Monatsh. Chem. 1974, 105, 46.
[5]
S. Jähnigen, E. Brendler, U. Böhme, E. Kroke, Chem. Commun. 2012, 48, 7675.
[6]
S. Jähnigen, U. Böhme, E. Brendler, G. Heide, E. Kroke, “Silikat-Phosphat-Materialien (SiOPs)
- Verfahren zu deren Herstellung und Anwendungen”, Deutsche Patentanmeldung 10 2012 011
034.0, Anmeldetag 05.06.2012.
[2]
[3]
Poster 138
Saturday 9:00 - 11:30
195
Synthesis of benzo[1,4]oxazin-3-one derivatives with potential
biological activity
Małgorzata Śmist, Michalina Adaszyńska, Halina Kwiecień
West Pomeranian University of Technology, Szczecin – Al. Piastów 42 – Szczecin – POL
[email protected]
The benzo[1,4]oxazine scaffold is an interesting structural unit which occurs in a large
number of biologically active natural and synthetic compounds. Some of them were
found to be antibacterial and antifungal agents. For example, ofloxacin[1] is a drug
active against Gramnegative bacteria, while the analogues of fluconazole were found
to be a novel class of antifungal agents active against Candida albicans.[2] Moreover,
natural derivatives of benzo[1,4]oxazine were found to be plant allelochemicals, wellknown for their phytotoxic activity and for taking part in the defense strategies of
Gramineae, Ranunculaceae, and Scrophulariceae plants.[3]
The aim of our research was to obtain novel halo-substituted benzo[1,4]oxazin-3ones as the compounds with potential antifungal and pharmacological properties.
The synthesis starts from 2-nitrophenols (1) and methyl 2-bromoalkanoates (2) and
proceeds by reductive cyclization of methyl 2-(2-nitrophenoxy)alkanoates (3) to give
the desired benzo[1,4]oxazepin-3-ones (4). The dibromo derivatives (6) were finally
obtained by further bromination of unsubstituted 2-alkylbenzo[1,4]oxazin-3-ones (5).
According to our expectations some of the products exhibited antifungal activity (in
vitro tests).
Scheme 1.
[1]
A. Kleeman, J. Engel, Pharmaceutical substances, Thieme, Stuttgart-New York, 4th Edition,
2001.
[2]
H. B. Borate, S. R. Maujan, S. P. Sawargave, M. A. Chandavarkar, S. R. Vaiude, V. A. Joshi,
R. D. Wakharkar, R. Iyer, R. G. Kelkar, S. P. Chavan, S. S. Kunte, Bioorg. Med. Chem. 2010,
20, 722-725.
[3]
H. M. Niemeyer, J. Agric. Food Chem. 2009, 57, 1677-1696.
196
Saturday 9:00 - 11:30
Poster 139
Synthetic applications of
3-alcoxycarbonyl-4-alkynylcoumarins
Amparo Sanz-Marco, Gonzalo Blay, José Ramón Pedro
Química Orgánica – Universitat de València – Dr. Moliner no 50 – Burjassot – ESP
[email protected]
The 3,4-dihydrocoumarin ring system constitutes the core of many natural products
and biologically active compounds.[1] In this context, we have described the enantioselective synthesis of 4-substituted dihydrocoumarins through a new Zn-bis(hydroxyamide)-catalyzed conjugate addition of terminal alkynes. Because of the synthetic versatility of the triple bond compounds like 1 can be used as building blocks in organic
synthesis.
In this communication, we describe this synthetic potential by carrying out different transformations involving the coumarin skeleton and/or the triple bond. Thus,
the triple bond can be totally or partially hydrogenated to give C -4 alkylated 2 or
alkenylated 3 dihydrocoumarins, respectively. On the other hand, hydrogenation and
descarboxylation, followed by reduction of the lactone and Mitsunobu reaction give
alkynylated chromane 4 used in the synthesis of others chromanes with antihypertensive activity.[2] Besides, by gold-catalyzed cyclization leads to fused acetal 5 having
the tetrahydrofuro[2,3-b]benzofuran skeleton characteristic of fungal metabolite aflatoxins and other natural products.[3] All these synthetic transformations are carried
out with excellent yields and without loss of optical purity.
Financial support from the Ministerio de Ciencia e Innovación and FEDER (CTQ200913083) and from Generalitat Valenciana (ACOMP/2012/212 and ISIC/2012/001) is acknowledged. A S-M thanks the MICINN for a pre-doctoral grant (FPI).
[1]
a) F. Roelens, K. Huvaere, W. Dhooge, M. Van Cleemput, F. Comhaire, D. de Keukeleire, Eur.
J. Med. Chem. 2005, 40, 1042; b) A. Kumar, B. K. Singh, R. Tyagi, S. K. Jain, S. K. Sharma,
A. K. Prasad, H. G. Raj, R. C. Rastogi, A. C. Watterson, V. S. Parmar, Bioorg. Med. Chem.
2005, 13, 4300.
[2]
a) E. Tyrell, K. Mazloumi, D. Banti, P. Sajdak, A. Sinclair, A. Le Gresley, Tetrahedron Lett.
2012, 53, 4280; b) E. Tyrrell, K.-H. Tesfa, I. Greenwood, A. Mann, Bioorg. Med. Chem. Lett.
2008, 18, 1237.
[3]
S. Bakirdere, S. Bora, E. G. Bakirderel, F. Aydin, Y. Arslan, O. T. Komesli, I. Aydin, E.
Yildirim, Centr. Eur. J. Chem. 2012, 10, 875.
Poster 140
Saturday 9:00 - 11:30
197
Diversity oriented synthesis in the row of 4-Quinalones
Mariia Miliutina, Anton Ivanov, Peter Langer, Viktor O. Iaroshenko
Organic chemistry – University of Rostock – Albert Einstein str. 3a – 18059-Rostock –
GER
[email protected]
Wide application of quinolones in plenty of medicinal spheres motivates to go further
in search for new efficient and rapid approaches to synthesis of differently substituted
representatives of this structural type.[1-3]
Herewith we present convenient method for synthesis of 4-quinolones via [5+1] cyclization of o-chloroaryl acetylene ketones 3 and primary amines 4 (Scheme 1). Starting
from 2-chloro-5-nitro-benzoic acid chloranhydride 1 and varying appropriate acetylenes
2 and amines 4 on the step of cyclization we afforded a row of differently substituted
4-quinolones with yields from good to excellent.
Besides we showed 4-quinolones as a substrate for further functionalizations. Among
them are bromination, arylation by Susuki-Miaura cross-coupling reaction and introduction of trifluoromethyl group instead of bromine in third position of the 4quinolone skeleton as well as reduction of nitrogroup to aminogroup, change of the
latter to bromine with subsequent arylation towards sixth position of the molecule.
Novel polysubstituted compounds 5 and 6 obtained by the mentioned methods are
of considerable interest as potentially bioactive agents.
Scheme 1. Reagents and conditions: (i) 0.01 eq. Pd(PPh3 )2 Cl2 , 0.02 eq. CuI, THF,
1.3 eq. Et3 N, 1.3 eq. of appropriate acetylene, r.t., 6 h; (ii) 1.7 eq. of appropriate amine,
2 eq. K2 CO3 or K3 PO4 , DMF, 120◦ C, 6 h.
[1]
L. A. Mitscher, Chem. Rev. 2005, 105, 559-592.
Cl. Mugnaini, Ch. Falciani, M. d. Rosa, A. Brizzi, S. Pasquini, F. Corelli, Tetrahedron 2011,
67, 5776-5783.
[3]
V. O. Iaroshenko, I. Knepper, M. Zahid, R. Kuzora, S. Dudkin, A. Villinger, P. Langer, Org.
Biomol. Chem. 2012, 10, 2955-2959.
[2]
198
Saturday 9:00 - 11:30
Poster 141
Studies Towards the Total Synthesis of Glyceollines
Marcus Blümel, Susann Baier, Peter Metz
Fachrichtung Chemie und Lebensmittelchemie – University of Techology Dresden –
Bergstraße 66 – 01062 Dresden – GER
[email protected]
The glyceollins, as a subgroup of isoflavonoids, belong to the naturally anabolized
polyphenols. In case of fungal, viral, or bacterial attack these phytoalexins are formed
and act as anti-microbial agents.[1] For the reason of their structural similarity to human hormones, such as 17β-estradiol (E2 ), the isoflavonoids in general and glyceollins
in particular are able to interact with the human hormone balance. Thus, a broad
spectrum of applications results in order to treat diseases associated with unbalanced
hormone level, such as breast cancer, atherosclerosis, and osteoporosis.[2,3,4] Consequently, these glyceollins have attracted much attention in the past decades.
The first total synthesis of racemic as well as (+)-, and (-)-glyceollin was published
by Erhardt and coworkers in 2008 and recently scaled up to multigram-scale. As
key step a Sharpless oxidation with stoichiometric amounts of OsO4 was used.[5,6]
For our approach toward the glyceollin total synthesis we used a gold catalyzed cyclization. Coupling of two fragments derived from commercially available 4-bromo resorcinol 4 is supposed to yield our key intermediate, the orthogonal protected isoflavene 5.
A catalytic epoxidation of the central double-bond of isoflavene 5 should open access
to an enantioselective route without using great amounts of toxic OsO4 . Previous research in our group suggests a successful synthesis of (-)-glyceollins if the enantiopure
epoxide intermediate is gained.
[1]
T. Aoki, T. Akashi, S.-I. Ayabe, J. Plant Res. 2000, 113, 475-488.
V. A. Salvo, S. M. Boue, J. P. Fonseca, Clin. Cancer Res. 2006, 12, 7159-7164.
E. W. Raines, R. Ross, J. Nutr. 1995, 125, S624-S630.
[4]
T. Usui, Endocrine Journal 2006, 53, 7-20.
[5]
R. S. Khupse, P. W. Erhardt, Org. Lett. 2008, 10, 5007-5010.
[6]
A. Luniwal, R. Khupse, M. Reese, J. Liu, M. El-Dakdouki, N. Malik, L. Fang, P. Erhardt,
Org. Process Res. Dev. 2011, 15, 1149-1162.
[2]
[3]
Poster 142
Saturday 9:00 - 11:30
199
Design, synthesis and transformation of some
heteroannulated 3-aminopyridines-purine isosteres with
exocyclic nitrogen atom
Qnar Araqelyan, Ashot Gevorgyan, Satenik Mkrtchyan, Marcelo Vilches-Herrera,
Dmitro Ostrovskyi, Muhammad S.A. Abbasi, Linda Supe, Ani Hakobyan,
Viktor Iaroshenko
Faculty of Chemistry – University Rostock – Albert Einstein str. 3a, 18059 Rostock –
Rostock – GER
[email protected]
Purines and purine-like scaffolds are compounds with extensive application portfolio
in the life science and medicine sector. The substances from the purine/pseudopurine
family have been having a significant impact on drug design and drug-development.[1]
Recently, laboratory of Iaroshenko have published a number of methods related to
the synthesis of various heterocycle condensed pyridine/pyrimidine derivatives via
the [3+3] heteroannulation reaction of pyridine/pyrimidine moiety on the core of
electron-rich aminoheterocycles and anilines involving set of 1,3-CCC- and 1,3-CNCdielectrophiles.[2] Continuing this research synthesis of 1-deazapurines and isosteres
bearing the exocyclic nitrogen atom at position-3 was developed basing on the formal
[3+3]-cyclization reaction of nitro-malonaldehyde with the set of electron-rich aminoheterocycles (Figure 1). Through the functionalization of the purine-like scaffolds
synthesized the diversity of compounds furnished in the possition-3 with aryl, alkinyl,
and vinyl rests, were obtained (Figure 1).[3]
Figure 1. Synthesis of 1-deazapurines and isosteres bearing the exocyclic nitrogen
[1]
a) W. B. Parker, Chem. Rev. 2009, 2880; b) P. G. Baraldi, M. A. Tabrizi, S. Gessi, P. A.
Borea, Chem. Rev. 2008, 238.
[2]
a) S. Mkrtchyan, V. O. Iaroshenko, S. Dudkin, A. Gevorgyan, M. Vilches-Herrera, G. Ghazaryan, D. Volochnyuk, D.Ostrovskyi, Z. Ahmed, A. Villinger, V.Y. Sosnovskikh, p. Langer, Org.
Biomol. Chem. 2010, 5280; b) V. O. Iaroshenko, S. Mkrtchyan, A. Gevorgyan, M. VilchesHerrera, D. V. Sevenard, A. Villinger, T. V. Ghochikyan, A. Saghiyan, V. Ya. Sosnovskikh, P.
Langer, Tetrahedron 2012, 2532.
[3]
V.O. Iaroshenko, M. Vilches-Herrera, A. Gevorgyan, S. Mkrtchyan, K. Arakelyan, D. Ostrovskyi, S. A. A. Muhammad, L. Supe, A. Hakobyan, A. Villinger, D.M. Volochnyuk, A. Tolmachev,
Tetrahedron 2013, in press, DOI: 10.1016/j.tet.2012.11.026.
200
Saturday 9:00 - 11:30
Poster 143
A Trispyrazolylborato Iron Cysteinato Complex as a
Functional Model for the Cysteine Dioxygenase
Madleen Sallmann, Christian Limberg
[email protected]
The cysteine dioxygenase (CDO) is a non-heme mononuclear iron enzyme that catalyzes the irreversible oxidation of cysteine by dioxygen to yield cysteine sulfinic acid,
which is the first major step in cysteine catabolism in mammalian tissues.[1] While
the function of many oxygenating non-heme iron enzymes could be successfully imitated within the last decades using molecular model compounds,[2] to date there are
hardly any reports in the literature on biomimetic models for the CDO.
Unlike other mononuclear non-heme iron dioxygenases, the active sites of which typically contain a 2-histidine-1-carboxylate coordination motive, the iron ion of CDO is
bound by three histidine ligands.[1] To this unit, the substrate cysteine coordinates
through the sulfur atom and the nitrogen atom as a chelating ligand.
Here we present the successful coordination and dioxygenation of a protected cysteinato ligand to a (His)3 FeII analogue (see Scheme):[3] In complex [TpM e,P h FeCysOEt],
the TpM e,P h ligand excellently mimics the (His)3 -coordination sphere and also the
function is simulated, as treatment with dioxygen mainly leads to cysteine sulfinic
acid. 1 is thus the hitherto most realistic model for the active site of the CDO.
[1]
C. A. Joseph, M. J. Maroney, Chem. Commun. 2007, 3338-3349.
a) M. Costas, M. P. Mehn, M. P. Jensen, L. Que, Jr., Chem. Rev. 2004, 104, 939-986; b) W.
Nam, Acc. Chem. Res. 2007, 40, 465-465; c) I. Siewert, C. Limberg, Chem. Eur. J. 2009, 15,
10316-10328; d) S. Friedle, E. Reisner, S. J. Lippard, Chem. Soc. Rev. 2010, 39, 2768-2779.
[3]
M. Sallmann, I. Siewert, L. Fohlmeister, C. Limberg, C. Knispel, Angew. Chem. Int. Ed.
2012, 51, 2234-2237.
[2]
Poster 144
Saturday 9:00 - 11:30
201
Cell culture analysis of selectin-binding bioactive
nanoparticles
Isabella Tavernaro ∗ , Katja Trinkaus† , Léa Bouche‡ , Figen Beceren-Braun ,
Jens Dernedde , Hans-Ulrich Reissig‡ , Katrin Susanne Lips† , Sabine Schlecht∗
∗
Institue of Inorganic and Analytical Chemistry – Justus Liebig University Giessen –
Heinrich-Buff-Ring 58 – 35392 Giessen – GER
†
Laboratory of Experimental Trauma Surgery – Justus Liebig University Giessen –
Kerkrader Str. 9 – 35394 Giessen – GER
‡
Institute of Organic Chemistry – FU Berlin – Takustr. 3 – 14195 Berlin – GER
Institute of Laboratory Medicine, Clinical Chemistry and Pathobiochemistry –
Charité Berlin – Hindenburgdamm 30 – 12203 Berlin – GER
[email protected]
Interest in nanoparticles and their possible use in medical applications has significantly
increased in recent years. Although still at the beginning of its development, first
successful results indicate the great potential of this research area.
Some ligands tend to bind only weakly to their complementary receptors in biological
systems. Stronger binding or enhanced inhibition can be achieved by the use of
multivalent interactions.[1] Due to their remarkably high surface-to-volume ratio in
combination with their high stability, nanoparticles are well suited as templates for
the multivalent presentation of functional groups. Because of this, they are used in
this project for the immobilization of potential selectin-inhibitors. Selectins are a
natural class of carbohydrate binders, and play an essential role in the inflammation
process.
We synthesized water-soluble and biocompatible nanoparticles of different sizes with a
terminally functionalized organic thiol shell, to present multivalently selectin ligands
to the respective lectins. This multivalent presentation of selectin-binding structures
led to highly improved binding properties compared to the monovalent structures.[2]
Tests were conducted to investigate the behavior of the functionalized nanoparticles
in cell cultures.
[1]
[2]
G. M. Whitesides et al. Angew. Chem. 1998, 110, 2908-2953.
M. Roskamp et al. Org Biomol. Chem. 2011, 9, 7448-7456.
202
Saturday 9:00 - 11:30
Poster 145
A new approach to α-(trifluoromethyl)benzyl substituted
oxaziridines
Greta Utecht, Emilia Obijalska, Grzegorz Mlostoń
Organic and Applied Chemistry – University of Lodz, Faculty of Chemistry –
Tamka 12 – Lodz – POL
[email protected]
The chemistry of organofluorine compounds is intensively developed part of modern
organic chemistry. Insertion of fluorine atoms to the molecules causes significant
changes in their chemical, biological and physical properties, in comparison with
their nonfluorinated analogues.[1,2] Perfluorinated oxaziridines were used as powerful
oxidation agents.[3]
The synthesis of new, N -substituted oxaziridines 3,4 bearing an α-(trifluromethyl)benzyl substituent at C(3) was achieved by m-CPBA oxidation of the corresponding α-hydroxy-α-(trifluoromethyl)benzyl imines 1,2 and their trimethylsilyl protected
derivatives, respectively. In all cases, mixtures of diastereoisomers were formed. Resulting compounds 3,4 were used in the model reaction of oxidation of tioanisole to
mono-S -oxide.
R1 =Ph, p-MeOC6 H4 , p-NO2 C6 H4 R2 =t-Bu, i-Pr
[1]
P. Kirsh, Modern Fluoroorganic Chemistry, Wiley-VCH, Weinheim, Germany, 2004.
[2]
L. Carroccia, S. Fioravanti, L. Pellacani, C. Sadun, P.A. Tardella, Tetrahedron 2011, 67,
5375-5381.
[3]
V.A. Petrov, G. Resnati, Chemical Reviews 1996, 96 (5), 1809-1823.
Authors thank the National Science Center (Poland) for financial support (Grant ‘SONATA’ #
DEC-2011/03/D/ST5/05231)
Poster 146
Saturday 9:00 - 11:30
203
Cisplatin–COX Inhibitor Conjugates
Wilma Neumann, Evamarie Hey-Hawkins
Institute of Inorganic Chemistry – Universität Leipzig – Johannisallee 29 –
04103 Leipzig – GER
[email protected]
Cisplatin is one of the most widely used drugs in the treatment of cancer. However, conventional platinum-based chemotherapy is often associated with strong side
effects, and the efficacy of anti-tumour drugs is strongly limited by intrinsic and
treatment-induced resistance of tumour cells. An enzyme which is overexpressed in
several tumour tissues and is involved in tumour onset and progression is COX-2,
an isoform of cyclooxygenase (COX).[1] Clinical studies revealed that targeting the
COX-2 pathway is a promising strategy for the prevention and treatment of tumours.
Furthermore, promising results were obtained with combinatorial treatments with
chemotherapeutic agents, such as cisplatin, and COX inhibitors.[2]
These observed synergistic effects could be improved by combining both molecules in
one compound. A covalent bond between the chemotherapeutic agent and the COX
inhibitor should ensure a concerted transport of the drugs through the body and
uptake into tumour cells. Furthermore, binding of the coupled COX inhibitor at COX2 could prevent an efflux of the platinum complex. Besides an increased accumulation
of the drugs in the tumour cells, coupling of cisplatin with COX inhibitors could
further enhance the efficacy of the chemotherapeutic agent by enabling a simultaneous
action of both drugs in COX-2 overexpressing tumour cells.
[1]
[2]
N. Ghosh, R. Chaki, V. Mandal, S. C. Mandal, Pharmacol. Rep. 2010, 62, 233-244.
M. Ogino, S. Minoura, Int. J. Clin. Oncol. 2001, 6, 84-89.
204
Saturday 9:00 - 11:30
Poster 147
Metal-Free Iodine(III)-Promoted Direct Intermolecular
C-H-Amination Reactions of Acetylenes
Peter Becker , José A. Souto, Álvaro Iglesias, Kilian Muñiz
ICIQ – Av. Països Catalans 16 – Tarragona – ESP
[email protected]
Ynamides represent a unique building block for organic synthesis and they have been
referred to as a modern functional group.[1,2] The synthesis of ynamides through
a direct CN bond forming process between amides and acetylenes is an attractive
method. This has been reported using copper in either stoichiometric or catalytic
amounts, however, more efficient metal-free processes are needed for the preparation
of ynamides.[3-5]
A particularly interesting preparation of ynamides was reported by Stang,[5] using hypervalent iodine(III) chemistry.[6] The reaction requires the formation of acetylenyl
iodonium(III) salts 1 and suitable nitrogen nucleophiles, usually in their metallated
form, which react in a Michael-type addition followed by aryl migration to form the
corresponding ynamide product.[7] This method suffers from limitations such as the
need to individually perform both metallated amides and acetylenyl iodonium(III)
salts 1.
Here, we present the development of an alternative, direct, metal-free oxidative C(sp1)N bond forming reaction using economically interesting terminal acetylenes and defined hypervalent iodine(III) reagents.[8] This method provides a simple, rapid and
robust protocol for the synthesis of a diverse series of ynamides in a single-step
operation.[9]
[1]
K. A. DeKorver, A. G. Lohse, R. Hayashi, Z. Lu, Y. Zhang, R. P. Hsung, Chem. Rev. 2010,
110, 5064.
[2]
For reviews see [1] and (a) G. Evano, A. Coste, K. Jouvin, Angew. Chem. Int. Ed. 2010,
49, 2840; (b) J. A. Mulder, K. C. M. Kurtz, R. P. Hsung, Synlett2003 , 1379; (c) C. A. Zificsak,
J. A. Mulder, R. P. Hsung, C. Rameshkumar, L.-L. Wei, Tetrahedron 2001, 57, 7575.
[3]
T. Hamada, X. Ye, S. S. Stahl, J. Am. Chem. Soc. 2008, 130, 833.
[4]
A. Laouiti, M. M. Rammah, M. B. Rammah, J. Marrot, F. Couty, G. Evano, Org. Lett. 2012,
14, 6.
[5]
(a) C. Zhang, N. Jiao, J. Am. Chem. Soc. 2010, 128, 28; (b) W. Jia, N. Jiao, Org. Lett.
2010, 12, 2000.
[6]
P. Murch, B. L. Williamson, P. J. Stang, Synthesis 1994, 1255.
[7]
For a review on the chemistry of hypervalent acetylenyl iodine(III) reagents see: V. V. Zhdankin,
P. J. Stang, Tetrahedron 1998, 54, 10927.
[8]
For chemistry of hypervalent iodine(III) reagents see: (a) V. V. Zhdankin, P. J. Stang, Chem.
Rev. 2008, 108, 5299; (b) V. V. Zhdankin, P. J. Stang, Chem. Rev. 2002, 102, 2523; (c) P. J.
Stang, V. V. Zhdankin, Chem. Rev. 1996, 96, 1123; (j) M. Ochiai, Chem. Rec. 2007, 7, 12; (l)
M. S. Yusubov, A. V. Maskaev, V. V. Zhdankin, Arkivoc 2011, 1, 370.
[9]
J. A. Souto, P. Becker, Á. Iglesias, K. Muñiz, J. Am. Chem. Soc. 2012, 134, 15505.
Poster 148
Saturday 9:00 - 11:30
205
Aminomethylphosphonic Systems Bearing 5-membered
Heteroaromatic Moiety and Their Properties
Agnieszka Matusiak ∗ , Jarosław Lewkowski∗ , Anna Agnieszka Klimczak† ,
Janusz Szemraj† , Piotr Rychter‡ , Robert Biczak‡
∗
Department of Organic Chemistry, Faculty of Chemistry – University of Lodz –
†
Department of Medicinal Biochemistry – Medical University of Lodz –
Mazowiecka 6/8 – Lodz – POL
‡
Environment Protection and Biotechnology – Jan Dlugosz University –
13/15 Armii Krajowej Av. – Czestochowa – POL
[email protected]
Several N -aryl substituted aminophosphonates have been synthesized since a last
decade[1,2] and our scientific group has contributed to this topic too.[3] Kraicheva et al.
have reported recently that diethyl N -4-methylphenylamino(2-furyl)methylphosphonate
showed in vitro action towards several tumor cell lines.[4] Therefore, we synthesized
several new N -aryl-substituted aminomethyl phosphonates derived from furanic series
in hope of their cytostatic activity.
Aminophosphonates 4e-g and imines 2a-f were analyzed in the viewpoint of influence
on cancer cell lines. For the experiments, KYSE 30, KYSE 150 and KYSE 270,
esophageal cancer cell lines were chosen and immortalized esophageal cell line HET 1
A was used as a control group. Toxicity was evaluated using the MTT assay. Among
our 12 aminophosphonates a few of them were found to be cytotoxic, but only 4a
had IC5 0 lower than 100 µM and acted as a potential cancer drug. SAR studies were
attempted.
In this communication, we will present results of these pharmacological studies.
Moreover some of the imines showed interesting biological properties. It demonstrated
significant phytotoxicity parameters for radish (Raphanus sativus) and oats (Avena)
after adding the appropriate amounts of imines to the soil.
Reactions of Schiff bases 2a–f with phosphites 3a–c.
[1]
X.-J. Mu, M.-Y. Lei, J.-P. Zou, W. Zhang, Tetrahedron Lett. 2006, 47, 1125-1127.
S. Chandrasekhar, S. Jaya Prakash, Tetrahedron Lett. 2001, 42, 5561-5563.
[3]
A. A. Klimczak, A. Kuropatwa, J. Lewkowski, Szemraj, J. Med. Chem. Res. 2012, 21, DOI
10.1007/s00044-012-0065-3.
[4]
I. Kraicheva, A. Bogomilova, I. Tsacheva, Europ. J. Med. Chem. 2009, 44, 3363-3367.
[2]
206
Saturday 9:00 - 11:30
Poster 149
Stereoselective Amine-Catalyzed Elongation of unprotected
Carbohydrates
Benjamin Voigt, Anastassia Matviitsuk, Rainer Mahrwald
Institute of Chemistry – Humboldt-University Berlin – Brook-Taylor-Str. 2 – Berlin –
GER
[email protected]
Chain elongated carbohydrates - higher carbon sugars - are important compounds
with biologically fundamental properties. Nature realizes these important transformations, apparently effortless, through a deployment of distinctly working aldolases
and ketolases with extremely high degrees of stereoselectivity. However this high
specificity is limited to a small number of substrates. Also, not all possible stereoisomers can be accessed by enzymatic transformations.
We have developed an organocatalyzed aldol addition of unprotected carbohydrates
to 1.3-dicarbonyl compounds without using the classical tedious protecting and deprotecting procedure. In addition condensation reaction and subsequently rearrangements are avoided following this protocol.
These investigations show great advantages in terms of time and atom economy. Also,
this operationally simple transformation mimics aldolase-catalyzed transformations,
which were identified in many biochemical processes. Further optimization and enlargement of this methodology to more general C-C bond formation processes of
unprotected carbohydrates are under way.
[1]
Benjamin Voigt, Ulf Scheffler, Rainer Mahrwald, Chem. Commun. 2012, 48, 5304-5306
Poster 150
Saturday 9:00 - 11:30
207
Unexpected transformation of diarylethenes induced by
secondary amines
Dmytro Sysoiev ∗ , Ulrich Groth∗ , Elke Scheer†
Chemistry – Konstanz University – Universitätsstr., 10 – Konstanz – GER
†
SFB 767 – Konstanz University – Universitätsstr., 10 – Konstanz – GER
∗
[email protected]
Diarylethenes can undergo a reversible transformation between two geometrically and
electronically different states by irradiation at different wavelengths. In general, the
"open" state is a mixture of rotamers, which turns into diastereomers in "closed"
state in UV light and forms by-products by further continuous irradiation. When
condensating malononitrile and difurylethene bearing an aldehyde group with piperidine as a catalyst, our attention was drawn to an unusual colour change of the reaction
mixture to deep purple. Successful isolation of reproducibly formed new product and
its structure analysis allowed us to suggest an irreversible cyclization pathway for
diarylethenes in absence of irradiation.
208
Saturday 9:00 - 11:30
Poster 151
Synthesis of a Tripodal Germanium Based Ligand Precursor
and its Reactivity at Ruthenium
Roy Herrmann, Thomas Braun
Institut für Chemie – Humboldt-Universität zu Berlin – Brook-Taylor-Straße 2 – Berlin –
GER
[email protected]
The design of podand-type ligand backbones often allows an elaborated adjustment
of their steric and electronic properties at the metal center to provide a high flexibility
and versatility at the ligand backbone. Examples for heavier group 14 elements in
the backbone of tetradentate tripodal ligands are rare, whereas tetradentate tripodal
ligands with group 13 and 15 elements as backbone atoms are well established.[1]
The reaction of the germane [Ge(H)(2-C6 H4 PPh2 )3 ] with [Ru(Cl)2 (PPh3 )3 ] in the
presence of an excess of NEt3 results in the formation of the ruthenium complex
[Ru(Cl)Ge(2-C6 H4 PPh2 )3 ] (1) (Scheme 1), which bears the Ge(2-C6 H4 PPh2 )3 entity
as a tetradentate tripodal ligand. The Ge-Ru bond length of complex 1 is at the
shorter end of Ge-Ru distances which are reported in the literature and the value
is comparable to the Ge-Ru distances in a couple of known ruthenium germylene
complexes.
Treatment of complex 1 with HCl results in a cleavage of one of the Ge-C bonds to
give the ruthenium complex [Ru(Cl)Ge(Cl)(2-C6 H4 PPh2 )2 (PPh3 )] (2) (Scheme 1).
Therefore, the podand-type ligand can be transformed into a pincer-type ligand. The
Ge(Cl)(2-C6 H4 PPh2 )2 unit represents a rare example for pincer-type ligands with
germanium in the backbone.
Scheme 1: Formation and reactivity of ruthenium complex 1.
[1]
I. Kuzu, I. Krummenacher, J. Meyer, F. Armbruster, F. Breher, Dalton Trans. 2008, 58365865.
Poster 152
Saturday 9:00 - 11:30
209
Approaches to synthesis of gold(III) carboxylate complexes
Nailya Akhmadullina ∗ , Aleksandra Borissova† , Oleg Shishilov‡
Baikov Institute of Metallurgy and Material Science of RAS – Leninsky pr., 49 –
Moscow – RUS
†
Nesmeyanov Institute of Organoelement Compounds of RAS – Vavilova st., 28 –
Moscow – RUS
Kurnakov Institute of General and Inorganic Chemistry of RAS – Leninsky pr., 31 –
Moscow – RUS
∗
‡
[email protected]
There are two general approaches to synthesis of carboxylate complexes. The first
one is reactions of binary carboxylates with different ligands. This approach is used
for all noble metals excluding gold, since gold binary carboxylates are very unstable
compounds which are extremely difficult to isolate. The second approach is a substitution of other acido ligands by carboxylate groups. This reaction works perfectly for
halide complexes if silver(I) carboxylate is used as a halide acceptor. The method is
applicable for both gold(I) and gold(III) compounds.
We tested different approaches to synthesis of gold(III) carboxylate complexes. First
we tried to prepare gold(III) acetates using reaction of chlorides [(L)AuCl2 ]Cl (L
= bipy and phen) with sodium acetate in glacial acetic acid at 80-100C. However,
it was found that for complex with phenanthroline the reaction leads to significant
rearrangement of gold coordination sphere and formation of [(phen)AuCl2 ][AuCl4 ]
complex instead of any carboxylate derivative.
Four-coordinated cationic gold(III) chloride complexes [(L)AuCl2 ]BF4 (L = bipy,
phen) react with silver(I) carboxylate RCO2 Ag (R = CH3 , CMe3 , CF3 ) in acetonitrile
media giving corresponding carboxylate derivatives [(L)Au(RCO2 )2 ]BF4 , which were
fully characterized including X-Ray diffraction study of [(bipy)Au(CF3 CO2 )2 ]BF4 .
At the same time pseudo five-coordinated gold(III) complexes LAuCl3 (where L =
2,9-dimethyl-1,10-phenanthroline and 2,2’-bisquinoline) do not form stable products
in the reaction, most likely, due to unfavourable steric features of the proposed carboxylate compounds. Finally, we carried out IR-spectroscopic studies for all the
prepared complexes in order to explain their stability and reactivity.
We are grateful to the Council of the President of the Russian Federation for young
scientists for financial support (project 977.2012.3).
Molecular structure of [(bipy)Au(CF3 CO2 )2 ]BF4
210
Saturday 9:00 - 11:30
Poster 153
Push-Pull Chromophores with Planarized Triphenylamine
Donors
Bettina Gliemann, Michael Grunst, Milan Kivala
Department of Chemistry and Pharamcy, Institute of Organic Chemistry I –
Friedrich-Alexander-Universität Erlangen-Nürnberg – Henkestrasse 42 – Erlangen – GER
[email protected]
About 40 years ago, Hellwinkel and co-workers realized planarized triphenylamine
scaffolds by connecting the three benzene rings of triphenylamine via carbonyl- or
dimethylmethylene-bridging units.[1] While numerous chromophores consisting of triphenylamine donors and various acceptors connected through a suitable π-conjugated
linker have already been investigated in organic light emitting diodes (OLEDs) and
dye-sensitized solar cells, such combinations involving the bridged triphenylamines as
donors have not been thoroughly investigated yet.[2]
Here, we report the synthesis and optoelectronic properties of a series of novel pushpull chromophores involving the planar triphenylamine donor decorated with various
electron acceptors (A).
Figure 1. Schematic set-up of synthesized push-pull chromophores.
[1]
a) D. Hellwinkel, M. Melan, Chem. Ber. 1971, 104, 1001-1016; b) Z. Fang, T.-L. Teo, L. Cai,
Y.-H. Lai, A. Samoc, M. Samoc, Org. Lett. 2009, 11, 1-4.
[2]
a) Z. Jiang, T. Ye, C. Yang, D. Yang, M. Zhu, C. Zhong, J. Qin, D. Ma, Chem. Mater. 2011,
23, 771-777; b) K. Do, D. Kim, N. Cho, S. Paek, K. Song, J. Ko, Org. Lett. 2012, 14, 222-225.
Poster 154
Saturday 9:00 - 11:30
211
Novel Metallasilatrane Complexes: Neutral Monomers and
Cationic Dimers
Gisela Warncke, Jörg Wagler
Inst. f. Anorg. Chem. – TU Bergakademie Freiberg – Leipziger Straße 29 –
09596 Freiberg – GER
[email protected]
The first metallasilatrane complexes, which are group 14 relatives of the nowadays
widely explored metallaboratrane compounds [1] , bear the interesting structural motif
of a dative TM→Si bond. The first representatives of these methimazole-buttressed
paddlewheel-shaped complexes (with TM = Ni2+ , Pd2+ , Pt2+ )[2] exhibited very poor
solubility in various solvents, which causes difficulties for characterization (e.g. NMR
spectroscopy) and potential applications (e.g. homogeneous catalysis) in solution.
Hence, their special molecular structures and 29 Si NMR spectroscopic properties were
established by crystal structure analyses, solid state NMR spectroscopy and quantum
chemical calculations.[3]
With the aid of bulkier substituents (such as t-butyl or 2,6-dimethylphenyl) at the
silatrane cage the solubility of metallasilatrane complexes was enhanced remarkably.
In addition to neutral monomeric molecules, upon replacement of the TM-bound
anion these compounds can form dimeric dications. The unexpected TM···TM contact of the latter is unbridged and can be rationalized by the spatial demand of the
substituent R1 .
[1]
M. Spicer, J. Reglinski Eur. J. Inorg. Chem. 2009, 1553.
a) J. Wagler, E. Brendler Angew. Chem. Int. Ed. 2010, 49, 624; b) J. Wagler, A. F. Hill, T.
Heine Eur. J. Inorg. Chem. 2008, 4225.
[3]
L. A. Truflandier, E. Brendler, J. Wagler, J. Autschbach Angew. Chem. Int. Ed. 2011, 50,
255.
[2]
212
Saturday 9:00 - 11:30
Poster 155
Conjugates of ruthenium(II)-polypyridyl complexes with
fluorene-based electron donors
Ralf Albrecht, Christoph Tzschucke
Department of Chemistry and Biochemistry – Freie Universität Berlin – Takustr. 3 –
[email protected]
Ruthenium(II)-polypyridyl complexes covalently attached to electron donor or electron acceptor units have been frequently used as model systems for light induced electron transfer and charge separation.[1] We describe the synthesis of electron donor conjugates of ruthenium(II)-polypyridyl complexes. As ligands, substituted bipyridines
were prepared by palladium-catalyzed direct arylation of pyridine N -oxides and subsequent reduction.[2]
As electron donor, 9,9-diarylfluorenes, with different redox potentials were prepared
and attached to the ruthenium(II) complex by an amide linkage. Correlation of the
redox potentials and the light induced charge separation behavior will be discussed.
Ruthenium(II)-polypyridyl complexe with fluorene-based electron donor.
[1]
D. Polyansky, D. Cabelli, J. T. Muckerman, E. Fujita, T. Koizumi, T. Fukushima, T. Wada, K.
Tanaka, Angew. Chem. Int. Ed. 2007, 46, 4169; C. Herrero, B. Lassalle-Kaiser, W. Leibl, A.
W. Rutherford, A. Aukauloo, Coord. Chem. Rev. 2008, 252, 456; A. Magnuson, M. Anderlund,
O. Johansson, P. Lindblad, R. Lomoth, T. Polivka, S. Ott, K. Stensjö, S. Styring, V. Sundström,
L. Hammarström, Acc. Chem. Res. 2009, 42, 1899.
[2]
S. Duric, C. C. Tzschucke, Org. Lett. 2011, 13, 2310.
Poster 156
Saturday 9:00 - 11:30
213
Photophysical, Photochemical and BQ Quenching Properties
of Zinc Phthalocyanines with Fused Extended Conjugation
Gulsah Gumrukcu ∗ , Gulnur Keser Karaoglan∗ , Ali Erdogmus∗ , Ahmet Gul† ,
Ulvi Avciata∗
∗
Chemistry – Technical University of Yildiz – Davutpasa / 34210 – Istanbul – TUR
†
Chemistry – Technical University of Istanbul – Maslak / 34469 – Istanbul – TUR
[email protected]
Metallophthalocyanines (MPcs) derivatives display interesting chemical and physical
properties, so they have been studied extensively.[1] The PDT properties of the phthalocyanine dyes are strongly influenced by the presence and nature of central metal
ion and substituents introduced on the periphery of the phthalocyanines. Metallation
of phthalocyanine with transition metals gives dyes with short lifetimes.[1]
The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II) phthalocyanines containing four Schiff’s base substituents attached directly on peripheral positions are reported. The group effects on pheripheral position and the continual conjugation of the phthalocyanine molecules on the
photophysical and photochemical properties are also investigated. General trends
are described for photodegradation, singlet oxygen and fluorescence quantum yields
of these compounds in dimethylsulfoxide (DMSO), dimethylformamide (DMF) and
tetrahydrofurane (THF). The fluorescence of the substituted zinc (II) phthalocyanine
complexes is effectively quenched by 1,4-benzoquinone (BQ) in the solvents used.
[1]
C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyanines, Properties and Applications, vols. 1–4,
VCH, New York, 1989, 1993, 1996.
[2]
H. Ali, J. E. van Lier, Chem. Rev. 1999, 99, 2379.
214
Saturday 9:00 - 11:30
Poster 157
The circular dichroism spectroscopy application for
determination of 2,2’-spirobi-1,3-benzodioxol derivates
absolute configuration.
Ewa Wrona, Mateusz Brela, Maria Owińska, Barbara Rys
Department of Organic Chemistry – Faculty of Chemistry, Jagiellonian University –
[email protected]
Circular dichroism is one of the methods for determination the spiranes absolute configuation, including 2,2‘-spirobi-(1,3-benzodioxoles) and 2,2’-spirobi-(1,3-benzodioxol4-carboxylic) acids, which obtained diastereoisomers, have been separated via fractional crystallization.
For each of the compounds, several circular dichroism spectra had been computed
(TD-DFT, B3LYP, 6-311G** ). In all cases two counter Cotton effects have been
noticed. The wave length for both the effects (c.a. 200nm) is different to the one
predicted (c.a. 230nm for π → π* benzoic acid transfer). Furthermore, an analysis
of atomic orbitals indicates, that the Cotton effects are not due to exciton coupling.
Nevertheless, the bands observed still follow the correlation between the Cotton effects
abundance and the chirality of molecule. Thus, having based on the circular dichroism spectroscopy as well as computational chemistry calculations the determination
of synthetized compounds absolute configuration was possible.
The CD spectra of (P)-2,2’-spirobi-(1,3-benzodioxol-4-carboxylic) acid
N,N’ -di-[(1S )-phenylethyl]amide; theoretical (left) and experimental (right)
[1]
J. Grochowski, M. Rutkowska, B. Rys, P. Serda, G. Snatzke, Chem. Ber. 1992, 125, 1837.
M. Clpas, N. Parinello, C. Saá, J.A. Varela, S. Caccamese, C. Rosini, Tetrahedron: Assymetry
2006, 17, 1387.
[3]
N. Harada, K. Nakanishi, Circular dichroic spectroscopy - exciton coupling in organic chemistry, Mill Valey, CA: University Science Books, 1983.
[2]
Poster 158
Saturday 9:00 - 11:30
215
Cycloadditions: Concerted vs Diradical Stepwise
Mechanisms. The Case of Nitrones Dimerization
David Roca-López , Tomás Tejero, Pedro Merino
Dpto. de Síntesis y Estructura de Biomoléculas –
Instituto de Síntesis Química y Catálisis Homogénea – Universidad de Zaragoza –
C/ Pedro Cerbuna, 12 – Zaragoza – ESP
[email protected]
The [3+2] cycloaddition reaction of olefinic dipolarophiles with 1,3-dipoles, such as
nitrile oxides or nitrones, is one of the best known and most widely used method for
constructing five-membered heterocycles.[1] Nitrile oxides easily dimerize to furoxans,
and the mechanism of the process has been already elucidated.[2] However, the analogous process with nitrones is a rarely reported event witnessed previously in few cases
for cyclic nitrones.
Recently, the cyclodimerization of several six-membered nitrones was investigated,[3]
but only configurational and conformational features of the dimers were studied, without shedding light on the mechanism, which remains in controversy. Especially, because the apparent dimerization process consists in an unfavored thermal [4π+4π]
cycloadition reaction, and no information exists to date about the electronic and
steric effects on dimerization of nitrones and the nature of the transition states for
such a process.
In this work, we report DFT studies (both open- and closed-shell) on the dimerization
of nitrones, first on a simple model and after on the 2,3,4,5-tetrahydropyridine-1-oxide,
using up to the PCM(dichloromethane)/M06–2X/cc–pVTZ level of calculation.
Concerted closed-shell mechanism (left) versus stepwise open-shell one (middle and right).
Acknowledgements:
D. R.-L. thanks the Spanish Ministry of Education (MED) for a FPU-Predoctoral grant.
The authors thank the computer resources from “Terminus” and technical assistance provided by
the Institute for Biocomputation and Physics of Complex Systems (BIFI) - University of Zaragoza
(UZ).
References:
[1]
Synthetic applications of 1,3-dipolar cycloaddition chemistry toward heterocycles and natural products. A. Padwa, W. H. Pearson (Eds.). John Wiley & sons: New York. 2002.
[2]
Z.-X. Yu, P. Caramella, K. N. Houk, J Org. Chem. 2003, 125, 15420-15425.
[3]
S. A. Ali, A. Alsbaiee, M. I. M. Wazeer, Phys. Org. Chem. 2010, 23, 488-496.
216
Saturday 9:00 - 11:30
Poster 159
1,8-Anthracene Bridged Ruthenium and Osmium Vinyl
Complexes as Possible Candidates for the Synthesis of
Anisotropic Supramolecular Rectangles
Daniel Fink , Evelyn Wuttke, Rainer Winter
Fachbereich Chemie – Universität Konstanz – Universitätsstr. 10 – Konstanz – GER
[email protected]
Discrete supramolecular objects featuring transition metal corners are in the focus
of current interest in the field of organometallic supramolecular chemistry. For the
preparation of rectangular shaped molecular objects 1,8-disubstituted anthracenes
are particularly suitable, because self-assembly of these molecular clips with bidentate bridging ligands such as bipyridines inevitably leads to the formation of the
desired structures. P. J. Stang and coworkers have already introduced these kinds
of supramolecular complexes in 2001[1] and a lot of further investigations have been
made ever since. The obtained structures mostly contain square planar Pt(II) or
Pd(II) metal centers. However, there is no known example for an anisotropic structure up to now, due to the fact that the required experimental procedures appear to
be far more challenging. Possible solutions might be the usage of partially protected
precursors or a combination of donor and acceptor molecules.
Herein we report the synthesis of two promising candidates as molecular acceptor clips for the formation of asymmetric supramolecular rectangles. The complex
[[RuCl(CO)(Pi Pr3 )2 ]2 (µ-CH=CH-anthracen-CH=CH-1,8)] was obtained by a hydrometallation reaction. It was possible to isolate the intermediate [Ru(CH=CH-anthracen-C≡CH-1,8)Cl(CO)(Pi Pr3 )2 ] thereby enabling the synthesis of the novel heterobimetallic complex [RuCl(CO)(Pi Pr3 )2 OsCl(CO)((Pi Pr3 )2 (µ-CH=CH-anthracenCH=CH-1,8)]. Despite the close structural similarity to a published complex[2] improved reversibilities of the redox processes are observed via cyclovoltammetric examinations, thus providing the possibility to perform spectroelectrochemical studies.
These point to sizable electronic coupling between the different metal sites in the
mixed-valent radical cations and, in agreement with the results EPR studies indicate
high ligand character of the corresponding SOMOs. Furthermore, the experimental
findings agree well with the results of accompanying DFT calculations.[3]
The vacant coordination sites located at the metal centers can be used to introduce
various donor functions leading to anisotropic molecular objects. Suitable donor clip
molecules have yet to be found and are in the focus of further studies.
[1]
C. J. Kuehl, S. D. Huang, P. J. Stang, Journal of the American Chemical Society 2001,
123, 9634-9641.
[2]
Y.-P. Ou, C. Jiang, D. Wu, J. Xia, J. Yin, S. Jin, G.-A. Yu, S. H. Liu, Organometallics 2011,
30, 5763-5770.
[3]
D. Fink Bachelor Thesis 2012.
Poster 160
Saturday 9:00 - 11:30
217
Attempts synthesize new 3- and 4- (trifluoromethyl)
azetidin-2-ones Staudinger reaction conditions
Rafal Kluza, Emilia Obijalska, Grzegorz Mloston
Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 –
Lodz – POL
[email protected]
(Trifluoromethyl) azetidin-2-ones combine the unique physical, chemical, biological
and synthetic utility resulting from the presence both of the CF3 group and the βlactam skeleton. For this reasons, compounds of this type functionalized with CF3
group are an attractive class of substrates for use in organic synthesis, as well as
substances with potential biological activity. The literature describes few examples of
methods of preparation of azetidin-2-ones bearing CF3 substituent at positions C(3)
or C(4) in heterocyclic ring.
The main goal of presented study was to develop method for obtaining new 4 or 3CF3 -β-lactams with usage a starting materials N-(tert-butylsulphinyl) imine derivated
from fluoral (1) and 3,3,3-trifluoropropionic acid (2).
Preparation of racemic substrate 1 was unsuccessful. In each case, product was isolated in a appropriate hemiaminalan form. That is why, all reactions were carried out
with commercially available (S )-1. Both used substrates 1 and 2 were not convenient
reagents for preparation desired compounds in Staudinger type reactions (with acid
chlorides, carboxylic acids or α-diazoketones). Only in the case of condensation (S )-1
with enolate anion generated from ethyl propionate gave 4 CF3 -β-lactam.
218
Saturday 9:00 - 11:30
Poster 161
N6 − α-Halogenacyl-derivatives of Sydnone Imines
Alina S. Samarskaya, Il’ia A. Cherepanov, Valery N. Kalinin
Chemistry of Organoelement Compounds –
A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences –
Vavilov St. 28, 119334 – Moskow – RUS
[email protected]
Sydnone imines are the most studied representatives of mesoionic heterocyclic compounds. Their synthesis and studying of their properties are of great interest because
of broad spectrum of sydnone imine’s pharmacological activity. Recently it was shown
that sydnone imines were effective exogenous donors of nitrogen oxide (NO) an unique
intracellular regulator of metabolism in living organism.
At the moment, there are only unitary examples of N6 − α-halogenacyl- derivatives
of sydnone imines at literature and their reactivity is virtually uninvestigated. The
aim of our study was to fill these existing gaps in the chemistry of sydnone imines.
We have obtained a wide range of N6 − α-halogenacyl-derivatives of sydnone imines
1 by the featured way of the interaction of chloroanhidrides of α-halogensubstituted
carboxylic acids with sydnone imines hydrochlorides.
It has been shown that these derivatives 1 are smoothly interact with different dialkylamines (Scheme 1) and S-nucleophiles (Scheme 2).
In addition, it has been shown that in case of N6 − α-(2-thio-3-cyanopyridines)acetylderivatives 4 the course of the reaction of intramolecular cyclisation (Thorpe-Ziegler
reaction) in 3-aminothienopyridines 5 is possible in good-to-excellent yields (Scheme
3).
Thus, a wide range of novel representatives of sydnone imines have bin obtained.
These derivatives are of great interest as potential pharmacological active compounds.
Poster 162
Saturday 9:00 - 11:30
219
(Iso)quinolinocoumarins: a novel class of bright fluorescent
dyes with large Stokes shift
Maksim V. Sednev , Shamil Nizamov, Vladimir N. Belov, Stefan W. Hell
Department of NanoBiophotonics – Max Planck Institute for Biophysical Chemistry –
Am Fassberg 11 – Göttingen – GER
[email protected]
Dyes with large Stokes shifts (80–200 nm) are easy to detect, due to minimal sensitivity losses caused by reabsorption of light. Large Stokes shifts also facilitate spectral separation of the emission signal from the scattered excitation light, as well
as from the background fluorescence of biological samples, which usually exhibits
only small Stokes shift.[1] Photostable and bright fluorescent dyes with large Stokes
shifts are rare and only few of them commercially available. Nearly all of them
contain the coumarin fragment as a fluorophore. Recently, we reported the synthesis of 3-heteroarylcoumarins emitting green light, possessing Stokes shifts of ca.
70 nm, and performing quite well in optical microscopy applications, in particular,
super-resolution imaging based on stimulated emission depletion (STED).[2] In the
present study, we show that the Stokes shift can be nearly doubled by fusion of the
coumarin system with the (iso)quinoline ring. For that, an ethene unit was incorporated between C-4 of the fluorophore and the pyridine ring (compound 3). The new
(iso)quinolinocoumarins 3 emit yellow or orange light and have the Stokes shifts of
ca. 140 nm. They were prepared from organotin precursors 1 and bromoheteroarylcarbaldehydes 2 using a Stille coupling reaction followed by cyclization of the intermediates in protic solvents and in the presence of a base. The large Stokes shifts
and the good quantum yields in polar solvents (30 % in methanol) suggest that the
modified (iso)quinolinocoumarins can be applied as photostable markers in multicolor
STED microscopy.
[1]
F. Vollmer, W. Rettig, E. Birckner, J. Fluoresc. 1994, 4, 65-69.
S. Nizamov, K. I. Willig, M. V. Sednev, V. N. Belov, S. W. Hell, Chem. Eur. J. 2012, 18,
16339-16348.
[2]
220
Saturday 9:00 - 11:30
Poster 163
Simple new method of synthesis alkyl nitrites
Tomasz Klucznik
Department of Chemistry – Gdansk University of Technology – Narutowicza 11/12 –
Gdansk – POL
[email protected]
Alkyl nitrites belong to a class of organic compounds with the general formula RONO,
where R is an alkyl group. Thus, they are esters of nitrous acid. Alkyl nitrites are
useful reagents for organic synthesis, an example for synthesis organic or inorganic
azides from compounds contain hydrazine group.
Classic methods of synthesis alkyl nitrites[1-4] base on add drop by drop cool alcohol
and acid solution to water solution of sodium or potassium nitrite. Nitrite solution
are cooling in water and brine bath. Control of temperature and adding reagents
to reaction mixture are crucial parts of alkyl nitrites synthesis. High temperature
favour hydrolysis and evaporation of final product. That the temperature control
is so important. But using the bath cooling in this case are ineffective. Time of
reaction are finally inacceptable long. Adding too much acid in one pot, iniciate
irreversible hydrolysis of alkyl nitrite. Final products of hydrolysis alkyl nitrites are
easy to identify reddish-brown nitrogen dioxide which leaves reaction mixture. That
are most important problems connection with alkyl nitrite synthesis.
My reply for that synthesis troubles are the new easy to implementation method of
synthesis alkyl nitrites. The key ideas are cancellation cool bath and change form of
sodium nitrite. I used the easiest self coolling mixture as ice blocks. Stoichiometric
(1,1eq) solution of sodium or potassium nitrite was cooling in the refrigerator as long
as they are not freeze to cubes. That form of sensitive reagent has many advantages.
Problem of add alcohol and acid solution is elimination too. Yields of this simply
method are good or very good. The most important part of my solution are easy
applicable to high scale production. Elimination adding reagents in portions and self
controlled temperature are promote this method to technology scale of production.
Ryc.1. The difference between two methods of synthesis alkyl nitrites
[1]
R. Adams, O. Kamm, J. Am. Chem. Soc. 1918, 40, 1285. [2] A. I. Vogel, Preparatyka
organiczna 1984, WNT, 347-348.
[3]
W. A. Noyes, Org. Synth. 1943, Coll. Vol. 2, 108; 1936, Vol. 16, 7.
[4]
R. A. Miller, Inorg. Synth. 1946, 2, 139.
Poster 164
Saturday 9:00 - 11:30
221
Synthesis, structure and electrochemical properties of novel
Co(III) complex with 2-acetylpyridine
S-methylisothiosemicarbazone
Marko Rodić, Mirjana Lalović, Ljiljana Vojinović-Ješić, Ljiljana Jovanović,
Vukadin Leovac
Faculty of Sciences – University of Novi Sad – Trg Dositeja Obradovića 3 – Novi Sad –
SRB
[email protected]
2-acetylpyridine thiosemicarbazone and its N(4)-substituted derivatives have wide
range of biological activity. This has been the main reason for intensive study of this
ligand group complexes with transition and non-transition metals. On the contrary, a
limited number of transition metal complexes with 2-acetylpyridine S-methylisothiosemicarbazone (HL) is known, of which only few mono-ligand Cu(II) and bis-ligand
Co(III) complexes have been characterized with X-ray analyses.
The paper is concerned with the crystal structure and electrochemical characteristics of the cobalt(III) complex with 2-acetylpyridine S-methylisothiosemicarbazone
(HL), of the coordination formula [CoL2 ][CoII pyCl3 ] · M e2 CO. X-ray crystallography revealed that Co(III) is situated in a slightly deformed octahedral environment
formed by six nitrogen atoms of the two L molecules in the meridional positions.
The ligands molecules coordinate with Co(III) in a usual way, i.e. via the pyridine,
azomethine, and isothioamide nitrogen atoms, each forming two five-membered metallocycles. Electrochemical studies of the complex in DMF showed that the electrode
processes are accompanied by chemical reactions and the corresponding mechanism
was proposed. The obtained complex was also characterized by elemental analysis,
conductometric measurements and UV–Vis and IR spectroscopy.
Molecular structure of the complex
222
Saturday 9:00 - 11:30
Poster 165
Reactions of 3-acylchromones with dimethyl
1,3-acetonedicarboxylate and 1,3-diphenylacetone: one-pot
synthesis of functionalized 2-hydroxybenzophenones,
6H-benzo[c]chromenes and benzo[c]coumarins
Iryna Savych, Alexander Villinger, Vyacheslav Sosnovskikh, Peter Langer,
Viktor Iaroshenko
Department of Chemistry – University of Rostock – Albert Einstein Str. 3a – GER
[email protected]
Chromones are very attractive targets for combinatorial library synthesis due to
their wide range of valuable biological activities.[1] The biological and industrial
importance of chromones has led to a considerable amount of synthetic work in
the field of 3-substituted chromones, especially 3-formylchromone[2] , which contain
three electrophilic centers. We envisaged that introduction of powerful electronwithdrawing groups as methoxalyl, polyfluoroacyl and aroyl into the 3-position of
chromone would increase its reactivity toward nucleophilic reagents. Unlike, these
3-substituted chromones 1-3 have not received much attention despite their potential interest as building blocks in organic synthesis via the reactions with 1,3-C,Cdinucleophiles. A fact prompting us to investigate their reaction with dimethyl 1,3acetonedicarboxylate and 1,3-diphenylacetone.
We are reporting now, that reactions of 3-substituted chromones 1-3 with dimethyl
1,3-acetonedicarboxylate and 1,3-diphenylacetone in the presence of DBU proceed at
the C-2 atom of the chromone system with pyrone ring-opening and subsequent formal
[3+3] cyclocondensation and led to the formation of functionalized 2-hydroxybenzophenones, 6H-benzo[c]chromenes and benzo[c]coumarins, depending on the substituent
at the 3-position (Figure 1).[3]
The obtained products constitute an important structural subunit of a variety of
biologically active compounds[4] , which are not readily available by other methods. In
further experiments we studied the base-mediated hydrolysis of the products 4,5. It is
also important to notice, that due to the strong UV-absorption properties synthesized
products can find a use in the preparation of the sun-protective materials and creams.
Figure 1. Synthesis of obtained products 4-7.
[1]
S. T. Saengchantara, T. W. Wallace, Nat. Prod. Rep. 1986, 465-475.
H. Chen, F. Xie, J. Gong, Y. Hu, J. Org. Chem. 2011, 76, 8495-8500.
Viktor O. Iaroshenko, Iryna Savych, Alexander Villinger, Vyacheslav Ya. Sosnovskikh, Peter
Langer, Org. Biomol. Chem. 2012, 10, 9344-9348.
[4]
(a) T. Tzanova, M. Gerova, O. Petrov, M. Karaivanova, D. Bagrel, Eur. J. Med. Chem. 2009,
44, 2724-2730; (b) R. W. Pero, D. Harvan, M. C. Blois, Tetrahedron Lett. 1973, 14, 945-948.
[2]
[3]
Poster 166
Saturday 9:00 - 11:30
223
Direct reductive amination of methyl
2-(2-formyl-4-nitrophenoxy)alkanoates. Synthesis of
2-alkyl-1,4-benzoxazepin-3-ones.
Agata Wrześniewska, Halina Kwiecień
West Pomeranian University of Technology, Szczecin – 42 Piastów Ave. – Szczecin – POL
[email protected]
Reductive amination is the reaction of aldehydes and ketones with ammonia or primary/secondary amines in presence of a selective reducing agent. It is one of the most
important tools in the synthesis of amines.[1]
Our previous research has shown that the reductive amination of methyl 2-(2-formylphenoxy)alkanoates with hydrazine leads to the formation of corresponding primary
amino esters, which immediately underwent cyclization to 1,4-benzoxazepin-3-ones.[2]
1,4-Benoxazepine derivatives are well-known as compounds possessing antidepressant
or antihistaminic properties.[3]
Here, we report the results of our study of direct reductive amination of methyl 2(2-formyl-4-nitrophenoxy)alkanoates 1 to the corresponding amino esters 3 via Schiff
base intermediates 2, followed by the cyclization of the obtained amino esters to the
1,4-bnzoxazepin-3-ones 4. The reductive amination process was carried out at ambient temperature with use of sodium triacetoxyborohydride as the selective reducing
agent and 1,2-dichloroethane as the solvent (Figure 1). The process of obtaining
1,4-benzoxazepin-3-ones by intramolecular cyclization of N-arylated amino esters 3
took several attempts using a variety solvents, catalysts, and different reaction times.
Optimal results were achieved when the amino esters were heated for 6h at 200-205o C.
All amino esters and 1,4-benzoxazepin-3-ones are new compounds and their structures
were confirmed by spectroscopic methods.
Figure 1. Synthesis of N -phenyl-2-alkyl-7-nitro-1,4-benzoxazepin-3-ones from methyl
2-(2-formyl-4-nitrophenoxy)alkanoates.
[1]
S. Gomez, J. A. Peters, T. Maschmeyer, Adv. Synth. Catal. 2002, 344, 1037.
H. Kwiecień, M. Szychowska, Synth. Comm. 2007, 37, 3599.
[3]
H. Kwiecień, M. Śmist, A. Wrześniewska, Curr. Org. Synth. 2012, 9, 828.
[2]
224
Saturday 9:00 - 11:30
Poster 167
Valence isomery in phenoxyl ferrocenyl radicals
Andreas Neidlinger , Katja Heinze
Institute of Inorganic and Analytical Chemistry – Johannes Gutenberg-University –
Duesbergweg 10-14 – Mainz – GER
[email protected]
Electron transfer (ET) is one of the fundamental and most important phenomena in
chemistry and biology. Mixed-valence and mixed metal compounds are extremly valuable systems for studying optically and thermally driven electron transfer reactions.
We have been engaged in the synthesis of oligopeptides built from 1-aminoferrocene1’-carboxylic acid[1] which can be oxidized to mixed-valent ferrocene/ferrocenium
peptides.[2,3]
Unlike ET between chemically similar moieties, ET between chemically different
building blocks is less well explored, even though dissimilar redox partners play a
crucial role in many biological ET systems, e.g. in photosystem II where phenoxyl
radicals in the form of tyrosyl radicals are one of the central redox sites between the
special pair P680 and the oxygen evolving complex.[4] Interestingly, the formal redox
potentials of the biologically relevant phenolate/phenoxyl pair and the organometallic
ferrocene/ferrocenium pair can be very similar when using appropriate substituents.
We have designed 2,4-di-tert-butyl-6-(2-ferrocenyl-carbamoyl)-phenol H-1, which, after deprotonation to 1− , provides the chemically very different redox centers phenolate and ferrocene with similar redox potentials.[2,3,5]
A priori it is not obvious which redox site of the dissymmetric phenolate-ferrocene
conjugate 1− will be oxidized in 1. (valence ambiguity). The behavior of this system
was probed by cyclic voltammograms, UV/Vis/NIR, IR and EPR spectroscopy under
oxidizing and alkaline conditions in different solvents. Density Functional Calculations
were also performed in different solvents to interpret the findings.
[1]
K. Heinze, M. Schlenker, Eur. J. Inorg. Chem. 2004, 2974-2988.
D. Siebler, M. Linseis, T. Gasi, L. M. Carrella, R. F. Winter, C. Förster, K. Heinze, Chem.
Eur. J. 2010, 17, 4540-4551.
[3]
D. Siebler, C. Förster, K. Heinze, Dalton Trans. 2011, 40, 3558-3575.
[4]
J. M. Mayer, I. J. Rhile, F. B. Larsen, E. A. Mader, T. F. Markle, A. G. DiPasquale, Photosynthesis Research 2006, 87, 3–20.
[5]
R. Wanke, L. Benisvy, M. L. Kuznetsov, M. F. C. Guedes da Silva, A. J. L. Pombeiro, Chem.
Eur. J. 2011, 17, 11882-11892.
[2]
Poster 168
Saturday 9:00 - 11:30
225
Lacunary dodecavanadate clusters: Versatile building blocks
for transition metal functionalized polyoxovanadates
Katharina Kastner , Carsten Streb
Department Chemie und Pharmazie –
Friedrich-Alexander-Universität Erlangen-Nürnberg – Egerlandstraße 1 – Erlangen –
GER
[email protected]
Polyoxometalates (POMs) are metal oxide clusters based on high-valent early transition metals such as Mo, W or V.[1] Reactivity as well as wide structural diversity
make POMs interesting candidates for applications in areas such as electronic and
magnetic molecular materials, catalysis, medicine and materials science.[2] Despite
the wide structural variety of POM clusters, the targeted synthesis of a cluster framework for specific applications is still a huge challenge as formation mechanisms are
hard to predict and control. Here, we present a promising route which enables us to
access a new family of transition-metal substituted polyoxovanadate clusters through
targeted syntheses with predictable outcome. A novel, chloride- templated dodecavanadate cluster featuring two hexagonal coordination sites was developed based our
earlier work on cluster assembly under non-aqueous conditions.[3] The cluster is used
as a molecular host for the binding of a wide range of transition metals whilst retaining the original cluster framework. The concept is closely related to the classical
use of organic ligands, allowing us to consider the dodecavanadate cluster as stable,
purely inorganic ligands. The modification of the physical properties and electronic
and magnetic structure of transition-metal substituted clusters are explored and selective metal substitution will be employed for the development of stable and highly
active molecular catalysts.
Figure 1 Reaction scheme of the syntheses of transition metal (Fe, Co, Cu) containing
polyoxovanadate clusters starting with a chloride templated dodecavanadate cluster as a
molecular host.
[1]
M. T. Pope, Y. Jeannin, M. Fournier, Heteropoly and isopoly oxometalates, Springer-Verlag
Berlin, 1983.
[2]
Special polyoxometalate issue: L. Cronin, A. Müller (guest eds.), Chem. Soc. Rev. 2012,
7325-7648.
[3]
(a) J. Tucher, L. C. Nye, I. Ivanovic-Burmazovic, A. Notarnicola, C. Streb, Chem. Eur. J.
2012, 18, 10494-10453; (b) J. Forster, B. Rösner, R. H. Fink, L. C. Nye, I. Ivanovic-Burmazovic,
K. Kastner, J. Tucher, C. Streb, Chem. Sci. 2013, DOI: 10.1039/c2sc20942j; (c) K. Kastner, B.
Puscher, C. Streb, Chem. Commun. 2013, DOI:10.1039/C2CC36638J.
226
Saturday 9:00 - 11:30
Poster 169
Advanced materials in controlled drug delivery systems
Anna Dabrowska, Marta Gawel, Agnieszka Kierys
Department of Adsorption – Faculty of Chemistry,Maria Curie-Sklodowska University –
Pl. M. Curie-Sklodowskiej 3, 20-031 – Lublin – POL
[email protected]
Multi-component inorganic/organic composites have attracted great interest as a new
class of porous solids with potential application in gas separation, catalysis, drug
delivery systems or host for inclusion compounds. The silica gel is considered to be a
fascinating and interesting material for many applications due to its porous internal
structure and morphological characteristics. Therefore, the use of silica gel as fillers
is growing in particular due to the silanol groups presence on its surface which make
it easily modifiable with different functional groups.
One can easily observe the development made in recent years in the areas of polymer
science, biomaterials, composite systems, and other related fields which has resulted in
great medical and pharmaceutical progress. Particular significance is the progress that
has been made in the areas of the controlled drug delivery systems. The undoubted
advantage of these systems is the sustained release of a drug at a therapeutic level over
the long period of time. As a consequence, the dosing frequency can be considerably
reduced without losing of effectiveness of therapeutic activity. Therefore, a much
attention and efforts are devoted to prepare a new materials which could be used in
the controlled drug delivery systems.
It was demonstrated that the release of the drugs out of polymer-based carrier systems
can be achieved by controlling a simple diffusion process.[1] However, the effectiveness
of such delivery systems, is limited by the e.g. stability, porosity or biocompatibility of the carriers network. Therefore, by using the polymer-silica composites as a
drug carrier matrix the formation of an appropriate porosity and an improvement of
stability of the polymeric network can be achieved.
In this paper we present the polymer-silica composite which can serve as a carrier
in drug release system. The composite was synthesised by the method which consist
in swelling of preformed porous polymer particles in tetraethoxysilane TEOS.[2,3] It
has been shown that this composite exhibits a relatively high porosity within both
the polymer and silica component. Because of an interaction between the system
components during the swelling and the condensation of SiO2 in polymer matrix, the
diffusion of the drug is significantly limited and can be controlled. We demonstrate
the profiles of naproxen release and report on the composite system characteristics
through porosity, TEM, SEM and NMR studies.
[1]
A. Bernkop-Schnürch, S. Scholler, R. G. and Biebel, “Development of controlled drug release
systems based on polymer-cysteine conjugates”, Journal of Controlled Release 2000, 66, 39.
[2]
R. Zaleski, A. Kierys, M. Grochowicz, M. Dziadosz, J. Goworek, “Synthesis and characterization
of nanostructural polymer–silica composite: Positron annihilation lifetime spectroscopy study”,
Journal of Colloid and Interface Science 2011, 358, 268.
[3]
R. Zaleski, A. Kierys, M. Dziadosz, J. Goworek, I. Halasz, “Positron annihilation and N2
adsorption for nanopore determination in silica-polymer composites”, RSC Advances 2012, 2,
3729.
Poster 170
Saturday 9:00 - 11:30
227
The physicochemical properties of novel porphyrazines
possessing an alternate system of 2,5-dimethylpyrrol-1-yl and
dimethyloamino peripheral substituents
Tomasz Koczorowski ∗ , Wojciech Szczolko∗ , Lukasz Sobotta† , Marcin Wierzchowski∗ ,
Piotr Fita‡ , Aleksandra Orzechowska , Kvetoslava Burda , Jadwiga Mielcarek† ,
Tomasz Goslinski∗
∗
Department of Chemical Technology of Drugs – University of Medical Sciences –
†
Department of Inorganic and Analytical Chemistry – University of Medical Sciences –
‡
Institute of Experimental Physics, Faculty of Physics – University of Warsaw –
Hoza 69 – Warsaw – POL
Faculty of Physics and Applied Computer Science –
AGH University of Science and Technology – al. Mickiewicza 30 – Kracow – POL
[email protected]
Introduction
For the last 30 years, porphyrazines (Pzs) substituted at their β-positions with nitrogen, oxygen or sulfur residues have been synthesized and subjected to various
physicochemical as well as biological studies.[1] Pzs have been investigated as potential photosensitizers for biomedical, analytical applications, and as compounds for
materials chemistry.[2] Although, there are many examples of Pzs containing peripherally annulated heteroarene rings[3] , there are limited data on Pzs substituted directly
at their β-position with five-membered heteroaromatic rings.[4,5]
Results and Discussion
In the course of our research, novel Pzs containing peripheral 2,5-dimethylpyrrol-1-yl
and dimethylamino groups were synthesized, purified and characterized using NMR
and X-ray crystallography. Spectroscopic studies performed on Pzs encompassed
steady state absorption and emission measurements, fluorescence decays, femtosecond transient absorption spectra and thermoluminescence. Moreover, the potential
photosensitizing activity of novel Pzs was evaluated by measuring their ability for
singlet oxygen production using 1,3-diphenylisobenzofuran.
Fluorescent properties of the Pzs studied were typical for porphyrinoids with very low
dipole moment. Time resolved fluorescence studies revealed a significant difference of
fluorescence decays between metallated and free-base Pzs as well as a dependence of
excited-state lifetime on a particular metal ion. Transient absorption measurements
carried out in a 2 ns temporal window with femtosecond temporal resolution do not
indicate any excited-state processes other than energy relaxation and intersystem
crossing. Thermoluminescence measurements showed that Pzs containing Mg, Zn or
Fe ions in THF are able to stabilize metastable states under short (a half-width of
about 4 µs) saturating flash. This effect vanished in samples dissolved in pyridine.
[1]
S.L.J. Michel, B.M. Hoffman, S.M. Baum, A.G.M. Barrett Progress in Inorganic Chemistry;
Karlin K.D., Ed., J. Wiley & Sons: New York, 2001, 50, 473-590.
[2]
R. R. Allison, C. H. Sibata, Photodiagn. Photodyn. Ther. 2010, 7, 61.
[3]
M.P. Donzello, C. Ercolani, P.A. Stuzhin, Coord. Chem. Rev. 2006, 250, 1530.
[4]
Q. Luo, S. Cheng, H. Tian Tetrahedron Lett. 2004, 45, 7737.
[5]
S. Szczolko, L. Sobotta, P. Fita, T. Koczorowski, M. Mikus, M. Gdaniec, A. Orzechowska, K.
Burda, S. Sobiak, M. Wierzchowski, J. Mielcarek, E. Tykarska, T. Goslinski Tetrahedron Lett.
2012, 53, 2040.
This study was supported by the National Science Centre under Grant No. N N404 069440.
228
Saturday 9:00 - 11:30
Poster 171
A Bunch of Novel Cobaltocenium Cations on the Way to
Azo-Bridged Bicobaltocenes
Anne Wolter , Jürgen Heck
Department of Chemistry – University of Hamburg – Martin-Luther-King-Platz 6 –
20146 Hamburg – GER
[email protected]
Molecular photochromic switches are molecules that can be changed reversibly between two different (meta)-stable states due to irradiation with light of an appropriate
wavelength. These two isomers have different chemical and physical properties. The
change of the properties can be useful in various photonic devices.[1]
A very important photochromic switch is the well-investigated azo-group. The azoswitch changes its properties by irradiation due to a change of the configuration, a
E-Z photoisomerisation (Fig.1). The E -isomer is planar and elongated, the Z -isomer
is bent and more compact.[2]
In our working group we investigate the interaction of paramagnetic oligonuclear
metallocene derivatives[3] in particular azo-bridged paramagnetic metallocenes. Our
target is to link two paramagnetic metallocenes with an azo-bridge. Due to the
configurationally change of the bridge the magnetic exchange coupling J 1,2 (Fig.1a)
could change significantly between two paramagnetic cobaltocene moieties and, thus,
changes the magnetic properties of the whole molecule as well. On the way to the
azo-cobaltocene novel functionalized cobaltocenium cations could be synthesized in
several steps (Fig.1b).
Figure 1. a) E-Z photoisomerisation of the azo-switch b) Key compounds on the way to
the azo-cobaltocene
[1]
M. Irie, Chem. Rev. 2000, 100, 1685-1716. [2] M. Kurihara, H. Nishihara, Coord. Chem.
Rev. 2002, 226, 125-135. [3] a) N. Pagels, O. Albrecht, D. Görlitz, A. Y. Rogachev, M. H.
Prosenc, J. Heck, Chem. Eur. J., 2011, 17, 4166-4176. b) S. Trtica, M. H. Prosenc, M. Schmidt,
J. Heck, Inorg. Chem., 2010, 49, 1667-1673.
Poster 172
Saturday 9:00 - 11:30
229
Transition Metal-Bismuth Donor-Acceptor Interactions
Supported by Ambiphilic PBiP Pincer Ligands
Carolin Tschersich, Christian Limberg
Institut für Chemie – Humboldt-Universität zu Berlin – Brook-Taylor-Str. 2 – Berlin –
GER
[email protected]
Although bismuthanes can act as donor ligands for transition metal ions,[1] they
do not possess a donor strength comparable to e.g. the one of phosphanes, their
lighter homologues. By contrast BiIII compounds often show distinct Lewis acidic
properties, especially if electronegative ligands, X, are bound.[2]
The σ-donor behavior of electron rich transition metal ions towards unsaturated Lewis
acidic main group elements has been demonstrated some time ago, and very recently
also compounds have been reported, where transition metal complex fragments act
as donors for saturated Lewis acidic centers like SiIV , SnIV and SbV .[3] Such interactions are also conceivable for Bi centers and the possibility to influence the reactivity
and catalytic activity (selectivity) of a late-metal complex by Lewis acidic bismuth
moieties appears highly attractive. However, closed-shell M-Bi interactions, for M
representing a late transition metal, are still virtually unexplored.
To stabilize complexes exhibiting such metallic contacts with pronounced MBi character, we have developed an ambiphilic ligand system, where a Lewis acidic Bi–X unit
is combined with two Lewis basic phosphane donor functions that may serve to place
the Bi atom close to a transition metal center. After the successful synthesis of such
PBiP pincer ligands, we have tested their potential to establish MBi interactions
for d8 -configurated PtII characterized by a filled Lewis basic d2z orbital, and for AuI ,
since the latter can be expected to lead to large relativistic effects. We report on the
results of our efforts that led to complexes incorporating strong PtBi and AuBi
interactions.[4]
[1]
a) S. Roggan, C. Limberg, Inorg. Chim. Acta. 2006, 359, 4698-4722; b) H. Braunschweig, P.
Cogswell, K. Schwab, Coord. Chem. Rev. 2011, 255, 101-117.
[2]
W. Clegg, R. J. Errington, G. A. Fisher, D. C. R. Hockless, N. C. Norman, A. G. Orpen, S. E.
Stratford, Dalton Trans. 1992, 1967-1974.
[3]
a) A. Amgoune, D. Bourissou, Chem. Commun. 2011, 47, 859-871; b) C. R. Wade, F. P.
Gabbaï, Angew. Chem. Int. Ed. 2011, 50, 7369-7372.
[4]
a) C. Tschersich, C. Limberg, S. Roggan, C. Herwig, N. Ernsting, S. Kovalenko, S. Mebs,
Angew. Chem. Int. Ed. 2012, 51, 4989–4992; b) T.-P. Lin, I.-S. Ke, F.P. Gabbaï, Angew.
Chem. Int. Ed. 2012, 51, 4985-4988.
230
Saturday 9:00 - 11:30
Poster 173
Surface functionalization of hybrid core/shell nanoparticles
based on rare earth ions for bio-applications
Sangeetha Balabhadra, Marcin Runowski, Stefan Lis
Department of chemistry – University of Adam Mickiewicz – Grunwaldzka 6 – Poznań –
POL
[email protected]
Nanoparticles coated with organic compounds are an interesting new class of materials. The organic coatings protect the nanoparticles against aggregation, control its
growth and give them the capability to work as receptors for biomolecules. Luminescent nanoparticles are an important class of novel functional materials because
they open a way to use the luminescence of inorganic compounds within an organic
environment. Inorganic compounds doped with lanthanide ions are widely used as
the luminescent materials in lighting, protecting and tracing techniques, as well as
displays, optical amplifiers, and lasers.[1,2] These modifications can be applied in a
hybrid type of nanomaterials, so called core/shell nanostructures.[3]
The doped lanthanide fluorides as core nanoparticles were synthesized via a simple coprecipitation process, then covered with silica and modified with amine groups. Further organic modification was performed using carboxylic acid chloride. The successful
reaction between amine and carboxylic acid was confirmed by FT-IR. The structure
and morphology of the obtained nano-composites were examined with TEM (Transmission electron microscopy) and powder X-ray diffraction. Spectroscopic properties
of nanomaterials were studied by measuring their excitation and emission spectra as
well as their luminescence decay curves.
Surface functionalized hybrid core/shell nanoparticles, doped with rare earth ions
emerging new class of bio-probes, which can be an alternative to conventional molecular probes such as lanthanide chelates and organic dyes. They attract growing attention due to its potential applications in areas as diverse as bio-detection, bioimaging,
owing to their superior features such as long luminescence lifetime, high chemical
stability, resistance to photobleaching, and low toxicity.
[1]
S. Zhou, D. Tu, Z. Chen, M. Huang, H. Zhu, E. Ma, X. Chen, J. Am. Chem. Soc. 2012,
134(36), 15083-15090.
[2]
S. Pate, B. K. Mishra, Talanta 2004, 62, 1005-1028.
[3]
J. Hughey, NNIN REU Research Accomplishments 2005, 55-57.
Poster 174
Saturday 9:00 - 11:30
231
An attempt to synthesize a metallocarbonyl cyclooctyne
derivatives
∗
Aleksandra Kubicka ∗ , Bogna Rudolf† , Emilia Fornal∗
Department of Organic Chemistry – University of Lodz, Faculty of Chemistry –
†
Chemistry Department – The John Paul II Catholic University of Lublin –
Al. Krasnicka 102 – Lublin – POL
[email protected]
The Cu(I)-catalysed azide-alkyne cycloaddition (CuAAC) is one of the best methods for connecting building blocks containing various functional groups by covalent
bounds and it is commonly applied in organic synthesis, surface and polymer chemistry or medicinal chemistry.[1] This reaction is known as an extremely fast and effective click reaction for bioconjugation. However, Cu(I) has undesirable cytoxicity
even at low concentrations.[2] Alternative to CuAAC is the strain-promoted alkyneazide cycloaddition (SPAAC) between cyclooctyne and azide. The use of SPAAC
for bio-conjugation was first described by Bertozzi and coworkers in 2004.[3] In an
attempt to develop a new method for the incorporation of metallocarbonyl labels
into biomolecules, we synthesized a metallocarbonyl cyclooctyne derivative which can
undergo highly efficient SPAAC reaction with azide or other 1,3-dipolar compounds.
Metallocarbonyl complexes display specific IR absorption bands assigned to the stretching vibrations of carbonyl ligands occurring in the range of 1850 to 2150 cm−1 , which
is usually free from absorption bands of biomolecules. Thus they can be applied as IRdetectable markers for the monitoring of biochemical processes such as ligand-receptor
or antigen-antibody interactions.[4]
[1]
J. E. Hein, V. V. Fokin, Chem. Soc. Rev. 2010, 39 (4), 1302-1315.
J. C. Jewett, E. M. Sletten, C. R. Bertozzi, J. Am. Chem. Soc. 2010, 132, 3688-3690.
[3]
N. J. Agard, J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc. 2004, 126, 15046-15047.
[4]
N. Fischer-Durand, M. Salmain, B. Rudolf, L. Dai, L. Juge, V. Guerineau, O. Laprevote,
A.Vessieres, G. Jaouen, Anal. Biochem. 2010, 407, 211-219.
[2]
232
Saturday 9:00 - 11:30
Poster 175
Synthesis and studies on the catalytic activity of new chiral
aziridinyl ligands
Szymon Jarzynski, Stanislaw Lesniak, Michal Rachwalski
Lodz – POL
[email protected]
Asymmetric synthesis is one of the most important areas of research in synthetic
organic chemistry and has wide-ranging industrial applications. It includes methods
and strategies for the preparation of chiral, enantiomerically pure compounds by using
stereoselective reactions. We would like to present the synthesis of series of chiral
ligands being aziridine alcohols which are built on achiral platform and application
of these ligands as chiral catalysts. All the ligands containing enantiomerically pure
aziridines, namely (S)-2-methylaziridine and (S)-2-isopropylaziridine were synthesized
in very good chemical yields.
All obtained products were applied as chiral catalysts in asymmetric addition of diethylzinc to benzaldehyde. These reactions were produced in good chemical yields
and very high enantiomeric excess values.[1,2]
[1]
S. Leśniak, M. Rachwalski, E. Sznajder, P. Kiełbasiński, Tetrahedron Asymmetry 2009, 20,
2311.
[2]
M. Rachwalski, S. Leśniak, P. Kiełbasiński, Tetrahedron Asymmetry 2010, 21, 2687.
Poster 176
Saturday 9:00 - 11:30
233
Alkylisocorroles and strategies towards biomimetic heme
analogs
Martin Hoffmann, Birte Böker, Benedikt Wolfram, Martin Bröring
Chemistry – Institute of Inorganic and Analytical Chemistry, TU Braunschweig –
Hagenring 30 – Braunschweig – GER
[email protected]
Site-directed mutagenesis of the peptide scaffold, especially in the active pocket region,
has long been the method of choice for the investigation of functional aspects in heme
proteins.[1] An alternative, but much less studied approach, is cofactor exchange.[2]
Extracting the native prosthetic group leads to the formation of an apoprotein, which
can be reconstituted with an artificial heme-analogous molecule afterwards.
Apart from modified porphyrins, other tetrapyrroles like phthalocyanine, porphycene
and corrole have been used in this regard.[2]
In comparison to the well-known tetrapyrroles porphyrin and corrole, 10-isocorrole
(short: isocorrole) beares a disubstituted 10-meso position (Fig. 1). Therefore it
exhibits characteristics of porphyrin (dianionic character) and corrole (smaller cavity),
but contains a non-aromatic, electronically distinct ligand backbone.[3]
In this poster the metal-templated synthesis of Nickel- and Palladium alkylisocorroles
is presented. Further strategies towards biomimetic heme analogs of the isocorrole
type are demonstrated.
Fig 1: Core-structures of porphyrin, isocorrole and corrole.
[1]
Y. Lu, S. M. Berry, T. D. Pfister, Chem. Rev. 2001, 101, 3047-3080.
L. Fruk, C.-H. Kuo, E. Torres, C. M. Niemeyer, Angew. Chem. 2009, 121, 1578-1603;
Angew. Chem. Int. Ed. 2009, 48, 1550-1574.
M. Bröring, F. Brégier, O. Burghaus, C. Kleeberg, Z. Anorg. Allg. Chem. 2010, 636, 1760-1766.
[3]
G. Hohlneicher, D. Bremm, J. A. Wytko, J. Bley-Escrich, J.-P. Gisselbrecht, M. Gross, M.
Michels, J. Lex, E. Vogel, Chem. Eur. J. 2003, 9, 5636-5642.
[2]
234
Saturday 9:00 - 11:30
Poster 177
Synthesis and Characterization of a New Phthalocyanine
Including Pentanuclear Zinc (II) Complexes
Gulnur Keser Karaoglan ∗ , Gulsah Gumrukcu∗ , Ali Erdogmus∗ , Ahmet Gul† ,
Ulvi Avciata∗
∗
Chemistry – Technical University of Yildiz – Davutpasa / 34210 – Istanbul – TUR
†
Chemistry – Technical University of Istanbul – Maslak / 34469 – Istanbul – TUR
[email protected]
Metallophthalocyanines (MPcs) derivatives display interesting chemical and physical
properties, so they have been studied extensively. MPcs enjoy many applications in
fields such as non-linear optics chemical sensors, semiconductors, liquid crystals and
catalysis.[1] The increasing importance and use of phthalocyanines as advanced materials have created impetus for design variables of the central metal ion and peripheral
substituents to reach the desired properties.[2]
In the present study, complexation on the periphery to obtain pentanuclear complex
has been accomplished through the reaction of the phthalocyanine carrying salicylideneimino ligating groups with zinc (II) complex of 8-hydroxyquinoline. The new
compounds have been characterized by elemental analysis FTIR, 1H-NMR, UV-Vis
and mass spectra.
[1]
G. K. Karaoglan, G. Gumrukcu, A. Koca, A. Gul, “The synthesis, characterization, electrochemical and spectroelectrochemical properties of a novel, cationic, water-soluble Zn phthalocyanine
with extended conjugation”, Dyes Pigm 2011, 88, 247-256.
[2]
H. Kantekin, Y. Gok, M. B. Kilicaslan, I. Acar “Synthesis and characterization of new metalfree and nickel(II) phthalocyanines containing hexaazadioxa macrobicyclic moieties”, J. Coord.
Chem. 2008, 61 (2), 229-236.
Poster 178
Saturday 9:00 - 11:30
235
Transformations of 2-(2-cyano-2-carbamoyl-1-ethynyl)-3-oxo1-cyclohexen-1-olates in
water
Mariia Vodolazhenko ∗ , Nikolay Gorobets∗ , Oleg Zhikol‡ , Sergey Desenko∗
∗
Department of Heterocyclic Compounds Chemistry –
SSI “Institute for Single Crystals” NAS of Ukraine – Lenin ave. 60 – Kharkiv – UKR
‡
Department of X-ray Diffraction Studies and Quantum Chemistry –
SSI “Institute for Single Crystals” NAS of Ukraine – Lenin ave. 60 – Kharkiv – UKR
[email protected]
A simple method for synthesis of polyfunctional resonance stabilized 2-(2-cyano-2carbamoyl-1-ethynyl)-3-oxo-1-cyclohexen-1-olates 4 has been previously introduced
by our group.[1] These solts have high solubility in water or alcohols and act as reactive
intermediates in the synthesis of various heterocyclic compounds. In this report our
study of their transformations in water under different conditions is presented.
Screening of the reaction conditions[2] for one-pot three-stage selective synthesis of
2-pyrons 6 we found that in the presence of acid the desired compounds 6 are formed
as a main product of the reaction and 2-pyridones 7 as by-products.[3]
Interestingly, that in pure water the transformation of the salts 4 has changed its
direction towards 3-cyano-2-pyridones 8. This method for synthesis of 8 is more
simple then our previous one,[4] and allowed us to understand some aspects of the
reaction mechanism.
Since the direct hydrolysis of a cyano group requires much more vigorous reaction
conditions than the applied for the hydrolysis of salts 1, we believe that both products
6 and 7 are formed via intermediate 2-iminopyrans 5. This suggestion was confirmed
by quantum chemical calculations using DFT B3LYP/aug-cc-pvdz method.
Synthesis of the salts 4 and their transformations in water
[1]
S. A. Yermolayev, N. Yu. Gorobets, E. V. Lukinova, O. V. Shishkin, S. V. Shishkina, S. M.
Desenko, Tetrahedron 2008, 64, 4649-4655.
[2]
M. A. Vodolazhenko, N. Yu. Gorobets, S. A. Yermolayev, V. V. Musatov, V. A. Chebanov, S.
M. Desenko, RSC Advances 2012, 2, 1106-1111.
[3]
N. Yu. Gorobets, B. H. Yousefi, F. Belaj, C. O. Kappe, Tetrahedron 2004, 60, 8633-8644.
[4]
S. A. Yermolayev, N. Yu. Gorobets, S. M. Desenko, J. Comb. Chem. 2009, 11, 44-46.
236
Saturday 9:00 - 11:30
Poster 179
Utilization of cross-coupling reactions
for the synthesis of 3D-NLOphores
Elisabeth Ziemann, Jürgen Heck
Institute of Applied and Inorganic Chemistry – University of Hamburg –
Martin-Luther-King-Platz 6 – 20146 Hamburg – GER
[email protected]
In times of persistent growing information technology markets there is by nature a
great demand for more efficient data transmission methods. Nonlinear optical (NLO)
active materials play a very important role for this enhancement, but to increase the
application range it is necessary to optimize the NLOphores, especially in terms of
response time and size of the examined NLO-effect.[1]
Besides examining dendritic structures[2] we are directed towards so-called
“3D-NLOphores” which are based on a 1,3,5-trisubstituted benzene ring coordinated
to a cationic cyclopentadienyl-ruthenium unit serving as an acceptor, metallocenes
fulfill the donor function.
Their NLO-activity has already been successfully characterized using Hyper-RayleighScattering (e.g. compound A)[3] , our ongoing research now focusses on tuning this
effect (quantified by the value β0 ) by expanding the π-electron-system, varying the
metal centers, the substitution pattern of acceptor and donor function, and the
counter ion (compound B).
The expansion of the π-electron-system should be achieved by the introduction of
ethinylbridges. To prevent observed undesired C-C-cleavage processes[4] we needed
to investigate different synthetic routes for example including Hiyama-, Sonogashiraand Stille-cross coupling reactions. We are presenting the different results of these
approaches and the characterization of the new ethinylferrocene-substituted complex
[RuCp(C6 H3 (C ≡ C − F c)3 )]+ .
[1]
N. J. Long, Angew. Chem. 1995, 107, 37-56.
J. Holtmann, E. Walczuk, M. Dede, C. Wittenburg, J. Heck, G. Archetti, R. Wortmann, H.-G.
Kuball, Y.-H. Wang, K. Liu, Y. Luo, J. Phys. Chem. B, 2008, 112, 14751.
[3]
S. Steffens, M. H. Prosenc, J. Heck, I. Asselberghs, K. Clays, Eur. J. Inorg. Chem. 2008,
1999–2006. [4] S. Steffens, Dissertation, University of Hamburg, 2005.
[2]
Poster 180
Saturday 9:00 - 11:30
237
Synthesis and complexation abilities of new indazole
derivatives with expected cytostatic activity
Jacek Kujawski ∗ , Hanna Popielarska∗ , Beata Drabinska∗ , Anna Myka∗ ,
Sabina Smusz‡,† , Rafal Kurczab† , Andrzej Bojarski†
∗
Department of Organic Chemistry – Poznan University of Medical Sciences –
†
Department of Medicinal Chemistry –
Institute of Pharmacology, Polish Academy of Sciences – Smetna 12 – Krakow – POL
‡
Faculty of Chemistry – Jagiellonian University – Ingardena 3 – Krakow – POL
[email protected]
A series of new dimeric indazole derivatives 5 (A) was obtained by a four-step synthesis that included classical aromatic nucleophilic substitution, Vicarious Nucleophilic
Substitution of Hydrogen (VNS) ortho to the nitro group, reduction of the latter
functionality and cyclization to a pyrazole ring by diazotization. The use of Raney
nickel together with hydrazine hydrate as a source of molecular hydrogen allowed for
considerable shortening of the hydrogenation time. As the resulted amines 4 were
usually insoluble in water, the diazotization was carried out in solid phase using the
microwave method (MAOS). The preliminary biological tests showed that some of
the final products 5 had cytotoxic activity in cell-based bioassays.[1] The cytotoxicity
mechanism may be connected with the compounds ability either to complex metal
ions present at the active sites of proteins or to bond with the nucleic base pairs.
Thus, the simulation of complexation with magnesium ions was performed for compound 5b (B) on this account.[2] Moreover, the theoretical calculations (long range
DFT- B3LYP/6-31G(d,p), and QTAIM methods), using the Gaussian G09 program,
showed the ability of compound 5b to form strong and weak hydrogen bonds with
guanine, cytosine,[3] as well as uridine (C). Some physicochemical properties of the
compounds 5 (log P and pKa) were additionally calculated based on machine learning
algorithms – support vector regression and multilayer perceptron.
Synthesis of indazole derivatives 5 and complexes of 5b wit Mg (B) and uridine (C).
[1]
E. Totoń, E. Ignatowicz, M.K. Bernard, J. Kujawski, M. Rybczyńska, J. Phys. Pharmacol.
2012, submitted.
[2]
J. Kujawski, M. Doskocz, H. Popielarska, A. Myka, J. Kruk, M. K. Bernard, Polyhedron 2013,
submitted.
[3]
J. Kujawski, H. Popielarska, B. Drabińska, E. Jodłowska, J. Adamus, K. Czaja, A. Myka,
M. K. Bernard, “New pyrazole derivatives with potential biological activity: theoretical studies
on complexation of small-molecule ligands” 5th Conversatory on Medicinal Chemistry, Lublin,
13-15.09.2012.
Investigations were supported by PCSS grant No. 96/2011, SBN grant No. 126/2012, polish
National Science Centre (NCN) grants No. N N401 642340 and NNZ2/02478, EU scholarship
for PhD students (Poznan, WUP, Task 8.2.2. PO KL 2011-2012).
238
Saturday 9:00 - 11:30
Poster 181
Synthesis and properties of C-phosphonate nucleotide
analogues bearing alkyne moiety for labeling via CuAAC
reactions
Sylwia Walczak , Joanna Kowalska, Błażej Wojtczak, Jacek Jemielity
Division of Biophysics, Institute of Experimental Physics, Faculty of Physics –
University of Warsaw – Zwirki i Wigury 93 – Warsaw – POL
[email protected]
“Click chemistry” is a modern approach towards the synthesis of compounds by joining
small units in high-yielding, stereospecific and simple reactions such as Cu-catalyzed
azide-alkyne cycloaddition. The considerable part of growing applications of CuAAC
includes modifications of nucleosides and oligonucleotides. Therefore, more and more
attention is paid to the synthesis of specifically designed analogues of nucleosides
that may be used as reagents for 1,3-dipolar Huisgen cycloaddition. In order to
take advantage of CuAAC as a powerful chemical strategy of joining our analogues
of nucleotides with different entities we synthesized the C-phosphonate analogue
of N7 -methyl-guanosine-5’-monophosphate with 4-butynyl substituent (m7 GppC4 H5 ;
Fig.1a). Both the presence of terminal alkyne and excellent solubility make it a good
substrate for click reaction with azide-modified molecules.
Having synthesized m7 GppC4 H5 , we ligated it in a simple click reaction to azidemodified fluorescent dyes (Fig.1c) and magnetic nanoparticles. The former compounds would enable biologists to visualize biomolecules interacting with their nucleic
part whereas the latter conjugates might be found applicable to modern technics of
the affinity chromatography. In order to explore whether triazole ring could mimic
phosphate moiety, we have synthesized dinucleotide cap analogue with triazole ring
within 5’-5’ phosphate bridge (Fig.1b). It may serve as a tool for selective inhibition or
activation of the processes in which cap structure is involved i.e. mRNA maturation,
intracellular transport, translation and degradation.
Fig.1. a) N7 -methyl-guanosine-5’-monophosphate with 4-butynyl substituent
(m7 GppC4 H5 ); b) The cap analogue with triazole ring within 5’-5’ triphosphate bridge;
c) m7 GppC4 H5 attached to fluorescent dye
Poster 182
Saturday 9:00 - 11:30
239
Mechanistic insight into the palladium(II)-catalyzed
oxidative cyclization of diaryl amines
Tobias Gensch, Ingmar Bauer, Hans-Joachim Knölker
Department of Chemistry – Technische Universität Dresden – Bergstraße 66 – Dresden –
GER
[email protected]
The palladium(II)-catalyzed oxidative cyclization of diarylamines to carbazoles is of
great importance for the construction of a wide range of natural products with the
carbazole structure[1] and is an example of a twofold direct C–H-activation for C–Cbond formation (Fig. 1 A). Insights into the mechanism of this transformation were
gained by isolating and characterizing an intermediate diarylpalladium(II) complex
(Fig. 1 B) that consists of a palladacycle connecting both aromatic rings.[2] This
complex undergoes facile conversion to carbazole and palladium(0) and was shown
to be catalytically active for the oxidative cyclization of diarylamines. Its isolation
was possible by the twofold chelation with coordinating, ortho-directing substituents
at the diarylamine. Characterization of this new class of palladium(II) complexes
offers an understanding of the mechanism of direct C–H-activation and reductive
elimination.
Figure 1. A : Oxidative cyclization of diarylamines to carbazoles catalyzed by Pd(II).
B: Example of a stable palladacycle intermediate of the oxidative cyclization.
[1]
a) I. Bauer, H.-J. Knölker, Top. Curr. Chem. 2012, 309, 203–253; b) A. W. Schmidt, K. R.
Reddy, H.-J. Knölker, Chem. Rev. 2012, 112, 3193–3328.
[2]
T. Gensch, M. Rönnefahrt, R. Czerwonka, A. Jäger, O. Kataeva, I. Bauer, H.-J. Knölker, Chem.
Eur. J. 2012, 18, 770–776.
240
Saturday 9:00 - 11:30
Poster 183
Hexaphenoxycyclotriphosphazen as a flame retardant for
transparent Polycarbonat
∗
Bert Käbisch ∗ , Ulrich Fehrenbacher∗ , Edwin Kroke†
Environmental Engineering – Fraunhofer – Joseph-von-Fraunhofer-Str. 7 – Pfintztal –
GER
†
Inorganic Chemistry – TU Bergakademie Freiberg – Leipziger Straße 29 –
Freiberg – GER
[email protected]
The protection of plastics with flame retardants is one of the important topics for
introducing a material to the market and for its end application. Because of new
regulations most of the current used flame retardants are evaluated because of their
toxicity and their environmental impact. Also by adding particular additive flame
retardants to a polymer the mechanical properties are most times negetively affected.
One of these properties is the transparancy of a polymer, e.g. polycarbonate, which
normally will be very negatively affected by using an particular additive flame retardant. Therefore, nonhazardous flame retardants with good compatibillity to the
polymer needs to be investigated. By introducing Hexaphenoxycyclotriphosphazen
(1) as a particalur flame retardant to protect polycarbonate it is possible to obtain a
trasparent material while using a particular, nonhazardous additive. The investigated
concentrations of 1 in polycarbonate are 0, 1, 2, 5 and 10 mass%. The mechanical
properties of the protected polymer, tenacity, tensile elongation, dynamic mechanical
analysis, Charpy impact and transparency were characterized. The flame retardancy
was evaluated with LOI and the UL94 test and shows, even with the big differnce of
the decomposition temperature of 1 and polycarbonate, a very promising effect.
Poster 184
Saturday 9:00 - 11:30
241
Bromodimethylsulfonium Bromide (BDMS) MediatedSynthesis of Urea via Lossen Rearrangement
Deepak K. Yadav , Arvind K. Yadav, Vishnu P. Srivastava, Geeta Watal, L. D. S. Yadav
University of Allahabad – Allahabad – IND
[email protected]
Bromodimethylsulfonium bromide (BDMS) was found to be a very efficient reagent
for Lossen rearrangement of hydroxamic acids to the corresponding isocyantes which
were subsequently trapped in-situ with various amines affording ureas in good to
excellent yields. The protocol is experimentally simple, mild and represents valuable
alternatives to phosgene-based approaches for the preparation of isocyanates.
Bromodimethylsulfonium bromide (BDMS); Lossen rearrangement; Hydroxamic acid; Isocyanates;
Ureas
242
Saturday 9:00 - 11:30
Poster 185
Synthesis of Phosphorylated Isoindolinone Derivatives
Piotr Zagórski ∗ , Andrzej Jóźwiak∗ , Dariusz Cal† , Mieczysław W. Płotka∗
Department of Organic Chemistry – University of Lodz – Tamka 12 – 91-403 Lodz –
POL
†
91-403 Lodz – POL
∗
[email protected]
Isoindolinone building block is present in many natural alcaloids like Lennoxamine.[1]
There are other synthetic drugs that contain isoindolinones moiety, for example
Pagoclone.[2] In recent years a lot of attention has been paid to the synthesis of
phosphorylated isoindolinone derivatives.[3-6] Our research aim is to enrich a modest library of new phosphonic acids and esters containing an isoindolinone structure.
A key step in the synthesis is lithiation of isoindolinone (1) using sec-buthyllithium
in tetrahydrofuran followed by a reaction of the generated lithiated species with diethyl vinylphosphonate (for products 2a) or diethyl(3-bromopropyl)phosphonate (for
products 2b).
[1]
J. R. Fuchs, R. L. Funk, Organic Letters 2001, 3, 3923-3925.
T. L. Stuk, B. K. Assink, D. T. Erdman, V. Fedij, S. M. Jennings, J. A. Lassig, R. J. Smith,
T. L. Smith, Organic Process Research & Development 2003, 7, 851-855.
[3]
J. L. Viveros-Ceballos, M. Ordonez, C. Cativiela, Tetrahedron: Asymmetry 2011, 22, 14791484.
[4]
A. Couture, E. Dienau, P. Woisel, P. Grandclaudon, Synthesis 1997, 12, 1439-1445.
[5]
G. O. Kachkovskyi, O. I. Kolodiazhnyi, Phosphorus, Sulfur and Silicon and the Related
Elements 2010, 185, 2441-2448.
[6]
M. Ordonez, G. D. Tibhe, A. Zamudio-Medina, J. L. Viveros-Ceballos, Synthesis 2012, 44,
569-574.
[2]
Poster 186
Saturday 9:00 - 11:30
243
Mesomorphic properties of some
4-(4-alkoxybenzylideneamino)azobenzenes
Anna Lesniak , Agnieszka Puchala
Institute of Chemistry – Jan Kochanowski University – Swietokrzyska 15G – Kielce –
POL
[email protected]
Azomethine compounds are important due to their applications in dyes, pigments,
functional materials and they were early recognized as the liquid-crystalline compounds. Azomethine bond (CH=N) incorporated into the molecular structure cause
increase the length and polarizability anisotropy of the molecular core in order to
enhance liquid crystal phase stability.
We present synthesis and the liquid crystalline properties of the series of 4-(4-alkoxybenzylideneamino)azobenzenes. The synthesis were carried out in a two-step process.
The starting 4-alkyloxybenzaldehydes were obtained in the usual way by the reaction
of 4-hydroxybenzaldehyde with the appropriate n-alkylbromide. 4-(4-Alkoxybenzylideneamino)azobenzenes were prepared by the condensation of the corresponding aldehydes with 4-aminoazobenzene using a microwave oven (PLAZMATRONICA RM800).
The use of such reaction conditions, compared to classical heating, reveals several features like: better selectivity, shorter reaction time and easier of work-up after reaction.
All final products were purified by chromatography on silica gel with chloroform as an
eluent and characterized by IR, NMR and mass spectroscopy. The mesophases of the
4-(4-alkoxybenzylideneamino)azobenzenes were studied by polarizing optical microscope (POM) and differential scanning calorimetry (DSC). Investigated compounds
exhibit nematic, smectic A and smectic B mesophases. We will discuss the influence
of an alkyl chain length on the mesophase sequence.
244
Saturday 9:00 - 11:30
Poster 187
Synthesis and structure of the first vanadium complex with
the Schiff base of salicylaldehyde and aminoguanidine
Mirjana Lalović, Marko Rodić, Ljiljana Vojinović-Ješić, Vukadin Leovac
Faculty of Sciences – University of Novi Sad – Trg Dositeja Obradovića 3 – Novi Sad –
SRB
[email protected]
The great interest in vanadium coordination chemistry in the context of medical
applications has arisen from the ability of vanadium complexes to promote the insulin mimetic activity in the treatment of human Diabetes mellitus. Despite the fact
that aminoguanidine (AG) shows wide range of pharmacological activity, vanadium
complexes with its Schiff bases are still unknown. Besides, only a few complexes of
salicylidene-aminoguanidine (SalAG) have been synthesized, so it seems worthwhile
to examine the synthesis and characteristics of the new ones.
Here we present the synthesis and structure of the ligand SalAG·HNO3 and its complex with dioxidovanadium(V). Single crystals of the ligand are obtained in the reaction of the ethanolic solutions of the aminoguanidine hydrogennitrate and salicylaldehyde in the presence of the acetic acid, while the reaction of ammoniacal solutions
of the ligand and NH4 VO3 resulted in formation of single crystals of the complex
[VO2 (SalAG−H)]. In this complex, SalAG is coordinated, as a monoanion, in a tridentate ONN mode, via oxygen atom of phenolic hydroxyl and nitrogen atoms of
azomethine and imino groups of the aminoguanidine fragment. Vanadium atom is
situated in almost ideal square-pyramidal environment (τ = 0.032), with the anion of
the chelate ligand and one oxido-ligand in the basal plane and the other oxido-ligand
in the apical position.
Molecular structure of the ligand and the complex
Poster 188
Saturday 9:00 - 11:30
245
Synthesis and Photophysical Properties of Some
Tetraalkynylpyridines
Andranik Petrosyan†,∗ , Peter Ehlers∗ , Tariel Ghochikyan† , Ashot Saghyan† ,
Peter Langer∗
∗
Leibniz-Institut für Katalyse an der Universität Rostock e.V. –
Albert Einstein Str. 29a – Rostock – GER
†
Faculty of Chemistry – Yerevan State University – Alex Manoogian 1 – Yerevan – ARM
[email protected]
Both in materials science and organic chemistry, polyethynylated carbon-rich molecules
are of particular interest because of their extended conjugated structure. Those kind
of molecules have potential as liquid crystals, nonlinear optical materials as well as
building blocks for robust graphite-like carbon networks.[1]
Encouraged by interesting structural, and potential properties of such compounds,
and based on the work done on polyhalogenated pyridines before,[2] a series of new
tetraalkynylpyridines were efficiently synthesized using multiple Sonogashira reaction
protocol.
After symmetrical tertraalkynyl compounds 1 were obtained via tetrafold Sonogashira
coupling, we optimized reaction conditions in order to reach selectivity. As a result,
dialkynylpyridine derivatives 2 were easily synthesized, which in fact, served as important starting point for making molecules 3 with mixed acetylene moieties.
In order to get insights into the impact of substituents in 4-position of the pyridine core, we studied the absorption and emission properties of the synthesized
tetraalkynylpyridines and already reported pentaalkynylpyridines.[2]
Pentaalkynylpyridines absorb and emit at lower energies and possess higher quantum
yields than tetraalkynylpyridines. While a sterically demanding isopropoxygroup in
the 4-position leads to the highest blue shift of the absorption and emission bands as
well as low quantum yields. This effect is based on a poorer conjugation caused by
steric repulsion of the functional groups.
Figure 1. Synthesis of products 1-3.
[1]
(a) U. H. F. Bunz, Y. Rubin, Y. Tobe, Chem. Soc. Rev. 1999, 28, 107; (b) F. Diederich,
Nature 1994, 369, 199. (with the references cited therein)
[2]
(a) P. Ehlers, A. Neubauer, S. Lochbrunner, A. Villinger, P. Langer, Org. Lett. 2011, 13,
1618-1621; (b) V. Engelhardt, J. G. Garcia, A. A. Hubaud, K. A. Lyssenko, S. Spyroudis, T. V.
Timofeeva, P. Tongwa, K. P. C. Vollhardt, SYNLETT 2011, 2, 0280-0284.
246
Saturday 9:00 - 11:30
Poster 189
Solventless selective phosgene-free N-carbonylation of
N-heteroaromatics (pyrrole, indole, carbazole) under mild
conditions
Francesco Iannone, Marianna Carafa, Valentina Mele, Eugenio Quaranta
Dipartimento di Chimica – Università degli Studi di Bari – Via E. Orabona 4 – Bari –
ITA
[email protected]
Organic carbonates (RO)2 CO (R = alkyl, aryl), nowadays available through phosgeneless routes even on an industrial scale,[1] are arousing greater interest as environmentally friendly carbonylating agents.[2] Very little is known about their utilization
in carbonylation reactions of N-heteroaromatic compounds HetNH to HetNCO2 R
(R = alkyl, aryl) derivatives (eqn (1)), which are important synthetic intermediates
for the preparation of a variety of chemicals,[3] including pharmaceutically relevant
substances and biologically active compounds.
HetN H + (RO)2 CO → HetN CO2 R + ROH
(1)
In this report we present a selective method for N-carbonylation of N-heteroaromatics
HetNH, such as pyrrole (1), indole (2) and carbazole (3), by a direct reaction with
diphenyl carbonate (DPC; eqn (1), R = Ph), used as environmental friendly carbonyl
active species in place of toxic and hazardous phosgene.[4]
The carbonylation reaction can be effectively catalyzed by 1,8-diazabicyclo[5.4.0]undec7-ene (DBU), which can act as a base catalyst by activating the HetNH substrate to
the more nucleophilic HetN− anion, and as a nucleophile catalyst by activating the organic carbonate trough the formation of ketene aminal phenyl 1,8-diazabicyclo[5.4.0]
undec-6-ene-8-carboxylate.[5]
The influence of reaction parameters (temperature, reaction time, DBU load,
DPC/HetNH molar ratio) on the productivity of the process has been also investigated. The synthetic methodology does not require severe temperature conditions, is
solventless, simple (only one step), efficient (high yield) and selective, and offers a new
solution to the synthesis of synthetically versatile HetNCO2 Ph derivatives through a
route alternative to the current traditional phosgenation methods.
[1]
(a) D. Delledonne, F. Rivetti, U. Romano, Appl. Catal. A 2001, 221, 241-251.
(a) M. Carafa, E. Quaranta, Mini-Rev. Org. Chem. 2009, 6, 168-183 and references therein;
(b) E. Quaranta, M. Carafa, F. Trani, Appl. Catal. B 2009, 91, 380-388; (c) M. Distaso, E.
Quaranta, Appl. Catal. B 2006, 66, 72-80; (d) M. Distaso, E. Quaranta, J. Catal. 2008, 253,
278-288.
[3]
M. Carafa, V. Mele, E. Quaranta, Green Chem. 2012, 14, 217-225.
[4]
M. Carafa, F.Iannone, V. Mele, E. Quaranta, Green Chem. 2012, 14, 3377-3385.
[5]
M. Carafa, E. Mesto, E. Quaranta, Eur. J. Org. Chem. 2011, 2458-2465.
[2]
Poster 190
Saturday 9:00 - 11:30
247
Porphyrazines containing styryldiazepine rings and their
liposomal formulations: preparation, photochemical
properties and photodynamic activity against oral cancer cell
lines
Jaroslaw Piskorz ∗ , Krystyna Konopka† , Nejat Düzgünes† , Tomasz Goslinski‡ ,
Jadwiga Mielcarek∗
∗
†
Department of Biomedical Sciences – University of the Pacific, School of Dentistry –
2155 Webster Street – San Francisco – USA
‡
[email protected]
Photodynamic therapy (PDT) is a novel, alternative, anticancer treatment, which
has also been used to cure cardiovascular, dermatological, and ophthalmic diseases
as well as various microbial infections. PDT consists of three factors: compound
(photosensitizer), oxygen, and light. Upon irradiation with light of specific wavelength
the photosensitizer undergoes activation and produces reactive oxygen species such
as singlet oxygen. As a consequence, it leads to the death of the treated tissue.[1]
Here we present our data on the synthesis of porphyrazines and tribenzoporphyrazines
containing styryldiazepine rings. Condensation reactions of known dicyanodiazepins
with 3,4,5-trimetoxybenzaldehyde and 1-methyl-2-imidazolecarbaldehyde led to the
novel 1,4-diazepine-2,3-dicarbonitriles containing arylvinyl substituents. However,
only diazepines with 3,4,5-trimetoxyphenyl groups subjected to macrocyclization reactions gave the desired macrocycles of sufficient stability.[2,3] Novel macrocyclic
compounds were characterized using various spectroscopic methods and extensively
investigated in photochemical studies. Moreover, their photodynamic activity was
examined in vitro using two human oral squamous cell carcinoma cell lines, HSC-3
cells derived from the tongue and H413 cells from the buccal mucosa. Magnesium
tribenzoporphyrazine (Pz1) revealed high activity against cancer cells even at low
concentrations and low light dose. Moreover, significantly higher cytotoxicity of Pz1
was observed after its incorporation into negatively charged liposomes (figure).
[1]
R.R. Allison, C.H. Sibata, Photodiagn. Photodyn. Ther. 2010, 7, 61.
T. Goslinski, J. Piskorz, D. Brudnicki, A.J.P. White, M. Gdaniec, W. Szczolko, E. Tykarska.
Polyhedron 2011 30, 1004.
[3]
J. Piskorz, E. Tykarska, M. Gdaniec, T. Gosliński, J. Mielcarek, Inorg. Chem. Commun. 20
(2012) 13.
[2]
This study was supported by the Polish Ministry of Science and Higher Education Grant No. N401
067238 and funds from the University of the Pacific, Arthur A. Dugoni School of Dentistry.
248
Saturday 9:00 - 11:30
Poster 191
Reactivity of InVO4 towards SrO in the solid state
Agnieszka Pacześna, Elżbieta Filipek
West Pomeranian University of Technology, Szczecin – Al. Piastów 42 – Szczecin – POL
[email protected]
The literature review has shown that InVO4 –SrO system and reactions taking place
in this system in the solid state in air have not been subject of research before our
investigations. The properties of the components of the InVO4 –SrO system are well
known.[1, 2] The compound InVO4 is formed in the V2 O5 –In2 O3 system and it melts
incongruently depositing solid In2 O3 at 1135 ◦ C.[3] The indium(III) ortovanadate(V)
crystallizes in the orthorhombic system, space group Cmcm.[4] There exist three polymorphic forms of InVO4 .[5] InVO4 was found to be a visible light driven photocatalyst
for H2 evolution from pure water.[1] Strontium oxide crystallizes in the cubic system,
space group Fm3m.[6] SrO is promising as catalyst for the transesterification of soybean oil to biodiesel.[2]
The aim of this research was, first of all, to investigate whether the reaction between
InVO4 and SrO yields new phase. For the experiments were prepared eight samples
with their compositions representing the whole components concentrations range of
the system under consideration. Weighed in suitable proportions reactants were homogenized and calcinated in the temperature range from 450 to 900 ◦ C in 24 h stages.
After each heating stage XRD examination was performed and selected samples were
additionally subjected to DTA/TG investigation.
The phase compositions of samples after the final heating stage have shown that
InVO4 with SrO react in the solid state in air giving among other a new compound.
However, they indicated that the SrO content in the new compound is ∼ 50.00 mol%.
On the base of XRD phase analysis of the all investigated samples, the two component
system InVO4 –SrO was divided into five subsidiary subsystems.
The investigations are continued, first of all, in order to establish the formula of new
compound.
[1]
J. Ye, Z. Zou, M. Oshikiri, A. Matsushita, M. Shimoda, M. Imai, T. Shisido, Chem. Phys.
Lett. 2002, 356, 221-226.
[2]
X. Liu, H. He, Y. Wang, S. Zhu, Catal. Commun. 2007, 8, 1107-1111.
[3]
M. Touboul, A. Popot, J. Therm. Anal. 1986, 31, 117-124.
[4]
M. Touboul, P. Tolédano, Acta Cryst. 1980, B36, 240-245.
[5]
M. Touboul, K. Melghit, P. Bénard, Eur. J. Solid State Inorg. Chem. 1994, 31, 151-161.
[6]
W. Primak, H. Kaufman, R. Ward, J. Am. Chem. Soc. 1948, 70, 2043-2046.
Poster 192
Saturday 9:00 - 11:30
249
Modeling the CO Oxidation Site of Nickel Containing
Carbon Monoxide Dehydrogenase - Carbonyl Ligand
Oxidation in a β-Diketiminato Nickel Complex by N2 O or O2
Bettina Horn, Christian Limberg, Christian Herwig, Michael Feist, Stefan Mebs
Institut für Chemie – Humboldt-Universität zu Berlin – Brook-Taylor-Straße 2 – Berlin –
GER
[email protected]
Although carbon monoxide is an important substrate in many industrial processes
such as hydroformylation, methanol synthesis, the Fischer-Tropsch and Monsanto
processes, or for the production of dihydrogen in the water gas shift reaction, CO
impurities in gases are often unwarranted, as they can poison catalysts employed to
convert respective gases, for instance H2 . Hence, catalysts have been developed to
selectively oxidize CO to the less harmful CO2 , and these are often based on noble
metals like gold.[1] In nature enzymatic systems do exist which utilize nickel centers
for the reversible conversion of CO to CO2 , namely carbon monoxide dehydrogenases
(CODH). Here water serves as the oxygen source, and during the reaction electrons
as well as protons are produced concomitantly.
Setting out with low coordinated β-diketiminato nickel carbonyl compounds[2] and
bearing the CODH reactivity in mind we were interested to investigate the reactivity
of a nickel(0) carbonyl complex against oxidizing reagents. As this complex is highly
sensitive towards hydrolysis, experiments employing water as the oxygen source (as
the enzyme) excluded themselves, though. Considering that CO oxidation requires
one O atom (formally H2 O → [O] + 2e− + 2H + ) we have chosen N2 O as the O
atom source, which has received increasing attention as an intriguing reagent for
oxidations during the last decades.[3] As an alternative oxidant O2 has been employed
successfully, too. Here we describe the first precedent case of an oxidation of carbonyl
ligands bound to low oxidation state nickel centers by both, N2 O and O2 , under
formation of a unique carbonate compound, K6 [LtBu N i(CO3 )]6 , which was fully
characterized.[4]
[1] H.-J. Freund, G. Meijer, M. Scheffler, R. Schlögl, M. Wolf, Angew. Chem. 2011, 123, 10242;
Angew. Chem. Int. Ed. 2011, 50, 10064.
[2] B. Horn, S. Pfirrmann, C. Limberg, C. Herwig, B. Braun, S. Mebs, R. Metzinger, Z. Anorg.
Allg. Chem. 2011, 637, 1169.
[3] V. N. Parmon, G. I. Panov, A. Uriarte, A. S. Noskov, Catal. Today 2005, 100, 115.
[4] B. Horn , C. Limberg , C. Herwig , M. Feist, S. Mebs, Chem. Commun. 2012, 48, 8243.
250
Saturday 9:00 - 11:30
Poster 193
Application of ’Click’ Cycloaddition for Synthesis of Sulfur
and Oxygen Containing Oligomeric System
Monika Stefaniak , Marcin Jasiński, Jarosław Romański
Department of Organic and Applied Chemistry – University of Łódź – Tamka 12 –
Łódź – POL
[email protected]
Macrocyclic system, for example crown ethers or cryptands containing the heteroaromatic moiety, such imidazole, pyridine etc., are well known and play very important role in supramolecular chemistry and coordination chemistry as a complexing
agents.[1] In last decade, independently of each other, Meldal and Sharpless turned
their attention to the introduction of Cu(I) as catalyst in the Huisgen 1,3-dipolar cycloaddition. In this reaction very stable 1,2,3-triazole ring is formed, which have very
interesting application in medicine or biotechnology.[2] We applied ’click’ approach to
prepare sulfur and oxygen containing macrocyclic systems with built-in 1,2,3-triazole
rings. We obtained compounds A, B, C with very good yields. The oligomer C
contains the Cookson’s ’birdcage’ moiety which increases its lipophilicity. It might be
interesting to test possibility of our compounds to complex ions of metals of group I
and II periodic table or also ions of metals of transitional groups.
[1]
J. L. Atwood, J. W. Steed, “Encyclopedia of Supramolecular Chemistry”, Taylor & Francis
Group, 2004.
[2]
M. Meldal, Ch. W. Tornoe, Chem. Rev., 2008, 108, 2952-3015.
Poster 194
Saturday 9:00 - 11:30
251
Ferrocenyl analogs of plinabulin as organometallic inhibitors
of tubulin polimerization
Anna Wieczorek ∗ , Damian Plażuk∗ , Andrzej Błauż† , Błażej Rychlik† ,
Janusz Zakrzewski∗
∗
Department of Organic Chemistry – University of Łódź – 12 Tamka St. –
91-403 Łódź – POL
†
Department of Molecular Biophysics – University of Łódź – 12/16 Banacha St. –
90-237 Łódź – POL
[email protected]
Organometallic compounds are among the promising drug candidates with strongly
enhanced anticancer activities. Ferrocene, one of the metallocenes, is the most widely
investigated organometallic compound. It is a redox active, stable in biological media
and nontoxic molecule. Ferrocene has shown only slight cytotoxic activity, whereas
when conjugated with biologically active compounds it provides some promising anticancer agents. In recent years many ferrocenyl compounds have been prepared which
have exhibited significant cytotoxicity[1,2] and anti-malarial activities[3] .
Microtubules are noncovalent polymers of the protein tubulin that are found in all
dividing eucariotic cells and in most differentiated cell types. Chemicals that target
microtubules distrupt and suppreses the function by inhibiting or promoting microtubule polimerization.[4]
Plinabulin 1 is a potent microtubule-targeting agent derived from the natural diketopiperazine “phenylahistin” 2. Plinabulin is now under phase II clinical trials as an
anticancer drug.[5]
We have synthesized ferrocenyl analogs of plinabulin (e.g. 3 and 4) of exhibiting
potent microtubule depolymerization and highly cytotoxic.
Acknowledgments: The authors are grateful for the financial support of Polish
National Science Centre (grant 2011/01/B/ST5/03933 years 2011-2014).
Figure A 1 plinabulin, 2 phenylahistin, 3-4 ferrocenyl analogs of plinabulin
[1]
S. Top, J. Tang, A. Vessières, D. Carrez, C. Provot, G. Jaouen, Chem.Commun., 955.
G. Gasser, I. Ott, N. Metzler-Nolte, J.Med.Chem. 2011, 54, 3.
M. Patra, M. G. Gassler, N. Metzler-Nolte, Dalton Trans. 2012, 41, 6350-6358.
[4]
A. Desai, T. J. Mitchison, Annu. Rev. Cell Dev. Biol. 1997, 13, 83.
[5]
Y. Yamazaki, K. Tanka, B. Nicholson, G. Deyanat-Yazdi, B. Potts, J.Med.Chem. 2012, 55,
1056-1071.
[2]
[3]
252
Saturday 9:00 - 11:30
Poster 195
Triazolopyridines: Reactions with dipolarophiles
Rosa Adam, Shamim Alom, Belen Abarca, Rafael Ballesteros
Organic Chemistry department – Universidad de Valencia –
Avda Vicent Andrés Estellés s/n Facultat de Farmacia – Burjassot (Valencia) – ESP
[email protected]
[1,2,3]Triazolo[1,5-a]pyridines 1 are simple heterocycles presenting in solution an equilibrium with its open form, which can be considered a diazo compound.[1,2] The aim of
this work has been to check if triazolopyridines are able to react as diazo compounds
in the presence of several diporalophiles. To achieve our objective we performed
reactions of triazolopyridines 1 with dipolarophiles (ethyl acrilate, ethyl propiolate
and DMAD) (Scheme 1). In the case of ethyl acrilate reactions we obtained the
corresponding pyridyl ciclopropanes 2 by the formation of the corresponding pyridyl
carbene.[3] However, in the cases of ethyl propiolate and DMAD, pirazoyl pyridines 3
were obtained demonstrating that a 1,3-dipolar cycloaddition reaction from the open
form of triazolopyridine can take place.
Scheme 1
[1]
C. Wentrup, Helv. Chim. Acta 1978, 1755.
F. Blanco, I. Alkorta, J. Elguero, V. Cruz, B. Abarca, R. Ballesteros, Tetrahedron 2008, 64,
11150.
[3]
B. Abarca, R. Ballesteros, F. Blanco, Arkivoc 2007, (iv), 297.
[2]
Poster 196
Saturday 9:00 - 11:30
253
Microwave and ultrasound assisted etherification of some
biphenols
Aleksandra Walczak , Magdalena Marcinkowska, Danuta Rasala
Intitute of Chemistry – Jan Kochanowski University – Swietokrzyska 15G – Kielce – POL
[email protected]
In the last few years there has been a growing interest in the use of new techniques
to improve classical organic synthesis. Thus, the obtain good yields within shorter
reaction time as well as higher selectivity both microwave irradiation and ultrasound
assisted procedures were used in the preparation of mono- and disubstituted ethers
of 4,4-biphenol and 4,4’-thiobiphenol.[1]
In conclusion, we hope that the application microwaves and ultrasound irradiation is
a very promising innovation and may stimulate further progress in the etherification
of biphenols in comparison to conventional methodologies.[2] Moreover, it should be
mentioned that a number of compounds under study show liquid crystalline properties.
[1]
[2]
M. Marcinkowska, D. Rasała, A. Puchała, A. Gałuszka, Heterocycl. Commun. 2011, 17, 191.
B. Orzeszko, D. Melon-Ksyta, A. Orzeszko, Synthetic Commun. 2002, 32, 3425.
254
Saturday 9:00 - 11:30
Poster 197
Enantioselective Additions of
(Trifluoromethyl)Trimethylsilane to α-Imino Ketones
Derived from Arylglyoxals
Emilia Obijalska, Alice Six, Grzegorz Mlostoń
Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 Street –
91-403 Lodz – POL
[email protected]
Synthesis of fluorinated compounds is an attractive topic in the synthetic chemistry.[1]
Special attention is focused on derivatives containing CF3 moiety because of their
potential applications.[1] One of the most popular reagents applied for incorporation
of CF3 group into organic molecules is (trifluoromethyl)trimethylsilane (Ruppert’sPrakash reagent, RPR).[2] The aim of present study was the elaboration of an new,
enantioselective method for preparation β-amino-α-(trifluoromethyl) alcohols which
are known as useful building blocks for synthesis of fluorinated derivatives. To the best
of our knowledge there is only one paper in which enantioselective method for preparation of such compounds is described.[3] In our preliminary studies we developed a simple method for synthesis of rac-β-NHR-α-CF3 alcohols 2 starting with α-iminoketones
1.[4] In crucial step, the chemoselective addition of RPR to the C=O, followed by simultaneous reduction of C=N bond and desilylation, is performed. Some successful
attempts of enantioselective reactions of Ruppert’s reagents with aldehydes and ketones are already reported.[5] Additions of RPR to 1 were carried out in the presence
of catalytic system (8R,9S)- or (8S,9R)-3/KF or K2CO3 and they led chemoselectively
to trimethylsilylethers. The latter compounds were converted into final products 2
in high overall yields (80-90%). However, the observed ee values remained low to
moderate (30-70%). The ee values were determined based on the 1H or 19F NMR
spectra registered for products 3 in the presence of (S)-(t-butyl)phenylthiophosphinic
acid ((S)-4) used as chiral solvating agent.
[1]
(a) Kirsh, Modern Fluoroorganic Chemistry, Wiley-VCH, Weinheim, 2004; (b) J.-P. Bégué,
D. Bonnet-Delpon, Bioorganic and Medicinal Chemistry of Fluorine, Wiley, Hoboken, New
Jersey, 2008.
[2]
G. K. S. Prakash, M. Mandal, J. Fluorine Chem. 2001, 112, 123.
[3]
F. Tur, J. M. Saá, Org. Lett. 2007, 9, 5079.
[4]
G. Mlostoń, E. Obijalska, A. Tafelska-Kaczmarek, M. Zaidlewicz, Journal of Fluorine Chem.
2010, 131, 1289.
[5]
(a) S. Mizuta, N. Shibata, M. Hibino, S. Nagano, S. Nakamura, T. Toru, Tetrahedron 2007,
63, 8521; (b) S. Mizuta, N. Shibata, S. Akiti, H. Fujimoto, Org. Lett. 2007, 9, 3707; (c) X. Hu,
J. Wang, W. Li, L. Lin, X. Liu, X. Feng, Tetrahedron Lett. 2009, 50, 4378.
Research were financed by the National Science Center in Poland (Grant ‘SONATA’ # DEC2011/03/D/ST5/05231)
Poster 198
Saturday 9:00 - 11:30
255
Synthesis and characterization of sandwich-type europium
(III) phthalocyanines with different substitutent
Ibrahim Erden, Merve Özdemir, Göknur Yasa, Fatma Aytan Kılıçarslan, Ali Erdogmus
Chemistry Department – Yildiz Technical University – Esenler-34210 – İstanbul – TUR
[email protected]
Phthalocynanines are usually synthesized starting from the appropriate phthalonitriles and their derivatives or their substitution yield as metal-free phthalociyanine
and metallophthalocyanines which obtained especially in high temperatures with the
presence of a suitable anhydrous metal salt. Sandwich-type porphyrinato and/or phthalocyaninato complexes, in which two planar and parallel conjugated p-systems are
held in close proximity by lanthanide metal cation between the two macro-tetrapyrrole
rings, have been intensively studied over several decades in both fundamental academic and applied fields.[1,2]
They are extensively used in printing inks, coatings, paints and plastics as blues and
greens pigments. The phthalocyanines find use also in catalyst for control of sulfur
effluents, lasers, lubricants, photography reagents for cancer therapy, optical information storage systems, photography and xerography, high energy density batteries,
chemical sensors, electrochoromic display devices and liquid crystal colour display
applications.[3-5]
In this study, we report the synthesis and characterization of different substituted phthalocyaninato sandwich-type rare earth complexes. The new compounds have been
characterized by elemental analysis, UV, FT-IR, 1H-NMR spectroscopy and mass
spectra. The effect of the solvents and metal on the photophysical and photochemical
parameters of the metallophthalocyanines are also reported.
[1]
C. C. Leznoff, A. B. P. Lever (Eds.), Phthalocyanines -Properties and Applications, vols.
1-4, VCH, New York, 1989-1996.
[2]
N. B. McKeown, Phthalocyanine Materials-Synthesis, Structure and Function, Cambridge
University Press, New York, 1998.
[3]
G. Yaşa, A. Erdoğmuş, A. L. Uğur, M. K. Şener, U. Avcıata, T. Nyokong, “Photophysical
andphotochemical properties of novel phthalocyanines bearing non-peripherally substituted mercaptoquinoline moiety”, Journal of Porphyrins and Phthalocyanines 2012, 16, 845-854.
[4]
B. Bosnich, C. K. Poon, M. L. ve Tobe, Inorg. Chem. 1965, 4, 1102.
[5]
R.P. Linstead, “Phthalocyanines”, J. Chem. Soc. 1934, 1016-1031.
256
Saturday 9:00 - 11:30
Poster 199
Substituent Influence on Charge Transfer Interactions in
α,α-Diferrocenylthiophenes
Matthäus Speck , Heinrich Lang
Inorganic Chemistry – Chemnitz University of Technology, Institute of Chemistry –
Strasse der Nationen 62 – D-09111 Chemnitz – GER
[email protected]
There is an enduring interest in the chemistry of ferrocenyl-substituted homo- and
hetero-aromatics, because such molecules can be regarded as model species for studying metal-metal electronic interaction. Furthermore, these π-conjugated organometallic compounds are qualified to design innovative electro-active materials like semiconducting polymers or molecular wires. The ferrocenyl moiety is a very promising
candidate for using it as a redox-active group with a good stability in the neutral
and in the oxidized state, enabling electrochemical reversible one-electron transfer
processes.[1,2] Within this presentation, the synthesis, properties and spectroelectrochemical studies of ferrocenyl-substituted thiophenes (type A and B molecules) are
reported. The influence of substituents on charge transfer interactions between the
iron centers will be discussed.
[1]
a) J. K. R. Thomas, J. T. Lin, J. Organomet. Chem. 2001, 637, 139; b) S. Ogawa, H.
Muraoka, R. Sato, Tetrahedron Lett. 2006, 47, 2479; c) F. Paul, S. Goeb, F. Justaud, G.
Argouarch, L. Toupet, R. F. Ziessel, C. Lapinte, Inorg. Chem. 2007, 46, 9036; d) R. Packheiser,
M. Lohan, B. Bräuer, F. Justaud, C. Lapinte, H. Lang, J. Org. Chem. 2008, 693, 2898; e) R.
Packheiser, P. Ecorchard, B. Walfort, H. Lang, J. Organomet. Chem. 2008, 693, 933; f) D.
E. Richardson, H. Taube, Coord. Chem. Rev. 1984, 60, 107. g) W. Kaim, B. Sarkar, Coord.
Chem. Rev. 2007, 251, 584.
[2]
a) S. C. Jones, S. Barlow, D. O’Hare, Chem. Eur. J. 2005, 11, 4473; b) S. Barlow, D.
O’Hare, Chem. Rev. 1997, 97, 637; c) I. M. Bruce, Coord. Chem. Rev. 1997, 166, 91; d) A.
Hildebrandt, D. Schaarschmidt, H. Lang, Organometallics 2011, 30, 556; e) A. Hildebrandt, U.
Pfaff, H. Lang, Rev. Inorg. Chem. 2011, 31, 111; f) A. Hildebrandt, H. Lang, Dalton Trans.
2011, 40, 11831; g) J. M. Speck, R. Claus, A. Hildebrandt, T. Rüffer, E. Erasmus, L. van As, J.
C. Swarts, H. Lang, Organometallics 2012, 31, 6373.
Poster 200
Saturday 9:00 - 11:30
257
Novel terminalalkynyl-substituted asymmetric zinc
phthalocyanine and its polymers via click reaction
Betul Nur Sen ∗ , Hatice Dincer∗ , Sinem Bayraktar† , Humeyra Mert Balaban†
∗
Chemistry – Istanbul Technical University – 34469 – Istanbul – TUR
†
Chemical Engineering – Hitit University – Uctutlar street number:10 – Corum – TUR
[email protected]
Phthalocyanines (Pcs) have been an area of increasing research for several years, due
to their applicability in a variety of fields, such as liquid crystals, semiconductors,
non-linear optics and electron transfer, among others.
Synthetic routes to symmetrical Pcs are relatively straightforward, starting from the
appropriately substituted phthalonitrile. However, unsymmetrical Pcs containing different substituents in the benzo rings are more difficult to obtain. In addition these
compounds provide the properties that can be used in advanced materials’ applications such as in particular non-linear optical properties.[1,2] Then the enormous
diversity of phthalocyanine - containing polymers, developed over thirty years of research, and offers the prospect of readily processed materials.[3] Recently, 1,3-dipolar
cycloadditions, from the reactions between alkynes and azides known as, “click reactions”, have been recognized as a useful synthetic methodology due to their being fast,
quantitative, reproducible, resistant to side reactions and highly tolerant to reaction
conditions.
In this study we aimed that the synthesis of asymmetric phthalocyanine-containing
polymers. For this purpose, firstly novel unsymmetrical terminalalkynyl substituted
zinc phthalocyanine will be synthesized from new 4-pent-4-ynyloxy-phthalonitrile and
4-tert-butylphthalonitrile using statistical condensation method. Then, ‘click’ reactions between azido-terminated polystyrene (PS) or poly(tert-butyl acrylate) (PtBA)
and alkynyl-terminated zinc phthalocyanine will yield Pc functional polymers. All
compounds will be characterized by 1 H NMR, 13 C NMR, FT-IR, UV-Vis, GPC and
elemental analysis.
[1]
F. Matemadombo, M. Durmus, C. Togo, J. Limson, T. Nyokong, “Characterization of manganese
tetraarylthiosubstituted phthalocyanines self assembled monolayers”, Electrochim. Acta 2009, 54
(23), 5557-5565.
[2]
Y. Q. Liu, Y. Xu, D. B. Zhu, T. Wada, H. Sasabe, X. S. Zhao, X. M. Xie, “Optical 2ndharmonic generation from langmuir-blodgett-films of an asymmetrically substituted phthalocyanine”, J. Phys. Chem. 1995, 99 (18), 6957-6960.
[3]
N.B. Mc Keown, J. Mater. Chem. 2000, 10 (9), 1979.
258
Saturday 9:00 - 11:30
Poster 201
Chemoselective additions of (trifluoromethyl)trimethylsilane
to C=N bond in α-imino ketones derived from arylglyoxals
Marcin Kowalski, Emilia Obijalska, Grzegorz Mlostoń
Department of Organic and Applied Chemistry – University of Lodz – Tamka 12 Street –
Lodz – POL
[email protected]
Synthesis of fluoroorganic compounds is a challenging topic of modern organic chemistry. Incorporation of fluorine atoms or perfluoroalkyl groups into the structure of organic molecules results in significant changes in their physical, chemical and biological
properties.[1] (Trifluoromethyl)trimethylsilane (so-called Ruppert’s-Prakash Reagent,
RPR) is one of the most convenient reagent used to nucleophilic trifluoromethylation of electrophilic subtrates.[2] The goal of presented study is to elaborate new,
simple procedure for synthesis of β-amino-β-(trifluoromethyl) alcohols of type 2 using easily available α-iminoketones 1 and (trifluoromethyl)trimethylsilane. There are
described in literature many methods for preparation of β-amino-α-(trifluoromethyl)
alcohols.[3] Relatively less papers concern preparation of β-amino-α-(trifluoromethyl)
alcohols. They are based on exploration of difficult available trifluoronitroethane or
N,S-ketals of trifluoropyruvaldehydes.[4] In the key step of our procedure additions
of RPR to 1 were performed in the presence of in situ generated HF (from KF or
KHF2) what allowed for activation of C=N bond. In optimised conditions adducts 2
were the main products. Further reduction of 2 led to desired aminoalcohols 3 with
very good diastereoselectivity.
Research were financed by the National Science Center in Poland (Grant ’SONATA’
# DEC-2011/03/D/ST5/05231)
[1]
(a) Kirsh, Modern Fluoroorganic Chemistry, Wiley-VCH, Weinheim, 2004; (b) J.-P. Bégué,
D. Bonnet-Delpon, Bioorganic and Medicinal Chemistry of Fluorine, Wiley, Hoboken, New
Jersey, 2008.
[2]
G. K. S. Prakash, M. Mandal, J. Fluorine Chem. 2001, 112, 123.
[3]
G. Mlostoń, E. Obijalska, H. Heimgartner, Journal of Fluorine Chem. 2010, 131, 830.
[4]
(a) A. K. Beck, D. Seebach, Chem. Ber. 1991, 124, 2897; (b) R. E. Marti, J. Heinzer, D.
Seebach, Liebigs Ann. 1995, 1193; (c) P. Bravo, M. Crucianelli, T. Ono, M. Zanda, Journal of
Fluorine Chemistry 1999, 97, 27.
Poster 202
Saturday 9:00 - 11:30
259
Reactivity of palladium carboxylate complexes towards
acetonitrile
∗
Oleg Shishilov ∗ , Nailya Akhmadullina† , Andrei Churakov∗ , Inessa Efimenko∗
Kurnakov Institute of General and Inorganic Chemistry of RAS – Leninsky pr., 31 –
Moscow – RUS
†
Baikov Institute of Metallurgy and Material Science of RAS – Leninsky pr., 49 –
Moscow – RUS
[email protected]
It’s well-known that nitriles undergo catalytic transformations, including C-C, C-N
and C-O coupling reactions with rearrangement of nitriles or dimerization of products
forming nitrogen-containing compounds of different types in the presence of complexes
of transition metals and especially platinum metals. We studied reactions of two
classes of palladium carboxylate compounds - binary carboxylates [P d(RCO2 )2 ]n and
nitrosyl carboxylates P d4 (N O)2 (RCO2 )6 - with acetonitrile in some common organic
solvents. Binary carboxylates are a basic class of palladium carboxylate complexes
and nitrosyl carboxylates were chosen due to potential multifunctionality of nitrosyl
groups. For instance, earlier it was shown that N Ox -species promote transfer of
oxygen and reoxidation of palladium in catalytic processes.
It was found that reaction of palladium acetate P d3 (µ-CH3 CO2 )6 with acetonitrile
in benzene leads to formation of binuclear complex of palladium(II) P d2 (C6 H4 -oC(CH3 )=N H)2 (µ-CH3 CO2 )2 , which contains coordinated 1-phenylethanimine that
forms as a result of C-C-coupling between nitrile and arene molecules. Reactions of
polynuclear nitrosyl carboxylate complexes P d4 (N O)2 (RCO2 )6 of palladium(II) with
acetonitrile in acetone in the presence of water lead to formation of complexes P d5 (µN O)(µ-C6 H11 CO2 )7 (µ, µ-CH3 C(=N )OC(=N )CH3 ) and P d5 (µ-N O)(µ-N O2 ) (µCM e3 CO2 )6 (µ, µ-CH3 C(=N )OC(=N )CH3 ), which are the first palladium complexes containing coordinated acetimidic anhydride. The complexes belong to a new
topological type of carboxylate palladium compounds with 5-nuclear cyclic metalcore. Acetimidic anhydride forms as a result of complicate hydration process conjugated with C-O-coupling. Also complex P d5 (µ-N O)(µ-N O2 )(µ-CM e3 CO2 )6 (µ, µCH3 C(=N )OC(=N )CH3 ) is the first fully characterized palladium carboxylate compound containing nitrosyl and nitrite groups together.
We are grateful to the Council of the President of the Russian Federation for young
scientists for financial support (project 966.2012.3).
Molecular structure of
P d5 (µ-N O)(µ-N O2 )(µ-CM e3 CO2 )6 (µ, µ-CH3 C(=N )OC(=N )CH3 )
260
Saturday 9:00 - 11:30
Poster 203
Didecyldimethylammonium salts of amino acids - the
characteristics and application directions
Paula Ossowicz ∗ , Zbigniew Rozwadowski∗ , Ewa Janus† , Ryszard Pilawka‡
∗
West Pomeranian University of Technology, Szczecin – 42 Piastów Ave. – Szczecin – POL
†
Institute of Organic Chemical Technology –
West Pomeranian University of Technology, Szczecin – Pulaski Str. 10 – Szczecin – POL
‡
Institute of Polymers – West Pomeranian University of Technology, Szczecin –
Pulaski Str. 10 – Szczecin – POL
[email protected]
Currently, the attention is focused on a new generation of ionic liquids, which are
derived from natural raw materials such as amino acids. Amino acid ionic liquids are
an alternative to ionic liquids, based solely on petrochemical raw materials. Amino
Acid Ionic Liquids derived from biorenewable raw materials are more biocompatible,
because of greater biodegradability in the environment and lower toxicity (ecotoxicity
and cytotoxicity).
The synthesis, identification and physical properties of didecyldimethylammonium
salts of L amino acids were presented. Identification was based on 1 H NMR, 13 C
NMR, FT-IR, UV-VIS analyses. The physical properties of new chiral ionic liquids,
for example the density, viscosity, surface tension, specific rotation, water content,
thermal stability (TG) and phase transformations (DSC) were determined. Didecyldimethylammonium salts of L-amino acids salts were soluble in water and were
also characterized by surface tension, critical micelle concentration and stabillity in
alkaline and acid solution.
Synthesis of didecyldimethylammonium salts of amino acids
Poster 204
Saturday 9:00 - 11:30
261
Design and Synthesis of a new Galanthamine Delivery
System
Mihaela-Liliana Ţînţaş, Lénaig Foucout, Sylvain Petit, Sylvain Oudeyer,
Cyril Papamicaël, Vincent Levacher
UMR CNRS 6014, IRCOF Rouen, INSA de Rouen – Rue Tesniere 1 –
Mont-Saint-Aignan – FRA
[email protected]
Galanthamine is one of the acetylcholinesterase inhibitors (AChEIs) prescribed as
anti-Alzheimer Disease (AD) drug. It has a distinct mode of action, not observed for
the other inhibitors, being a competitive and reversible AChEI; an allosteric modulator of nicotinic acetylcholine receptors improving their functioning by helping the
release of ACh; and modulates the levels of other neurotransmitters involved in dementia: glutamate, serotonin and GABA. The inhibiting properties of galanthamine
are considered quite modest, but its multiple actions make it one of the most efficient AD therapy drug. It was observed in numerous cases that long treatment with
galanthamine produces many side effects (eg. nausea, vomiting, diarrhea, dizziness,
etc.) causing treatment disruption. AD patients are dependent of continuous administration of AChEI to have day-to-day functioning and maximize their quality of life
as much as possible. A way to overcome the side-effects of a neuroactive drug is to
ensure a brain targeted transport to the active site mediated by a carrier. One such
chemical delivery system towards brain was developed by Bodor[1] and is based on dihydropyridine–pyridinium redox couple. The neuroactive drug is covalently linked to
a dihydropyridine moiety that plays the role of a lipoidal carrier towards brain. Dihydropyridine is an unstable and chemically fragile moiety. We developed a new stable
and assertive chemical delivery system based on a dihydroquinoline–quinolinium redox couple.[2,3] We applied this system to galanthamine, as schematically represented
below. This transformation represents a valuable drug modification strategy which
increases the chances of a site-specific and sustained delivery of galanthamine inside
brain. Dihydroquinoline moiety will ensure the transport of the drug to the central
nervous system through the lipophilic blood brain barrier (BBB) by passive diffusion.
Then oxidation into a charged quinolinium salt will prevent the system to cross back
the BBB again. Enzymatic cleavage will liberate galanthamine to target directly the
AChE implied in AD followed by its normal metabolism and clearance. Liberation of
the drug just inside the brain will lead to lower drug doses and less undesirable side
effects.
[1]
L. Prokai, K. Prokai-Tatrai, N. Bodor, Med. Res. Rev. 2000, 20, 367-416.
L. Foucout, F. Gourand, M. Dhilly, P. Bohn, G. Dupas, J. Costentin, A. Abbas, F. Marsais, L.
Barré, V. Levacher, Org. Biomol. Chem. 2009, 7, 3666-3673.
[3]
P. Bohn, N. Le Fur, G. Hagues, J. Costentin, N. Torquet, C. Papamicael, F. Marsais, V.
Levacher, Org. Biomol. Chem. 2009, 7, 2612-2618.
[2]
262
Saturday 9:00 - 11:30
Poster 205
Optical Anisotropy of Pb Nanowires on Si(557)
Arne Baumann ∗ , Jochen Räthel∗ , Eugen Speiser∗ , Daniel Lükermann† ,
Christopher Krich† , Christoph Tegenkamp† , Norbert Esser∗
∗
Nanostrukturen – Leibniz-Institut für Analytische Wissenschaften - ISAS - e. V. –
Albert-Einstein-Straße 9 – 12489 Berlin – GER
†
Institut für Festkörperphysik – Leibniz Universität Hannover – Appelstraße 2 –
30167 Hannover – GER
[email protected]
Reducing the dimensionality of metal films on semi-conductor surfaces can lead to the
appearance of interesting physical phenomena. Due to the high electron correlation it
could be not longer accurate to describe the electron gas by traditional Fermi liquid
theory. For example, the inherent instabilities of 1D electronic systems, like Peierls
instabilities, can entail the formation of charge and spin density waves, moreover the
systems may exhibit Luttinger liquid behavior. The goal of our work is to elucidate
these phenomena by the means of optical methods, such as reflectance anisotropy
spectroscopy (RAS).
Metal nanowire model systems involve noble metal, In or Pb nanowires on vicinal
Si or Ge surfaces. One particular interesting system is Pb on Si(557), where the
adsorption of approximately 1.3 monolayers of Pb onto the clean Si(557) surface
induces a reorganization of the surface structure. The clean Si(557) surface consists
of (111) oriented terraces and (112) oriented steps. After the adsorption of Pb low
energy electron dispersion patterns and scanning tunneling microscopy measurements
show an evenly stepped surface decorated with distant Pb nanowires.
At low temperatures (< 78 K) this system shows almost exclusively electronic conductivity parallel to the steps. Increasing the temperature above this temperature
causes a phase transition and enables conductivity perpendicular to the wires. A reordering of the surface induces a change in the electronic properties and with this also
in the dielectric function. Hence, in this clearly anisotropic system it is possible to
apply RAS, in connection with density functional theory based calculations, to study
the anisotropic optical transitions in the surface band structure. By comparing the
RAS spectra of the clean Si(557) surface with the Pb covered surface it is possible
to identify signals belonging to adsorption induced states. Furthermore, by carrying
out temperature dependant measurements it can be possible to observe the appearance of new anisotropic transitions below 78 K, indicating a change in the surface
band structure of the system, as well as changes in the optical conductance behavior
accompanying the phase transition.
Poster 206
Saturday 9:00 - 11:30
263
Micelle Formation
Marta Cybulak
Faculty of Chemistry – Maria Curie-Sklodowska University in Lublin –
pl. Marii Curie-Sklodowskiej 2 – Lublin – POL – Lublin – POL
[email protected]
The structure and thermodynamics of formation of mixed micelles is of great theoretical interest. Micelles are also often present and often integrally involved in practical
processes. For example, in a small pore volume surfactant flooding process (sometimes
called micellar floding), the solution injected into an oil field generally contains 5-12
weight % surfactant and the surfactant is predominately in micellar form in the reservoir water. In detergency, solubilization can be important, so micelles are generally
present in the detergent solution. In micellar – enhanced ultrafiltration, a separation
technique to remove dissolved organic from water, micelles effect the separation.
The Critical Micelle Concentration (CMC) is the lowest surfactant concentration at
which micelles form – the lower the CMC, the greater the tendency of a system to
form micelles. When the total fraction of surfactant equals the CMC, an infinitesimal
fraction of surfactant is present as micelles.
[1]
W.B. Gogarty, J. Pet. Technol. 1983, 35, 1581.
K. Shinoda in “Colloidal Surfactants”, K. Shinoda, T. Tanamushi, T. Nakagawa, T. Isemura,
Academic Press: New York, 1963, Chapter 1.
[3]
R.F. Kamrath, E.I. Frances, J. Phys. Chem. 1984, 88, 1642.
[4]
K. Shinoda, J. Phys. Chem. 1954, 58, 541.
[5]
K.J. Mysels, R.J. Otter, J. Colloid Sci. 1961, 16, 474.
[6]
B.W. Barry, J.C. Morrison, G.F. Russel, J. Colloid Interface Sci. 1970, 33, 554.
[2]
264
Saturday 9:00 - 11:30
Poster 207
Shear-induced structure formation in a mixture of a nonionic
associative polymer and anionic surfactant
Alena Tomsik , Jaroslav Katona, Sandra Njaradi
Department of Biotechnology and Pharmaceutical Engineering –
University of Novi Sad, Faculty of Technology –
Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia – Novi Sad – SRB
[email protected]
Mixtures of polymers and surfactants are commonly found in a wide range of consumer products. Interaction between polymers and surfactants influence different
properties of these products, e.g. stability, flow properties, phase behavior etc.[1-3] In
this work, influence of shear rate on flow properties of a mixture of hydroxypropylmethyl cellulose (HPMC), a nonionic associative polymer, and sodium dodecylsulfate
(SDS), an anionic surfactant was investigated. Binary mixtures composed of 0.70%
wt. HPMC and SDS concentration ranging from 0.00% to 2.00% wt. were prepared
in deionized water and in 0.01M NaCl. Rheological properties of the mixtures were
examined by determining the steady state viscosity under different shear rates. At
low shear rates, HPMC and SDS mixtures show Newtonian plateau where viscosity is
independent on shear rate. On further increase in shear rate, a typical shear thinning
behavior with a power low decrease in viscosity takes place. However, in mixtures
with SDS concentration higher than 0.15% SDS, above a critical shear rate an increase in viscosity accompanied with an increase in the first normal stress difference
occurs. The shear thickening behavior indicates shear induced structure formation
due to HPMC-SDS interaction. The shear thickening flow takes place in both water
and 0.01M NaCl binary mixtures. The critical shear rate is lower, while the viscosity
increase is more pronounced in the 0.01M NaCl mixtures than in the corresponding
deionised water mixtures. This is attributed to a stronger HPMC-SDS interaction
due to charge screening effect in HPMC-SDS complex by sodium cations. When
SDS concentration is higher than 1.50% wt. no shear thickening is observed in the
investigated shear rate range.
[1]
B. Nystrom, A.-L. Kjoniksen, B. Lindman, “Effect of temperature, surfactant, and salt on the
rheological behavior in semidilute aqueous systems of a nonionic cellulose ether”, Langmuir 1996,
12, 3233-3240.
[2]
J. M. Katona, V. J. Sovilj “Rheological investigation on dynamics and structure of separated
phases in polymer-mixture - ionic surfactant ternary mixtures”, Carbohydrate Polymers 2008,
74, 193-200.
[3]
J.M. Katona, V.J. Sovilj, L.B. Petrović, “Microencapsulation of oil by polymer mixture ionic
surfactant interaction induced coacervation”, Carbohydrate Polymers 2010, 79, 563-570.
Poster 208
Saturday 9:00 - 11:30
265
Studies of Dodecane/Water Interfaces by
Polarization-Dependent and Time-Resolved Second
Harmonic Generation
Michal Hamkalo, Piotr Fita
Faculty of Physics – Institute of Experimental Physics, University of Warsaw – Hoza 69 –
Warsaw – POL
[email protected]
Properties of organic dyes: eosin B, Rhodamine 640, Rhodamine 6G, Malachite
Green, and Sulforhodamine 101, at dodecane/water interfaces have been investigated
with polarization-dependent and time-resolved surface second harmonic generation
(SHG).[1,2] In this experimental technique an interface under study is illuminated
(probed) with a beam of femtosecond pulses and the second harmonic of the probe
beam is detected using a sensitive photodetector. Due to symmetry the second harmonic is generated only in a very thin layer separating two different phases, which
ensures high spatial selectivity.
This study was focused on polarization-dependent SHG, in which the probe beam is
linearly polarized and the plane of polarization can be continuously rotated using a
halfwave plate. Polarization of the detected second harmonic is selected by a polarizer
located after the sample and can be either parallel or perpendicular to the plane of
incidence. For both polarizations of the detected light its intensity is measured as a
function of the direction of polarization of the probe beam.
The investigation aims to describe the behavior of organic molecules at interfaces
between 2 non-mixing liquids. In polarization-dependent measurements 3 parameters
were varied: the dye concentration, the intensity of the laser beam and the age of
the sample. It has been found that both, the dye concentration and - surprisingly,
the probe beam intensity affect the polarization dependence of the second harmonic
intensity. Comparison of the results obtained for different conditions suggests that
the state of molecules at the surface changes and aggregates are formed at higher
dye concentrations. Nevertheless aggregation alone cannot explain all the observed
phenomena, therefore we will carry out additional time-resolved measurements which
should help to identify the processes occurring in molecules adsorbed at the interface.
[1]
[2]
K. B. Eisenthal, J. Phys. Chem. 1996, 100, 12997-13006.
J. C. Conboy, J. L. Daschbach, G. L. Richmond, J. Phys. Chem. 1994, 98, 9688-9692.
266
Saturday 9:00 - 11:30
Poster 209
Emission Properties of Quantum Dots Affected by the
Ligand Shell – Theory and Experiment
†
Susanne Leubner ∗ , Soheil Hatami† , Tommy Lorenz∗ , Jan-Ole Joswig∗ ,
Nikolai Gaponik∗ , Ute Resch-Genger† , Alexander Eychmüller∗
∗
Physical Chemistry – TU Dresden – Dresden – GER
BAM Federal Institute for Materials Research and Testing – Berlin – GER
[email protected]
In recent years semiconductor quantum dots (QDs) have drawn a broad interdisciplinary attention as an attractive choice for the use in light-emitting devices and
imaging techniques. This is strongly related to their superior optical properties compared to other classes of functional dyes, such as high photostability, large extinction
coefficient, tunable and narrow band gap luminescence and high photoluminescence
(PL) quantum yields.
Especially the PL quantum yield is a significant characteristic for the emission quality
and is often cited in literature. However, for valuable data on one hand a proper
determination procedure is crucial and on the other hand the understanding of particle
properties influencing the emission is of great importance. In detail, the optical
properties of the nanocrystals are affected by both the core material and the ligand
shell. As the surface chemistry of QDs can still be tuned after the synthesis, a complete
understanding of the impact of the stabilizing shell on the emission properties is
promising for the design of highly emitting materials.
Hence, this study discusses the proper experimental PL quantum yield determination
as well as the analytical study of the nanoparticle surface and its relation to the
PL quantum yield for the model system of aqueous synthesized CdTe nanocrystals
capped with thiols. The investigation of the ligand shell includes analytical techniques
together with theoretical calculations.
Poster 210
Saturday 9:00 - 11:30
267
N -Aminoalkylation of heterocycles with α-amidosulfones
Marc Montesinos Magraner , Gonzalo Blay, Rosa María Girón, José Ramón Pedro
Departament de Química Orgànica – Universitat de València – Dr. Moliner, 50 –
Burjassot – ESP
[email protected]
Nitrogen containing heterocycles are present in a vast number of natural products
and biologically active molecules.[1] So, the functionalization of these compounds is
an important goal in organic chemistry. However, the introduction of an aminoalkyl
group is less developed due to the low reactivity of imines as electrophiles.[2]
Recently, we have carried out the first regioselective aminoalkylation of indoles 1 with
α-amidosulfones (7) in either the C -3 or N -1 position under basic conditions. Both
methods are also useful to introduce different aminoalkyl moieties in other nitrogen
containing heterocycles.
In this communication we present an extension of the scope of the reaction of aminoalkylation on the nitrogen using different heterocycles as 7-azaindoles 2, purines 3, pyrrole
(4), benzimidazole (5) or indazole (6). Our method afforded heterocycles functionalized with an aminomethyl group bearing aryl, heteroaryl or alkyl substituents.
Financial support from the Ministerio de Ciencia e Innovación and FEDER (CTQ 200913083) and from Generalitat Valenciana (ACOMP/2012/212 and ISIC/2012/001) is acknowledged. M.M. thanks the Universitat de València for a pre-doctoral grant.
[1]
(a) I. S. Young, P. D. Thorntonb, A. Thompson, Nat. Prod. Rep. 2010, 27, 1801; (b) K.
Kumar, H. Waldmann, Angew. Chem. Int. Ed. 2009, 48, 3224; (c) R. Garg, S. P. Gupta, H.
Gao, M. S. Babu, A. K. Debnath, C. Hansch, Chem. Rev. 1999, 99, 3525.
[2]
(a) H. Zhang, C.-X. Lian, W.-C. Yuan, X.-M. Zhang, Synlett 2012, 23, 1339; X. (b) Mi, S.
Luo, J. Hea, J.-P. Chen, Tetrahedron Lett. 2004, 45, 4567; (c) W. Xie, K. M. Bloomfield, Y. Jin,
N. Dolney, P. G. Wang, Synlett 1999, 498.
268
Saturday 9:00 - 11:30
Poster 211
Surface modification of segmented copolymers via hydrolysis
and aminolysis
Agata Niemczyk , Zygmunt Staniszewski, Mirosława El Fray
Polymer Institute – West Pomeranian University of Technology, Szczecin –
10 Pułaski Street – Szczecin – POL
[email protected]
Polymeric implants are an important class of biomaterials, which have facilitated the
development of numerous prostheses and implants for orthopedic and cardiovascular
applications, which are exposed to prolonged contact with tissue. However, infections
are a common complication arising from the tissue-biomaterial interaction, leading to
clinically significant problems. The major role of implant susceptibility to infections
is associated with the adhesion of a pathogen to the implant surface, therefore one
of the strategies to obtain better surface resistance to microbial colonization is their
modification.
Poly(aliphatic/aromatic-ester) (PED) multiblock copolymers with different concentration of hard segment (poly(ethylene terephthalate) (PET)) and soft segments (dilinoleic acid (DLA)), namely 50, 55, 60, 65 and 70% wt. were modified to induce surface
hydrolysis and aminolysis, respectively. The chemical structure of the neat PET/DLA
is shown in Figure 1.
Hydrolysis of PET/DLA copolymers in concentrated alkaline solution produced a
carboxyl-enriched surface, and aminolysis in 1,6-hexanediamine /propanol solution
introduced amino groups. That surface functionalization leads to the negative (COO) or positive (NH3+) charges on copolymer surface thus providing activated groups
capable anchoring polyelectrolytes in a layer-by-layer process. The changes of surface
chemistry were monitored and verified mainly by FTIR spectroscopy.
Figure 1. Chemical structure of PET/DLA copolymers
Poster 212
Saturday 9:00 - 11:30
269
DFT-Study of the adsorption process of GaP-precursors on
Si(001)(2x1) in Metal Organic Vapour Phase Epitaxy
Phil Rosenow , Ralf Tonner
Fachbereich Chemie – Philipps-Universität Marburg – Hans-Meerwein-Straße 4 –
Marburg – GER
[email protected]
Lasers on silicon are of particular interest in optoelectronics and chip design. A system of great interest is the quarternary III/V-semiconductor Ga(NAsP). In order to
avoid lattice mismatches GaP is used as an intermediate layer.[1,2] The electronic
properties depend highly on the initial structure of the GaP-adlayer. Thus a DFTstudy has been started in order to gain a better understanding of the process using
the VASP code.
Calculations on gas-phase decomposition reactions suggest that hardly any decomposition occurs in the gas phase. Therefore surface reactions are supposed to play
an important role in the adsorption process. The reactivity of the surface is determined by the degree of hydration. Experimental studies of the silicon surface show
that under high temperature MOVPE reactions the surface is clean whereas at low
temperature conditions it is hydrated.[3]
Adsorption reactions at the hydrated are possible under insertion in Si-H or Si-Si
bonds or under release of dihydrogen or hydrocarbon ligands. Adsorption is preceded
by physisorption accompanied by activation of Si-H bonds.
Layer growth depends on residues attached to the adsorbed atoms. t-Butyl groups
block neighbouring adsorption sites whereas mere hydrogen atoms have hardly any
influence on adsorption. A notable exception is the case of gallium hydride species
where a borane-like species occurs which leads to strongly stabilized structures.
[1]
B. Kunert, K. Volz, J. Koch, W. Stolz, Appl. Phys. Lett., 2006, 88, 182108.
I. Németh, B. Kunert, W. Stolz, K. Volz, J. Cryst. Growth, 2008, 310, 1595.
[3]
U. Höfer, L. Li, T. F. Heinz, Phys. Rev. B, 1992, 45, 9485.
[2]
270
Saturday 9:00 - 11:30
Poster 213
Rapid Preparation of
∗
∗
15
N3 -labeled Enniatins
∗
Svenja Schloß , Matthias Proske , Irmtraut Zaspel∗ , Matthias Koch∗ , Ronald Maul∗
1.7 Lebensmittelanalytik – Bundesanstalt für Materialforschung und -prüfung (BAM) –
Richard-Willstätter-Straße 11 – Berlin – GER
†
Institut für Forstgenetik – Johann Heinrich von Thünen-Institut –
Eberswalder Chaussee 3a – Waldsieversdorf – GER
[email protected]
In the class of depsipeptides, the enniatins (ENN) are becoming increasingly significant. As secondary metabolites of various Fusarium species, they represent a common
source of food and feed contamination mainly affecting cereal products.[1] Due to the
limited data on the toxicity, occurrence, and contamination levels ENN are also referred to as “emerging mycotoxins”.[2] The detection of the analytes by means of mass
spectrometry has been found as a suitable method. However, coelution of matrix components may lead to ion suppression or ion enhancement effects in LC-MS-analysis.
Thus, for a reliable quantitation the use of isotope-labeled internal standards is advisable. All matrix effects influence the internal standard and the analyte in the same
way. Also losses during sample processing can be compensated by addition of the
isotope labeled internal standard at the beginning of the sample extraction.
The cultivation of Fusarium cultures and the isolation of unmarked ENN have been
successfully carried out. According to Hu et al., the four main compounds ENN A,
A1, B and B1 can be replaced with their 15 N3 -labeled versions by growing a strain
of Fusarium in an artificial culture medium with Na15 NO3 as sole nitrogen source.[3]
In variation from this, the labeled ENN were isolated by a modified rapid cleanup of
the mycelium.
After a solid-liquid extraction of the ENN from the homogenized fungal mycelium of
Fusarium avenaceum, a fractionation and purification was carried out on a normal
phase silica gel column with cyclohexane, ethyl acetate and methanol as eluents. The
fractions containing the target analytes were identified by subsequent LC-MS analysis
and evaporated to dryness. The residue was dissolved in methanol.
The pattern of the native ENN and the 15 N-ENN (single, double and triple labeled)
and the accurate masses were determined by LC-QToF-MS. Less than 2 percent of
unlabeled ENN was detected in the isolated standard. Hence, the obtained isotope
labeled ENN will be suitable for following quantitative LC-MS based ENN analyses
in food and feed.
[1]
Malachova et al., J. Agric. Food Chem. 2011, 28, 59(24), 12990-12997.
M. Jestoi, Crit Rev Food Sci Nutr. 2008, 48(1), 21-49.
[3]
Hu et al., J. Agric. Food Chem. 2012, 25, 60(29), 7129-36,
[2]
Poster 214
Saturday 9:00 - 11:30
271
Novel phthalocyanine derivatives possessing dietheroxy
substituents at non-peripheral positions as singlet oxygen
generators
Lukasz Sobotta ∗ , Marcin Wierzchowski† , Tomasz Goslinski† , Jadwiga Mielcarek∗
∗
†
[email protected]
Photodynamic therapy (PDT) is a novel promising treatment of cancer and precancer diseases, and of potential utility in bacterial and viral infections. In PDT
three components are necessary, such as photosensitizer, molecular oxygen and light
of an appropriate wavelength. Interestingly, an excited form of a drug interacts with
molecular oxygen in its tryplet state generating singlet oxygen. Singlet oxygen can
react with many biological cell components causing their destruction.[1] The photodynamic efficacy of three phthalocyanines (Pc-1, Pc-2, Pc-3) was studied and their
potential usefulness in photodynamic therapy was evaluated (Fig.1). The generation
of singlet oxygen by Pc-1 – Pc-3 was studied. 1,3-Diphenyloisobenzofuran (DPBF)
was used as a singlet oxygen quencher. The photooxidation process was investigated
in aerobic conditions and in an environment with limited access of oxygen (Fig.1).[1]
According to these studies, phthalocyanines Pc-1 and Pc-2 generate singlet oxygen,
but in the environment with limited access of oxygen this process occurs to a much
lesser extent. The quantum yield of singlet oxygen generation was estimated by comparing with the reference macrocycle (zinc phthalocyanine). Moreover, Pc-2 appeared
to be the most efficient photosensitizer among the series of macrocycles studied. The
following values of the quantum yield of singlet oxygen generation in DMF and DMSO
were found 0.32 and 0.30 for Pc-1, 0.46 and 0.34 for Pc-2, respectively.
Fig.1 Singlet oxygen assessment spectra of Pc-1 were plotted during measurement, inset
presents process of DPBF oxidation)
[1]
R. R. Allison, G. H. Downie, R. Cuenca, X. Hu, C. J. H. Childs, C. H. Sibata, Photodiagn
Photodyn 2004, 1, 27-42. [2] W. Szczolko, L. Sobotta, P. Fita, T. Koczorowski, M. Mikus, M.
Gdaniec, A. Orzechowska, K. Burda, S. Sobiak, M. Wierzchowski, J. Mielcarek, E. Tykarska, T.
Gośliński, Tetrahedron Lett. 2012, 53, 2040-44.
This study was supported by the National Science Centre under Grant No. N N401 067238.
272
Saturday 9:00 - 11:30
Poster 215
Incorporation and Organization of β-Peptides in Lipid
Membranes
Diana Petersen, Tatjana Polupanow, Ulf Diederichsen
Institute of Organic and Biomolecular Chemistry – Georg-August-University Göttingen –
Tammannstr. 2 – 37077 Göttingen – GER
[email protected]
Transmembrane proteins are spanning the lipid bilayer and acting as gateways for a
selective transport of small molecules across the membranes.[1] The structural similarities of one or more hydrophobic regions in terms of α-helices or α-helical aggregates
are common in transmembrane proteins.[2] Properties like folding, channel formation
and transmembrane signalling are essentially affected by the non-covalent interactions between the helix-motifs. Moreover, important are also the surrounding lipids
and their orientation in the membrane (Scheme 1).[3] In order to better understand
intermolecular interactions and organization of transmembrane proteins, we have chosen β-peptides as novel model system to study membrane assembly. β-Peptides are
promising motifs to show various secondary structures with high helical content.[4,5]
Therefore, various β-peptides with different hydrophobic side chains will be synthesized and examined regarding helix topology and membrane incorporation.
Scheme 1: Schematic illustration of potential peptide assembly based on molecular
recognition of helix side chains inside the membrane bilayer. Left: Aggregation via
electrostatic attraction between a positive charged lysine residue and a negative charged
glutamic acid side chain. Right: Helical assembly obtained by hydrogen bonding of two
asparagine residues.
[1]
K. Murata, K. Mitsuoka, T. Hirai, T. Walz, P. Agre, J. B. Heyman, A. Engel, Y. Fujiyoshi,
Nature 2000, 407, 599-605.
[2]
O.S. Andersen, R. E. Koeppe, Annu. Rev. Biophys. Biomol. Struct. 2007, 36, 107-130.
[3]
J. U. Bowie, Nature 2005, 438, 581-589.
[4]
D. Seebach, A. K. Beck, D. J. Bierbaum, Chem. Biodivers. 2004, 1, 1111-1239.
[5]
S. H. Gellman, Acc. Chem. Rev. 1998, 31, 173-180.
Poster 216
Saturday 9:00 - 11:30
273
Chromatographic retention parameters as predictors of the
biological activity of some aldopentose and aldohexose
derivatives
Strahinja Kovacevic, Lidija Jevric, Sanja Podunavac Kuzmanovic, Natasa Kalajdzija,
Eva Loncar
Department of Applied and Engineering Chemistry –
University of Novi Sad, Faculty of Technology – Bulevar cara Lazara 1 – Novi Sad – SRB
[email protected]
Chromatographic retention parameters, R0M and C0 , have been used to form mathematical models for prediction of the biological behavior of 1,2-O-izopropylidene
derivatives of aldohexoses and 1,2-O-cyclohexylidene derivatives of aldopentoses. The
biological activity of these molecules was confirmed in several scientific papers.[1−3]
In silico biological descriptors of the examined molecules, such as enzyme inhibition (EI), nuclear receptor ligand binding (NRL), kinase inhibition (KI), protease
inhibition (PI), ion channel modulation (ICM), G protein-coupled receptors binding
(GPCR), and Caco-2 cells permeability (Caco-2), were calculated by PreADMET [4]
and Molinspiration [5] software. The retention factors R0M and C0 were determined by
normal-phase thin-layer chromatography in the solvent systems cyclohexane : ethylacetate, cyclohexane : acetone, cyclohexane : dioxane, cyclohexane : tetrahydrofuran
and benzene : acetone, and silica gel as stationary phase.
The correlations between defined biological descriptors and retention parameters were
determined by statistical software Statistica 8.[6] Quadratic equations that relate R0M
and C0 with EI, PI, KI, NRL, ICM, GPCR and Caco-2 were established. The validity
of the generated mathematical models was confirmed by standard statistical measures
(correlation coefficient (r), the standard error of estimation (s), Fisher’s value (F)),
and cross-validation parameters (PRESS value, TSS value, Spress value, r2cv , r2adj ).[7]
Optimal values of the cross-validation parameters confirm predictive ability of the
estimated equations.
On the basis of the obtained results it can be concluded that etablished mathematical
models can be used for prediction of the biological behavior of the examined molecules.
It indicates that retention parameters obtained by normal-phase chromatography can
successfully predict some biological characteristics of the examined aldopentose and
aldohexose derivatives.
[1]
G. Catelani, F. D’Andrea, M. Landi, C. Zuccato, N. Bianchi, R. Gambari, Carbohydr. Res.
2006, 341, 538.
[2]
G. Catelani, F. D’Andrea, E. Mastrorilli, N. Bianchi, C. Chiarabelli, M. Borgatti, D. Martello,
R. Gambari, Bioorg. Med. Chem. 2002, 10, 347.
[3]
R. Trivedi, E. R. Reddy, Ch. Kiran Kumar, B. Sridhar, K. Pranay Kumar, M. Srinivasa Rao,
Bioorg. Med. Chem. Lett. 2011, 21, 3890.
[4]
preadmet.bmdrc.org
[5]
www.molinspiration.com
[6]
www.statsoft.com
[7]
S. Podunavac Kuzmanovic, D. Cvetkovic, S. Gadzuric, APTEFF 2011, 42, 251.
274
Saturday 9:00 - 11:30
Poster 217
Selective Oxidation of Methane over VOX Catalysts: Effect
of CO2 admixtures on formaldehyde selectivity
Enno Schönborn, Philipp Wallis, Claudio Pirovano, Narayana Kalevaru, Andreas Martin,
Sebastian Wohlrab
Leibniz-Institut für Katalyse e.V. – A.-Einstein-Str. 29a – Rostock – GER
[email protected]
The selective oxidation of methane to oxygenates is one of the challenging tasks in
catalysis. Promising catalytic systems with enhanced selectivity for formaldehyde are
based on vanadium oxide species supported on mesoporous silicas.[1, 2] In the present
work, we compare properties of differently prepared VOX catalysts supported on
mesoporous silicas (MCM-41, SBA-15) using different analytical methods. In addition, we show the influence of CO2 -admixtures on the catalytic performance of these
catalysts for the selective oxidation of methane to formaldehyde.
Isolated low-molecular VOX species are assumed to be the active sites in the selective
oxidation of methane.[3] However, analytic investigations of the catalysts prepared under different conditions showed concise differences related to preparation method as
well as supports used.[4] The catalytic oxidation experiments are congruent with the
analytical results. Besides such preparative developments, the process can be further
positively influenced by technological variations. Primarily, the total oxidation can
be suppressed by CO2 admixtures to the reactant feed. Fig. 1 shows such effect over
VOX /SBA-15 catalyst prepared by IWI method. Starting from a feed mixture of
7.5:1:4:7.5 (CH4 : O2 :N2 :CO2 ) methane conversion xCH4 was 5.6%. The formaldehyde selectivity SHCHO was found to be 19.6%. After 3 h the CO2 was substituted
by N2 and xCH4 increased while SHCHO decreased tremendously. If a continuous
flow of CO2 was used for the whole reaction time we observed only a slight increase of
xCH4 and appreciably lower decrease of SHCHO . It can be concluded that CO2 in the
feed reduces the overall conversion of methane while the selectivity to formaldehyde
is increased.
From this, we can conclude that CO2 admixtures to the reactant feed have a positive influence on the methane oxidation reaction which leads to enhancement of the
formaldehyde selectivity. Together with methods including rapid formaldehyde isolation from the reaction zone such CO2 admixtures to the feed help to reduce total
oxidation of methane to carbon dioxide.
Fig. 1. Influence of CO2 admixtures on the performance of VOX catalyst (T = 923 K;
cat. amount = 100 mg; GHSV = 180,000 lkg−1 h−1 , CH4 :O2 :N2 :admixture =
7.5:1:4:7.5, 6 h), left: xCH4 , right: SHCHO .
[1]
H. Berndt et al., J. Catal. 2000, 191, 384.
L.D. Nguyen et al., J. Catal. 2006, 237, 38.
[3]
V. Fornés et al., Appl. Catal. A: Gen. 2003, 249, 345.
[4]
C. Pirovano et al., Catal. Today 2012, 192, 20.
[2]
Poster 218
Saturday 9:00 - 11:30
275
One-step synthesis of tetrazolo[1,5-a]pyridines from pyridine
N -oxides
Shanshan Liu, Christoph Tzschucke
Department of Chemistry and Biochemistry – Freie Universität Berlin – Takustr. 3 –
D- 14195 Berlin – GER
[email protected]
Organic azides are important functional groups, they are used as precursors to primary amines[1] , nitrenes[2] , and triazoles[3] . Tetrazole is the predominant species in
the azide/tetrazole equilibrium of 2-azidopyridines. We seek an practical and convenient manufacturing route to introduce azides using cost efficient reagents. Different
sulfonyl and phosphoryl reagents and various solvents were compared in this reaction.
Various substituted tetrazolopyridines were prepared in good to excellent yield from
the corresponding pyridine-N -oxides. Reaction optimization and substrate scope will
be discussed.
Synthesis of tetrazolo[1,5-a]pyridines from pyridine N -oxides.
[1]
(a) A. Boruah, M. Baruah, D. Prajapati, J. S. Sandhu, Synlett 1997, 1253-1254; (b) M.
Vaultier, N. Knouzi, R. Carrie, Tetrahedron Lett. 1983, 24, 763-764; (c) H. J. Boyer, J. Am.
Chem. Soc. 1951, 73, 5865-5866.
[2]
(a) M.-L. Tsao, M. S. Platz, J. Am. Chem. Soc. 2003, 125, 12014-12025; (b) S. Murata, R.
Yoshidome, Y. Satoh, N. Kato, H. Tomioka, J. Org. Chem. 1995, 60, 1428-1434; (c) A. Albini,
G. Bettinetti, G. Minoli, J. Am. Chem. Soc. 1991, 113, 6928-6934.
[3]
(a) W. G. Lewis, L. G. Green, F. Grynszpan, Z. Radic, P. R. Carlier, P. R. Taylor, M. G. Finn,
K. B. Sharpless, Angew. Chem., Int. Ed. 2002, 41, 1053-1057; (b) Y. Angell, K. Burgess, J.
Org. Chem. 2005, 70, 9595-9598; (c) A. F. Brigas, Sci. Synth. 2004, 13, 861-915.
276
Saturday 9:00 - 11:30
Poster 219
Quinolinium based Dyes in Ionic Liquids - Synthesis,
Theoretical Calculations and Photophysical Properties
∗
Stella Schmode ∗ , Sebastian Reimann∗ , Nikolaus P. Ernsting† , Ralf Ludwig∗
Theoretical and Physical Chemistry – University of Rostock – Dr.-Lorenz-Weg/1 –
Rostock – GER
†
Physical Chemistry – Humboldt Universität zu Berlin – Brook-Taylor-Str./2 –
Berlin – GER
[email protected]
Ionic Liquids have attracted much attention in science and technology over the past
decades. First innovative applications are already established in the fields of chemical synthesis, catalysis, biochemical and pharmaceutical research as well as material
science.[1,2] Despite the impressive enhancements, the reasons of fundamental chemical properties like solvation behavior and acidity are often not completely understood.
Different spectroscopic methods can be used to probe inter- and intramolecular interactions in ionic liquids.[3]
Here we present a combination of spectroscopy with synthesis of new low melting salts
supported by DFT calculations. The structural unit of all examined compounds is
quinolinium. This heterocyclic molecule is substituted in N-position by alkyl groups
which results in a native zwitterionic molecule with a negative charge at the oxygen
and a positive one at the nitrogen atom. Low melting salts are formed by conversion
with acids containing weak coordination anions, e.g. triflate. Structural information
is given by NMR and MIR spectroscopy. The influence of different alkyl chain length
is studied by comparison of binding energy in terms of measured melting points and
calculated molecular energies.
[1]
N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev. 2008, 37 (1), 123-150.
J. Stoimenovski, D. R. MacFarlane, K. Bica, R. D. Rogers, Pharmaceutical Research 2010,
27 (4), 521-526.
[3]
A. Wulf, K. Fumino, R. Ludwig, Angew. Chem. Int. Ed. 2010, 49, 449-453.
[2]
Poster 220
Saturday 9:00 - 11:30
277
Targeting tumor cells by using drug-magnetic nanoparticles
conjugate
Anita Jarzebinska ∗ , Anna Maria Nowicka∗ , Agata Kowalczyk∗ , Mikolaj Donten∗ ,
Pawel Krysinski∗ , Zbigniew Stojek∗ , Ewa Augustin† , Zofia Mazerska†
∗
†
Department of Pharmaceutical Technology and Biochemistry –
Gdansk University of Technology – Narutowicza 11/12 – Gdansk – POL
[email protected]
A disadvantage of many drugs used in therapy of solid tumors is their cytotoxicity
against healthy tissues. Doxorubicin is especially toxic to the heart and the kidneys, which limits its therapeutic applications. Therefore, it is important to find a
carrier that can deliver the drug selectively to the tumor tissue. The binding of a
magnetic nanoparticle with a doxorubicin and applying a properly directed external
magnetic field might be a good alternative to such traditional forms of the drug like
liposomes and micels. The improved by us synthesis of the conjugate of doxorubicin
with iron-oxide magnetic nanoparticles allows a substantial depression of the aggregation process of the nanoparticles and therefore the examination of cytotoxicity of the
modified drug. It has been shown, by performing the electrochemical microbalance
measurements, that the use of magnetic field guarantees the efficient delivery of the
drug to the requested place. The change in the synthesis led to an increase in the
number of DOX molecules attached to one magnetic particle. It has also been found
that the release of the drug takes place below pH 5.8, which pH characterizes the cancer cells. We demonstrated that unmodified iron-oxide magnetic nanoparticles were
not cytotoxic toward human urinary bladder carcinoma cells UM-UC-3. Tumor cell
sensitivity of DOX-Np complex was slightly higher in comparison to identical concentration of doxorubicin alone. Therefore, the magnetic nanoparticles were shown to be
a good carrier for doxorubicin into the investigated tumor cells.
[1]
J. O’Shaughnessy, Oncologist 2003, 8, 1-2.
V. I. Shubayev, T. R. Pisanic II, S. Jin, Advanced Drug Delivery Rev. 2009, 61, 467-477.
[3]
S. M. Hussain, K. L. Hess, J. M. Gearhart, K. T. Geiss, J. J. Schlager, Toxicol.in Vitro 2005,
19, 975-983.
[4]
A. M. Nowicka, A. Kowalczyk, M. Donten, P. Krysinski, Z. Stojek, Anal. Chem. 2009, 81,
7474-7483.
[2]
278
Saturday 9:00 - 11:30
Poster 221
Synthesis and biological activity of novel phthalocyanines
with dietheroxy and nitroimidazolylethoxy moieties
Marcin Wierzchowski ∗ , Sebastian Lijewski∗ , Lukasz Sobotta† , Krystyna Konopka‡ ,
Michael Lee‡ , Nejat Düzgünes‡ , Ewa Tykarska∗ , Jadwiga Mielcarek† , Tomasz Goslinski∗
∗
Poznan University of Medical Sciences – Grunwaldzka 6 – 60-780 Poznan – POL
†
Poznan University of Medical Sciences – Grunwaldzka 6 – 60-780 Poznan – POL
‡
Department of Biomedical Sciences – University of the Pacific – 2155 Webster Street –
San Francisco, 94115 CA – USA
[email protected]
Phthalocyanines (Pcs) are aromatic macrocyclic compounds consisting of four isoindole fragments linked together with azomethine groups. These synthetic analogues
of natural porphyrinoids are known to possess wide applications in dyes industry,
in materials chemistry as sensors, molecular semiconductors and non-linear optical
materials, and as photosensitizers in photodynamic therapy. Medical applications
of phthalocyanines impose good solubility in water and increased accumulation in
pathologic tissues. The structure of Pcs may be modified by introducing substituents
at their peripheral and non-peripheral positions, as well as various metal ions into the
central cavity of a macrocycle. Good solubility in water can be reached by introducing polyetheric substituents[1] in non-peripheral positions. Increased accumulation
in hypoxic tissues such as cancer tissue can be reached by incorporating nitroimidazole moieties to the structure.[2] New compounds were synthesized according to the
procedure shown on Figure 1.
Newly synthesized phthalocyanines Pc-1, Pc-2, Pc-3, Pc-4 as well as the precursor
dinitriles 1 and 2 were fully characterized by NMR, UV-Vis, MS, HPLC. Additionally,
new dinitryles were characterized by combustion analysis and crystallographic data.
New phthalocyanines were tested for photodynamic activity against human oral squamous carcinoma cells HSC-3. The best activity was revealed by compound Pc-3
possessing two types of substituents – dietheroxy and nitroimidazolylethoxy. Pc-3
showed photocytotoxicity at the level of IC50 0.10 µM. Zinc compound Pc-2 was three
times more active than the magnesium Pc-1 and seems to be a promising compound
for further research.
This study was supported by the National Science Centre under Grant No. N401
067238.
Fig. 1
[1]
F. Lv, B. Cao, Y. Cui, T. Liu, Molecules 2012, 17, 6349-6361.
R. J. Abdel-Jalil, M. Übele, W. Ehrlichmann, W. Voelter, H. J. Machulla, J. Radioanal. Nucl.
Chem. 2006, 267, 557-560.
[2]
Poster 222
Saturday 9:00 - 11:30
279
Highly Chemoselective Metal-free Reduction of Phosphine
Oxides to Phosphines
Yuehui Li, Liang-Qiu Lu, Kathrin Junge, Matthias Beller
Leibniz-Institut für Katalyse – Albert-Einstein-Str. 29a – Rostock – GER
[email protected]
Chemoselective reductions of unsaturated compounds constitute an important tool
box for more benign organic synthesis. Little is known on the catalytic reduction
of related P=O bonds, which are thermodynamically highly stable. With a bond
energy of around 502 kJ/mol they are significantly more stable compared to typical
organic functional groups and the general order of bond energy stability is: P-O >
C-H > C-O > C-C > C-N).[1,2] Therefore, it is not surprising that highly chemoselective reductions of phosphine oxides until today represent an unsolved problem
although the resulting organophosphines represent valuable intermediates and ligands for transition-metal catalysis.[3] For the first time, unprecedented chemoselective reductions of phosphine oxides to phosphines proceed smoothly in the presence of
catalytic amounts of specific Brønsted acids. Utilizing inexpensive silanes, e.g. PMHS
or (EtO)2MeSiH, other reducible functional groups such ketones, aldehydes, olefins,
nitriles, and esters are well tolerated under optimized conditions.[4]
Chemoselective reduction of phosphine oxides.
[1]
S. B. Hartley, W. S. Holmes, J. K. Jacques, M. F. Mole, J. C. McCoubrey, Quart. Rev. 1963,
17, 204-223.
[2]
Y. Li, S. Das, S. Zhou, K. Junge, M. Beller, J. Am. Chem. Soc. 2012, 134, 9727-9732.
[3]
K. Ding, Z. Han, Z. Wang, Chem. Asian. J. 2009, 4, 32-41.
[4]
Y. Li, L.-Q. Lu, S. Das, S. Pisiewicz, K. Junge, M. Beller, J. Am. Chem. Soc. 2012, 134,
18325-18329.
280
Saturday 9:00 - 11:30
Poster 223
Determination of originality of fruit brandies using linear
regression analysis
Natasa Kalajdzija ∗ , Sanja Podunavac Kuzmanovic∗ , Lidija Jevric∗ ,
Strahinja Kovacevic∗ , Biljana Marosanovic† , Maja Lojovic†
∗
Department of Applied and Engineering Chemistry –
University of Novi Sad, Faculty of Technology – Bulevar cara Lazara 1 – Novi Sad – SRB
†
Department of Instrumental Analysis – SP Laboratory – Industrijska zona bb –
Becej – SRB
[email protected]
Production of fruit brandy should be based on the use of fruit from which fermentable
sugars are transformed into ethanol during fermentation. However, due to the manufacturers aim to achieve higher profits, they are increasingly resorting to the use of
sugar produced from sugar beet due to much lower purchase prices of raw materials.
Given that sugar beet belongs to the C3 -plants as well as fruit (apples, pears), the
addition of sugar that comes from sugar beet can be confirmed through isotope ratio
mass spectrometry analysis (IRMS) of stable isotopes of hydrogen in the molecule
of ethanol.[1] On average, 85% of deuterium originating from sugar during the fermentation process is being incorporated in the methyl-group, and 75% of deuterium
originating from water into methylene-group of ethanol molecules.[2] If alcoholic beverages are sweetened with sugar beet, analysis of ethanol will obtain δD values that
are significantly lower compared to the values obtained for the ethanol molecule that
is derived exclusively from fruit.[3]
The examination of apple and pear brandies that originate from the areas of the Republic of Serbia, confirmed the existence of dependence between the amount of added
sugar derived from sugar cane and the value of the stable isotopes of hydrogen in
ethanol molecule (δD). We analyzed six samples of brandy, and for each sample, by
using a linear regression analysis, a mathematical formulation was derived that describes the given linear dependence. Statistical parameters that prove the validation
of the model equations (Pearson’s correlation coefficients (r), the standard error of
estimation (s), Fisher’s value (F) and parameters of cross validation (PRESS value,
r2cv and r2adj )) were calculated using the software package Statistical System Number
Cruncher-NCSS 2007. The practical application of the equations is reflected in the
calculation of the amount of added sugar derived from sugar beets during the production of brandy on the basis of δD values, and it is necessary to know the type and
variety of fruit from which it is produced.
[1]
N. Christop, A. Rossmann, S. Voerkelius, Mitt. Klosterneuburg 2003, 53, 23.
M. Guček, J. Marsel, N. Ogrinc, S. Lojen, Acta Chim. Slov. 1998, 45, 217.
[3]
K. Ishida-Fujii, S. Goto, R. Uemura, K. Yamada, M. Sato, N. Yoshida, Biosci. Biotechnol.
Biochem. 2005, 69, 2193.
[2]
Poster 224
Saturday 9:00 - 11:30
281
Photogeneration of charge carriers in poly(N-vinylcarbazole)
doped with 2-(4-biphenylyl)-5-phenyl-1,3,4-oxadiazole and
tris(2-phenylpyridine) iridium
Anna Stefaniuk , Jarosław Jung, Ireneusz Głowacki
Department of Molecular Physics, Faculty of Chemistry –
Łódź University of Technology – Żeromskiego/116, 90-924 Łódź – Łódź – POL
[email protected]
Poly(N-vinylcarbazole) (PVK) and a mixture of PVK with 40 wt. % of 2-(4-diphenyl)5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PVK - PBD) are commonly used as an electroluminescent matrix.[1] PVK-PBD system is characterized by comparable transport
of holes and electrons. The high level of triplet excitons’ energy of carbazole groups
allows the effective energy transfer from the matrix to the phosphorescent dopant.[2]
Analysis of the spectral distribution of thermoluminescence spectrum confirms the
presence of the deep traps for holes and efficient recombination centers which are
located on the tris(2-phenylpyridine) iridium (Ir(ppy)3 ) particles. The addition of a
small amount (2 wt. %) of Ir(ppy)3 effectively quenches the excited states of PVK
and PBD-PVK.[3] A similar value of the triplet energy levels (∼ 3.2 eV) and the ability of the formation of triplet excitons in PVK and Ir(ppy)3 has a significant impact
on the generation of electron-hole pairs and their dissociation in a high electric field
in PVK-PBD systems doped with tris(2-phenylpyridine) iridium.
The aim of this work was to determine the quantum yield of photogeneration of
charge carriers by xerographic discharge method. Samples of PVK and PVK-PBD
doped with iridium complex (2 wt. %) with a thickness from 1,5 to 6 µm was obtained
by drop-casting method. Based on the analysis of the results of quantum efficiency of
photogeneration of charge carriers depending on the intensity of the electric field and
the excitation wavelength the photoconductivity of examined systems PVK and PVKPBD doped with iridium complex was rated. The results obtained for the samples
doped with Ir(ppy)3 show that the quantum efficiency of photogeneration of charge
carriers is significantly reduced in comparison with pure PVK. This is associated with
the effective capture of holes by Ir(ppy)3 particles. Addition of 40 wt. % of PBD
(which is characterized by a high mobility of electrons) to the PVK + Ir(ppy)3 system
results in an appearance of photoconductivity in the electric field from −4 · 105 V/m
to −3 · 107 V/m.
[1]
I. Glowacki, and Z. szamel, J. Phys. D: Appl. Phys. 2010, 43, 295101.
D.F. Prepichka, N. Meng, M.-M. Ling, “Phosphorescent polymer light-emitting diodes, Organic
light-emitting materials and devices”, Z. Li, H. Meng, Tylor Francis, Boca Raton 2007, 413-449.
[3]
Z. Szamel “Trapping and recombination of charge carriers in polymer electrophosphorescent
systems”, Ph.D. Thesis, Lodz University of technology, 2007.
[2]
282
Saturday 9:00 - 11:30
Poster 225
Detection of the Cyanotoxin Cylindrospermopsin in Brassica
Species
Katrin Kittler ∗ , Monika Schreiner† , Angelika Krumbein† , Matthias Koch∗ ,
Sascha Rohn‡ , Ronald Maul∗
∗
Analytical Chemistry; Reference Materials –
Federal Institute for Materials Research and Testing – Richard-Willstätter-Straße 11 –
Berlin – GER
†
Department of Quality Research –
Leibniz-Institute of Vegetable and Ornamental Crops – Theodor-Echtermeyer-Weg 1 –
Großbeeren – GER
‡
Institute of Food Chemistry – University of Hamburg – Grindelallee 117 –
Hamburg – GER
[email protected]
Cylindrospermopsin (CYN), a potent cyanobacterial hepatotoxin, occurs in freshwater bodies worldwide. Humans or animals get exposed to this toxin by ingestion,
skin contact, or inhalation predominantly when swimming in contaminated water.
Another known exposure route is the uptake of CYN containing seafood.[1] In many
countries it is common to use surface water for crop irrigation also from potentially
cyanotoxin-contaminated resources.[2] Therefore, an exposure to CYN by eating contaminated crops seems possible. The aim of this study was to clarify whether CYN is
taken up by plants and transported from the roots to the leaves. Different Brassica
species served as model crops, which were irrigated with CYN containing water.
In experiment 1 the roots of two leaf stage Brassica oleracea var. sabellica and
Brassica juncea plants were irrigated with a nutrient solution in an aeroponic system
for 30 days. The water contained pure CYN and CYN from an unpurified APH
extract (cCY N = 18-35 µg L−1 ). In experiment 2 Sinapis alba seedlings were used to
examine the concentration dependency for CYN uptake. Therefore, the plants were
exposed to concentrations in the range of 20 to 445 µg L−1 CYN for a growth period
of 3 days. The plant material from the two different experiments was freeze-dried,
extracted, and analyzed by HPLC-MS/MS.[3]
In all experiments performed, a significant uptake of CYN by the test plants was
observed. The CYN concentrations in the leaves reached up to 21 % of the concentration initially applied to the roots. Furthermore, a linear concentration dependency of the CYN absorption in the selected concentration range was determined for
Sinapia alba seedlings. The results indicate that CYN is systemically available to the
examined Brassica species. Thus, it seems possible that crop plants irrigated with
CYN-containing surface water may represent a significant source of this toxin within
the food chain.[3]
[1]
S. Kinnear, Mar. Drugs. 2010, 8(3), 542–564.
A. Peuthert, Environ. Toxicol. 2007, 22(4), 436-442.
[3]
K. Kittler, Food Chem. 2012, 133(3), 875-879.
[2]
Poster 226
Saturday 9:00 - 11:30
283
Characterization Anthocyanin by UV-Vis Spectroscopy and
HPLC Detection in Chokeberry
Jelena M. Brcanović, Aleksandra N. Pavlović, Snežana S. Mitić, Jovana N. Veljković,
Milan N. Mitić, Jovana Lj. Pavlović
Department of Chemistry – Faculty of Sciences and Mathematics, University of Niš –
Višegradska 33 – Niš – SRB
[email protected]
Aronia melanocarpa, native to eastern North America, is a member of the Rasaceae
family. Chokeberries are rich in phenolic compounds and have been reported to
have antioxidative effects in vitro and in vivo. It has been applied as a natural
antihypertensive and anti-atherosclerotic drug, mainly by the polyphenols and anthocyanins. The anthocyanins are water-soluble plant pigments with antioxidant, antiinflammatory, antimicrobial, anticancer, hepatoprotective, gastroprotective. In the
fruit, chlorogenic and neochlorogenic acids are dominant among the aromatic acids.
High contents of cyanidin-3-arabinoside, cyanidin-3-galactoside and (-)-epicatechin
are also typical of chokeberries.
In this study we have determined the total content of anthocyanins by the pHdifferential spectrophotometric method in five different samples (syrup, juice, berry,
dried tea and chokebbery tea infusions). Two dilutions were prepared, one with
potassium chloride buffer (pH 1.0) and the other with sodium acetate buffer (pH
4.5). Absorbance was measured simultaneously at 510 nm and 700 nm. The content
of total anthocyanins was expressed in mg of cyanidin-3-O-glucoside equivalents per
100 g of chokeberry or liter of juice (mg C3GE/g or mg C3GE/L). Total anthocyanins
content from different samples ranged from 1055.68 mg/100 g (infusion tea) to 56.757
mg/100 g (chokeberry). Total anthocyanins content from different solvents in chokeberry from 101.2 mg/100 g (solvent methanol 60%) to 28.71 mg/100 g (solvent water).
Total anthocyanins content from different samples in one solvent methanol 60% from
715.65 mg/100 g (dried tea) to 96.52 mg/100 g (chokeberry). Qualitative and quantitative determination of the content of anthocyanins and phenolic compounds was
measured by HPLC.
This research was supported by the Ministry of Education, Science and Technological
Development, grand number BI172047.
Key words: anthocyanins, chokeberry, HPLC, phenolic compounds
284
Saturday 9:00 - 11:30
Poster 227
Taylor Dispersion Analysis (TDA) for Liquid Diffusivity
Measurements
Bianka Sieredzinska ∗ , Magdalena Ligia Naurecka † , Anna Lewandrowska‡ ,
Aldona Majcher‡
∗
Faculty of Chemistry – the University of Warsaw – Pasteura 1 – Warsaw – POL
†
Faculty of Chemistry – Maria Curie-Sklodowska University in Lublin –
pl. Marii Curie-Sklodowskiej 2 – Lublin – POL
‡
Institute of Physical Chemistry – the Polish Academy of Sciences – Kasprzaka 44/52 –
Warsaw – POL
[email protected] - [email protected]
Taylor Dispersion Analysis is a method for the study of diffusion coefficient, which
was first described by Taylor (1953) and further developed by Aris (1954). It is based
on the measurements of effective molecular diffusion coefficient during flow through a
long, thin capillary with and without selector.[1,2,7] The analysis demonstrates that
it is possible to design an instrument that operates very nearly in accordance with
the simplest mathematical description of the dispersion of a solute pulse in a fluid
in laminar flow within a straight, circular cross-section tube. The small departures
of a practical instrument from the ideal are evaluated as corrections by means of
a general perturbation treatment that allows them to be examined one at a time.
The corrections considered include the effects of the finite volume of the injection
pulse, the finite volume of the concentration monitor, the coiling of the tube, and the
nonuniformity and noncircularity of the cross section, as well as the variation of the
fluid properties with composition.[3]
TDA is a typical chromatographic method, where the chromatographic column is
replaced by a capillary filled with an appropriate eluent (Tris-phosphate buffer, TrisHCl buffer). A small injection of the sample is applied to the system and the diffusion
coefficients of the free ligand and the free selector (l-phenylalanine, ribonuclease and
warfarin) is determined by TDA. The concentration of the ligand is the same as in
the experiment without selector. The concentration of the selector is the same as an
eluent. The effective diffusion coefficient of the ligand during the flow in the presence
of the selector depends on the diffusion coefficient of free and complexed ligand, and
also stability contact of the ligand-selector complex.[4] A method we used in our experiment was, ultrahigh pressure liquid chromatography (UHPLC). However, around
the world there are several other methods used to determine dispersion coefficient,
e.g. dynamic light scattering,[5] and nuclear resonance spectroscopy.[6]
TDA might be useful in the study of biological substances. There is a large group
of industrial processes that may find the dispersion coefficient parameter to be useful
in designating and analyzing new technological solutions. Furthermore, dispersion
coefficient along with hydrodynamic properties can deliver information both about
size and shape of macromolecules such as proteins.
[1]
R. Aris, Proc. Soc. Lond. A 1956, 235, 67-77.
A. Bielejewska, A. Bylina, K. Duszczyk, M. Fialkowski, R. Holyst, Anal. Chem. 2010, 82,
5463-5469.
[3]
A. Alizadeh, C. A. Nieto de Castro, W. A. Wakeham, Int. J. Thermophys. 1980, 1, 243-284.
[4]
M. Zuo, Y. Han, L. Qi, Y. Chen, Chin. Sci. Bull. 2007, 52, 3325-3332.
[5]
C. Yang, W. Li, Vu. Ch, J. Physic. Chem. 2004, 108, 11866-11870.
[6]
E. O. Stejskal, J. E. Tanner, J. Chem. Physics 1965, 42, 288-292.
[7]
M. Johnson, R. D. Kamm, J. Fluid Mech. 1986, 172, 329.
[2]
Poster 228
Saturday 9:00 - 11:30
285
Influence of substituent effect on structure of imidazole
N-oxide derivatives
Marlena Lukomska ∗ , Agnieszka Rybarczyk-Pirek∗ , Krzysztof Ejsmont† ,
Marcin Palusiak∗
∗
Structural Chemistry and Crystallography Group – University of Lodz –
Pomorska 163/165 – Lodz – POL
†
Crystallography Group – University of Opole – Oleska 48 – Opole – POL
[email protected]
Imidazole derivatives occur in biologically important systems and are used in agriculture and medicine.[1-4] Various medicaments based on imidazole and benzimidazole derivatives are applied in treatment of parasitic diseases like trichomoniasis or
Chang disease which are caused by protozoa Trichomonas vaginalis and Trypansoma
cruzi.[5,6] Since currently used drugs cause serious side effects, chemists are looking
for new more effective chemicals which in the same time could be less toxic. In that
light it is worth mentioning that some imidazole N–oxide derivatives were tested in
vitro against the mentioned protozoa[7] with positive results.
As continuation of broad studies on novel imidazole N-oxide derivatives the crystal
structures of six new compounds were determined by X–ray method. The analysis
of structural properties of individual molecules as well as intermolecular contacts in
crystals was performed. The influence of substituent effect on selected geometrical
parameters including parameters of intramolecular N − H · · · O(−) charge assisted
hydrogen bond will be discussed in this presentation.
Acknowledgment: Authors thank dr Marcin Jasiński (Department of Organic and
Applied Chemistry, University of Łódź) for crystal samples.
Fig.1:Molecular structure of the investigated compounds(R=H, CN, OCH3 , NO2 , CF3 , F)
[1]
M. R. Grimmett, Adv. Heterocycl. Chem. 1970, 12, 103.
M. R. Grimmett, Adv. Heterocycl. Chem. 1980, 27, 241.
[3]
M. R. Grimmett, in Comprehensive Heterocyclic Chemistry, Ed. K. T. Potts, Pergamon
Press, Oxford 1984, 5, 374.
[4]
K. Ebel, in Methoden der organischen Chemie (Houben-Weyl), Band E8c, Teil III, Ed. E.
Schaumann, G. Thieme, Stuttgart, 1994, 1.
[5]
H. Cerecetto, M. González, Current Topic Med. Chem. 2002, 2, 1185
[6]
C. Cosar, P. Ganter, L. Jolou, Presse Med. 1961, 69, 1069.
[7]
G. Aguirre, M. Boiani, H. Cerecetto, A. Gerpe, M. González, F. Sainz, A. Denicola, C. Ochoa
de Ocáriz, J. Nogal, D. Montero, J. A. Escario, Arch. Pharm. Pharm. Med. Chem. 2004, 337,
259.
[2]
286
Saturday 9:00 - 11:30
Poster 229
Crystallographic Description of Crystalline Nanostructures
Virginia Ramona Bucila ∗ , Davide M. Proserpio† , Mircea V. Diudea∗ ,
Miranda Petronella Vlad‡
∗
Department of Organic Chemistry –
Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering Cluj-Napoca –
Arany Janos Str.11 – Cluj-Napoca – ROU
†
Dipartimento di Chimica – Universita’ degli Studi di Milano –
Via Golgi, 19 - 20133 Milano, Italy – Milano – ITA
‡
Department of Finance and Accounting –
“Dimitrie Cantemir” Christian University Bucharest Fac. of Eco. Sci. of Cluj-Napoca –
56. Teodor Mihaly Street Cluj Napoca – Cluj-Napoca – ROU
[email protected]
The present work is dedicated to presenting the crystallographic description of some
studied nano crystalline networks as 3-periodic structures. For each structure, we determine the category to which it belongs (3-c net, 4-c net, 3,4-c net or other nets), its
point symbol, stoichiometry, vertex symbol, topos parameters and identify whether
the structure has a known or new topology, with the help of the TOPOS program
(a program package for multipurpose crystallochemical analysis) and additional programs we developed.
We also used a program called Systre designed to analyze periodic nets as they arise
in the study of extended crystal structures (as opposed to molecular crystals). Systre
uses a method called barycentric placement to determine the ideal symmetry of the
crystal net (optimal embedding) and to analyze its topological structure.
Poster 230
Saturday 9:00 - 11:30
287
Terahertz-Time-Domain-Spectroscopy (THz-TDS) as
Method for the Analysis of the Polymorphism in Aspirin
Sebastian Reimann, Christian Roth, Stella Schmode, Ralf Ludwig
Physical and Theoretical Chemistry – University of Rostock / Institute of Chemistry –
Dr.-Lorenz-Weg 1 – Rostock – GER
[email protected]
Nowadays, terahertz time domain spectroscopy (THz-TDS) has gained remarkable importance for characterization of materials, since THz spectroscopy has high sensitivity
to the conformation and structure of molecules as well as its adjacent environment.[1]
Especially lattice vibrations of molecular crystals occur at THz frequencies being incredibly sensitive to the intermolecular contacts of the crystal system.[2] Thus, variations in crystalline materials composed of identical molecules, such as polymorphs,
typically show unique THz vibrational spectra due to their distinct three-dimensional
structures.
Aspirin exhibits a fascinating and perplexing structural chemistry possessing two
polymorphs (form I and form II).[3] Exemplarily, we have chosen this ubiquitous
compound to develop a new procedure probing the phenomenon of polymorphism by
THz-TDS spectroscopy. Both, form I and form II, were synthesized and defined by Xray powder diffraction.[3] Subsequently, THz-TDS has been applied to identify both
polymorphs of Aspirin providing structural information of the molecules as well. The
observed THz features were compared to far-IR measurements and the final results
were verified theoretically by DFT calculations.
Scheme 1. Elucidating the polymorphism of Aspirin using THz spectroscopy.
[1]
a) S. L. Dexheimer (Ed.), Terahertz Spectroscopy - Principles and Applications, Taylor
Francis Ltd., Boca Raton, Florida, 2008; b) Y.-C. Shen, Int. J. Pharm. 2011, 417, 48-60; c) R.
M. Smith, M. A. Arnold, Appl. Spec. Rev. 2011, 46(8), 636-679.
[2]
M. D. King, E. A. Davis, T. M. Smith, T. M. Korter, J. Phys. Chem. A 2011, 115, 1103911044.
[3]
a) A. D. Bond, CrystEngComm 2012, 14, 2363-2366; b) A. D. Bond, K. A. Solanko, S.
Parsons, S. Redder, R. Boese, CrystEngComm 2011, 13, 399-401; c) A. D. Bond, R. Boese, G.
R. Desiraju, Angew. Chem. 2007, 119, 625-630.
288
Saturday 9:00 - 11:30
Poster 231
The influence of the reactants flow through the
reaction-stripping column on the 1,3-dichloropropan-2-ol
dehydrochlorination process
Anna Krzyżanowska, Eugeniusz Milchert
Institute of Organic Chemical Technology –
West Pomeranian University Of Technology – Pułaski Str. 10 – Szczecin – POL
[email protected]
As a result of 1,3-dichloropropan-2-ol dehydrochlorination reaction epichlorohydrin is
obtained. Epichlorohydrin is an important intermediate mainly use in the production
of epoxy resins.[1]
Commercially epichlorohydrin is manufactured by reacting allyl chloride with chlorine–water to obtain a mixture of chlorohydrins, which are then treated with milk
of lime to produce epichlorohydin.[2] Nowadays, last for research on the receipt of
epichlorohydrin from glycerol. This process based on the conversion of glycerol to
dichlorohydrins (mainly 1,3-dichloropropan-2-ol), and then dehydrochlorination to
epichlorohydrin (the GTE process).[3] In the literature, there are no reports concerning the process parameters of production of epichlorohydrin from 1,3-dichloropropan2-ol and the methods of realization of technological process itself.
The aim of doctoral thesis is study on the influence of technological parameters on
the continuously dehydrochlorination process in the reaction-stripping column. One
of this parameters is flow of 88 wt % aqueous solution of 1,3-dichloropropan-2-ol and
10 wt % milk of lime. The total reactants flow was changed (from 12.1 cm3 /min
to 70.0 cm3 /min) and the influence on the selectivity to the epichlorohydrin and
1,3-dichloropropan-2-ol conversion was studied.
Increasing the summary flow rate of reactants in the range of 12.1 to 70.0 cm3 /min, at
a constant flow of steam (4.3 dm3 /min), reduces the conversion of 1,3-dichloropropan2-ol from about 90% to 80%. The selectivity of epichlorohydrin is constant and is
approximately 99%. At summary total flow of reactants which is 70.0 cm3 /min, the
flooding of column is occur.
[1]
P. Czub, Z. Bończa-Tomaszewski, P. Penczek, J. Pielichowski. Chemia i technologia żywic
epoksydowych. PWN, Warsaw, 2002, 24-25.
[2]
E. Grzywa, J. Molenda. Technologia podstawowych syntez organicznych. WNT, Warsaw,
2008, 278-280.
[3]
B.M Bell, J.R. Briggs, Clean Journal, 2008, 36(8), 657-661.
Poster 232
Saturday 9:00 - 11:30
289
Determination of folic acid and its major derivatives by
capillary electrophoresis
Justyna Stachniuk , Radoslaw Dalkowski, Barbara Krawczyk, Dominik Szczukocki,
Robert Zakrzewski
Inorganic and Analytical Chemistry – University of Lodz, Faculty of Chemistry –
[email protected]
Folic acid (FA) is the simplest naturally occurring water soluble vitamin and most
stable form of folate, which is essential for humans. Mammals cannot synthesize folate
by themselves so it should be supplied with food. Folic acid has different important
functions in the human body while it is not biologically active. All the biological
functions of FA are performed by tetrahydrofolic acid (FH4 ) and other derivatives
which are generated in the presence of dihydrofolate reductase (DHFR). This FH4
is the main circulating form of folate which plays a major role in the red blood cells
synthesis and tissue development. This compound also facilitates the single carbon
transfer reaction for the synthesis of basic constituents of DNA and RNA and the
production of methionine from homocysteine. The supplementation of FA prevents
spina bifida and related neural tube birth defects.
Methotrexate (MTX) is an analog of folic acid. It is a potent FA antagonist which
acts as an inhibitor of DHFR leading to DNA damage and cell death. During the
last-half century MTX has been widely used in large doses for the treatment of acute
lymphoblastic leukemia, as an anti-inflammatory and immunosuppressive drug, in
low doses in the treatment of rheumatoid arthritis and other diseases. Today, due
to its antiproliferate activity, MTX is mainly used in the treatment of leukemia,
lymphomas as well as certain solid tumors. As a chemotherapeutic drug for tumors,
methotrexate is usually used in high doses, which causes same side effects such as
vomiting, myelosuppression, hepatotoxicity, nephrotoxicity and neurotoxicity. That
is why, high doses of MTX are always followed by folinic acid (FNA) rescue leading
to an increase of reduced folates in the cellular concentration.
Due to the importance of FA, toxic side effects of MTX and rescue value of FNA, their
concentration in nutrition supplements, pharmaceutical preparations and plasma or
urine should be regularly monitored. In literature several analytical methods, including HPLC and CE, can be found to quantify mentioned compounds separately.[1,2]
These separation techniques are powerful due to their high resolution, high efficiency,
rapid separation of analytes and minimum operation cost. Thus, in this study we
evaluate and validate a reliable CE method with UV detection for measuring the
concentration of FA, FNA and MTX in biological samples. The starting conditions
for the development of these compounds were calculated from the CE conditions of
a validated method for some organic acids.[3] The method was optimized by testing
the following parameters: the used buffer concentration and pH, time of injection and
temperature.
[1]
E. Deconinck, S. Crevits, P. Baten, P. Courselle, J. De Beer, J. Pharm. Biomed. Anal. 2011,
54, 995-1000.
[2]
S. Zhao, H. Yuan, Ch. Xie, D. Xiao, J. Chromatogr. A 2006, 1107, 290-293.
[3]
I. S. L. Lee, M. C. Boyce, M. C. Breadmore, Food chemistry 2011, 127, 797-801.
290
Saturday 9:00 - 11:30
Poster 233
Calcium Fructoborate Influence on Inflammation
Anca-Mihaela Bulearca, Andrei Bita, Romulus Ion Scorei
research department –
Bioboron Research Institute from Natural Research Ltd., Craiova, Dolj, Romania –
Strada A.I.Cuza, nr. 15, bloc Patria, sc.B, ap.11, etaj 2, Craiova, Dolj, Romania –
Craiova, Dolj County – ROU
[email protected]
Several population-based clinical studies have shown that the level of C-reactive protein (CRP), an immune recognition protein, is a sensitive marker of inflammation.
Calcium fructoborate (CF) is a sugar-borate ester (SBE), patented complex of calcium, fructose and boron found naturally in fresh and dried fruits, vegetables and
herbs, and wine. Published clinical researches indicate that CF significantly reduces
serum levels of CRP in humans, suggesting this unique plant-mineral complex controls
the inflammation.
Poster 234
Saturday 9:00 - 11:30
291
Design, Synthesis and Biological Study of
4-(Polyfluoroalkyl)-1,2-dihydropyrazolo[3,4-b]pyridin-3-ones
and corresponding Nucleosides - new
6-Polyfluoroalkyl-containing Purine Isosters as potential
Drug-like Scaffolds
Linda Supe ∗ , Robert Begunk† , Janine Hussner† , Henriette Meyer zu Schwabedissen† ,
Katrin Sternberg† , Viktor O. Iaroshenko∗
∗
Institut für Chemie – Universität Rostock – Albert-Einstein Str. 3a – Rostock – GER
†
Institut für Biomedizinische Technik – Universität Rostock –
Friedrich-Barnewitz-Straße 4 – Rostock – GER
[email protected]
Nucleosides furnished with fluorine functionality either in sugar or in the heterocyclic
part take a special place among biologically active molecules. Development of fluorinated nucleosides became the result of the extensive antiviral and anticancer research
stimulated by emergence of acquired immunodeficiency syndrome (AIDS) and tumours. To date there are known several marketed drugs so called fluorinated purine
and pyrimidine antimetabolites clinically broadly used for the treatment numerous of
cancers and viral infections.[1]
In this work performed reactions include synthesis of 1H -pyrazolo[3,4-b]pyridin-3ones 3 and corresponding nucleosides 4 (Fig.1). Besides peracylated ribofuranose,
corresponding glycose and rhamnose derivatives were used giving according nucleosides in good to excellent yields. Catalytic reduction of pyridine ring 3 was carried
out successfully.
Preliminary biological evaluation library of more than 150 compounds, and subsequent optimization by the additional hit-to-lead study resulted in the identification
of several representatives with strong antagonistic action on human smooth muscle
cells. Lead compounds LS 009 and LS 057 are now under study as novel, cell-selective
drug-candidate for endovascular implants.
Fig. 1. Synthesis of perfluoralkyl group containing purine-like scaffolds.
[1]
(a) K. L. J. Kirk, Fluor. Chem. 2006, 127, 1013-1029; (b) W. K. J. Hagmann, Med. Chem.
2008, 4359-4369; (c) V. Gouverneur, K. Müller, Fluorine in Pharmaceutical and Medicinal
Chemistry, Imperial College Press 2012, ISBN-10: 1-84816-634-6; (d) P. Shah, A. D. J. Westwell, Enzyme Inhib. Med. Chem, 2007, 22, 527–540; (e) P. Liu, A. Sharon, C. K. J. Chu, Fluor.
Chem. 2008, 129, 743-766; (f) S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem. Soc.
Rev. 2008, 37, 320-330.
292
Saturday 9:00 - 11:30
Poster 235
PNA/PNA Recognition Mediated Ligation Strategy
Applying a Photosensitive Linker
Cornelia H. Panse, Stephen Middel, Ulf Diederichsen
Institute of Organic and Biomolecular Chemistry – Georg-August-University Göttingen –
Tammannstr. 2 – Göttingen – GER
[email protected]
The photochemical properties of o-nitrobenzene compounds are known for more than
hundred years,[1] whereas photocleavable groups based on this concept have been
introduced in the 1960s.[2] Since then, photodeprotection and cleavage are well established in various fields of research.[3] Our aim is to use the photocleavable unit to
cleave PNA oligomers after these oligomers served in a ligation reaction. PNA/PNA
recognition facilitates nearly unlimited orthogonal ligation sites (Scheme 1). Herein,
PNA covalently attached to the peptide brings the functionalized centres of the
two peptides in close proximity by PNA/PNA base pair recognition. Following the
PNA-mediated peptide ligation the PNA strands need to be cleaved off using the onitrobenzene derivate. For this purpose a photocleavable linker was synthesized based
on the 3,4-dimethylnitrobenzene structure, which is known to have enhanced quantum
yields and photon absorption properties compared to the unsubstituted nitrobenzene
derivative.[4] For functionalization with PNA an ethyne moiety was introduced in
benzylic position of the nitrobenzene ring.[5] In preliminary experiments it was shown
that the photolabile group at the N -terminus of a peptide was uncaged within 30 minutes of UV exposure. Furthermore, functionalization with a resin bound PNA strand
applying copper mediated click chemistry is possible. In near future PNA-mediated
ligation experiments will be explored.
Scheme 1: Strategy for the PNA/PNA mediated ligation using a photocleavable
auxiliary.
[1]
P. Silber, G. Ciamician, Chem. Ber. 1901, 34, 2040.
A. Patchornik, B. Amit, R. B. Woodward, J. Am. Chem. Soc. 1970, 92, 6333.
[3]
C. Brieke, F. Rohrbach, G. Mayer, A. Heckel, Angew. Chem. Int. Ed. 2012, 51, 8446.
[4]
K. Schaper, M. Etinski, T. Fleig, Photochem. Photobiol. 2009, 85, 1075.
[5]
J. A. Baccile, M. A. Morrell, R. M. Falotico, B. T. Milliken, D. L. Drew, F. M. Rossi,Tetrahedron
Lett. 2012, 53, 1933.
[2]
Poster 236
Saturday 9:00 - 11:30
293
HPLC screening and evaluation of antioxidative capacity of
Hylotelephium spectabile (Boreau) H. Ohba x telephium (L.)
H.Ohba leaf and flower extracts, fractions and their
hydrolysates
Snezana Jovanovic ∗ , Goran Petrovic∗ , Bojan Zlatkovic† , Aleksandra Djordjevic∗ ,
Olga Jovanovic∗ , Vesna Stankov-Jovanovic∗ , Violeta Mitic∗ , Marija Ilic∗ ,
Gordana Stojanovic∗
∗
Visegradska 33 – Nis – SRB
†
Department of Biology and Ecology –
University of Niš, Faculty of Sciences and Mathematics – Visegradska 33 – Nis – SRB
[email protected]
Hylotelephium genus is well-known due to a wide range of pharmacological effects
(anti-inflammatory, anti-radiation, antiviral, anticancer, etc.). Leaf juice locally heals
wound, skin disease and spots, and relieves the pain caused by cold to the ear. Investigated plant, Hylotelephium spectabile (Boreau) H. Ohba x telephium (L.) H.Ohba,
a taxon of hybrid origin is grown as an ornamental and medicinal plant across Serbia.
China and Japan are natural habitats of H. spectabile (Autumn Joy, Ice plant) while
H. telephium (Orpine, Livelong, Frog’s-stomach, Midsummer-men, Witch’s Moneybags,etc.) is native to Eurasia. Wide use of plant in traditional medicine induced our
interests to examine chemical composition and antioxidative activity of plant MeOH
extracts, its fractions and hydrolysates. Experimental work included preparation of
fresh leaves and flowers MeOH extracts and liguid-liguid partition of each extract to
obtain hexane, EtOAc and BuOH fractions. Except hexane fraction, MeOH extracts
and theirs fractions were hydrolysed. HPLC chromatograms showed that extracts
contain mostly quercetin and kaempferol glycosides, as confirmed by the composition
of hydrolysates whose main components were quercetin and kaempferol. Evaluations
of antioxidant activity were done by applying the following assays: DPPH assay,
ABTS assay and Total reducing power assay (Fe3+ to Fe2+ ). Additionally total
flavonoid content (based on flavonoid affinity to form complex with AlCl3 ) and total phenols (by Folin-Ciocalteu reagent based on reduction of Mo6+ to Mo5+ ) were
determined. Flower EtOAc fraction showed best activity for all performed assays.
Leaf samples have lower activity then corresponding flower samples. Flower samples
(EtOAc, BuOH fractions and their hydrolysates) are better DPPH radical and ABTS
radical cation scavengers than rutin, excluding BuOH fraction against ABTS radical cation. In non hydrolysed samples (mgml−1 ) values for total flavonoid content,
expressed as rutin equivalents, was ranged from 57.20 to 121.33 µgml−1 and in hydrolysed from 101.98 to 539.16 µgml−1 . Range values of total phenol content (gallic
acid equivalents), for non hydrolysed samples was from 53.33 to 960.00 µgml−1 and
for hydrolysed samples from 173.33 to 1946.67 µgml−1 .
Acknowledgements: The research was supported by the Serbian Ministry of Education, Science and Technology Development (Grant no 172047).
Keywords: Hylotelephium spectabile (Boreau) H. Ohba x telephium (L.) H.Ohba,
flavonoids, HPLC, antioxidative activity
294
Saturday 9:00 - 11:30
Poster 237
Location of tetraarylporphyrin in sterically stabilized
liposomes
Natalia Szydłowska, Monika Dzieciuch, Mariusz Kepczynski, Maria Nowakowska
Faculty of Chemistry – University – Ingardena 3 – Krakow – POL
[email protected]
The aim of our studies was to determine partitioning of tetraarylporphyrin (mTHPP)
to sterically stabilized liposomes (SSL). Liposomes are spherical vesicles formed by
some amphiphilic compounds, e.g., phosphatidylcholines and are considered as a
model of biological membranes. Incorporation of lipids with covalently attached
poly(ethylene glycol) (PEG) into liposomal bilayer membranes causes significant stabilization of liposome suspensions, prevents their aggregation and inhibits protein
and cellular interactions with liposomes thereby considerably prolonging their blood
circulation time. These vesicles are known as pegylated or SSL liposomes and are applied as effective drug delivery supports.[1,2] The interactions between mTHPP and
SSL were studied using fluorescence methods. POPC liposomes containing one of the
quenchers were prepared by sonication.[3] A series of doxyl-spin labeled molecules:
3β-doxyl-5α-cholestane (CSL), 5-doxyl stearic acid (5-SASL) or 16-doxyl stearic acid
(16-SASL) was used in the measurements. The final concentration ratio between
POPC and the quencher in the sample was 80:20. The vertical localization of the fluorophore in a membrane was calculated according to the parallax method. The basic
idea of parallax method is to compare the amount of fluorescence quenching caused
by quenchers which are located at two different depths in the bilayer.[4] mTHPP was
quenched mostly by CSL and 16-SASL. The shallow position of mTHPP in the pegylated membrane indicates that the porphyrin tends to escape to the PEG layer. An
additional method to obtain the information about the relative vertical depth location of membrane-bound fluorophores in a membrane is quenching of the porphyrin
fluorescence with copper ions. Fluorescence quenching is associated with a collisional
quenching constant, KSV, which is obtained from the Stern–Volmer equation. The
KSV value for mTHPP in non-pegylated liposomes is much lower than for mTHPP in
pegylated liposomes, which suggests that the porphyrin in SSL is situated superficially
in the bilayer.
[1]
M.C. Woodle, “Controlling liposome blood clearance by surface-grafted polymers”, Adv. Drug
Deliv. Rev. 1998, 32, 139-152.
[2]
S. Piperoudi, D. Fatouros, P. V. Ioannou, P. Frederik, S.G. Antimisiaris, “Incorporation of
PEG-lipids in arsonoliposomes results in formation of highly stable arsenic-containing vesicles”,
Chem. Phys. Lipids 2006, 139, 96-106.
[3]
M. Kepczynski, M. Kumorek, M. Stepniewski, T. Róg, B. Kozik, D. Jamróz, J. Bednar, M.
Nowakowska, “Behavior of 2,6-Bis(decyloxy)naphthalene Inside Lipid Bilayer”, 2010.
[4]
A. Chattopadhyay, E. London, Biochemistry 1987, 26, 39.
Poster 238
Saturday 9:00 - 11:30
295
Total Polyphenol, Flavonoid Contents and Antioxidant
Capacity of Chokeberry
Jovana N. Veljković, Jelena M. Brcanovic, Aleksandra N. Pavlovic, Snezana B. Tosic,
Milan M. Stojkovic, Dusan Ð. Paunovic, Branka T. Stojanovic
Višegradska 33, 18000 Niš, Serbia – Niš – SRB
[email protected]
The purpose of the present study was to evaluate small and high molecular phenolics,
flavonoid and antioxidant activity of Aronia melanocarpa. Small berries such as black
chokeberry (Aronia melanocarpa) represent one of the important sources of potential
healthpromoting phytochemicals because these fruits are rich in compounds with
high antioxidant properties.The objective of our research was to evaluate the total
polyphenol and flavonoid contents as well as antioxidant activity of five different
products aronia in six different solvents.
Total polyphenol content was determined spectrophotometrically according to the
Folin-Ciocalteu method (λ=760 nm), using gallic acid (GA) as a standard, and ranged
from 66.68 mg/g (aronia dried tea, solvent acetone) to 4.25 mg/g (juce of aronia,
solvent acetone). The total flavonoid content in selected chokeberry samples was determined according the aluminum chloride spectrophotometric method (λ=510 nm).
Catechin was chosen as a standard and the results expressed in milligram catechin
equivalents per gram of extract (mg CE/g). Results are ranged from 52.2 mg/g (aronia
dried tea, solvent acetone) to 3.52 mg/g (syrup, solvent water). DPPH radical scavenging activity, 2,2’-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) radical cation
scavenging activity (ABTS), ferric reducing-antioxidant power (FRAP) and reducing
power assay Fe(III) to Fe(II) (RP) were used to assess the antioxidant capacity (AC)
of chokeberry. These assays, based on different chemical mechanisms, were selected
to take into account the wide variety and range of action of antioxidant compounds
present in selected chokeberry samples. All samples showed antioxidant power. The
results obtained in this work are generally consistent with literature data.
This research was supported by the Ministry of Education, Science and Technological
Development, grant number BI172047
Keywords: total phenols, flavonoids, antioxidant capacity, chokeberry.
296
Saturday 9:00 - 11:30
Poster 239
A Dinuclear, Molecular Iron(II) Silicate with two High-Spin,
Square Planar FeO4 Units
Denise Pinkert ∗ , Serhiy Demeshko† , Fabian Schax∗ , Beatrice Braun∗ , Franc Meyer† ,
Christian Limberg∗
∗
Institut für Chemie – Humboldt-Universität zu Berlin – Brook-Taylor-Str. 2 – Berlin –
GER
†
Institut für Anorganische Chemie – Georg-August-Universität Göttingen –
Tammannstraße 4 – Göttingen – GER
[email protected]
For four ligand donor atoms surrounding a metal ion, tetrahedral and square planar
ligand geometries have to be considered. The comparison of the ligand field stabilization energies of high-spin and low-spin configurations provides a rationale, why a
certain structure and electron configuration is stable and others are not. Square planar geometry implicates a large separation of the dx2 −y2 orbital from the remaining
d orbitals, which is beneficial if only those are filled, in particular if the ligand field is
strong. Consequently, for metal ions with more than 4 d electrons and a square planar
ligand geometry low-spin configurations are preferred and compounds with high-spin
configuration are rare.
Recently Klüfers[1] et al. and Doerrer[2] et al. reported the first molecular compounds containing high-spin, square planar FeO4 units which are not coordinated by
a macrocyclic ligand and discussed the prerequisites for this unusual structural motif.
In our work, we set out employing the known tripodal organotrisilanol LH3 [3] as a
ligand precursor which was reacted with iron(II)-triflate after deprotonation of the
Si-OH groups with sodium methanolate. The resulting product contains two FeII
centers in square planar coordination spheres spanned by two trisiloxane ligands. The
remaining two negative charges are compensated by two sodium ions (additionally
binding Et2 O co-ligands).[4] This compound extends the sparse knowledge in this
field with regard to molecular chemistry to dinuclear compounds, to 6-membered
chelate rings and also to silanolate ligands; it thus approaches the situation in the
natural iron silicate Gillespite[5] or in certain ceramics[6] where also square planar
FeO4 units have been found. Overall for the first time edge-sharing of FeO4 units has
been observed.
[1]
X. Wurzenberger, H. Piotrowski, P. Klüfers, Angew. Chem. Int. Ed. 2011, 50, 4974-4978.
S. A. Cantalupo, S. R. Fiedler, M. P. Shores, A. L. Rheingold, L. H. Doerrer, Angew. Chem.
Int. Ed. 2012, 51, 1000-1005.
[3]
M. Veith, A. Rammo, O. Schütt, V. Huch, Z. Anorg. Allg. Chem. 2010, 636, 1212-1221.
[4]
D. Pinkert, S. Demeshko, F. Schax, B. Braun, F. Meyer, C. Limberg, Angew. Chem. Int. Ed.
2013, accepted.
[5]
A. Pabst, Am. Mineral. 1943, 28, 372–390.
[6]
Y. Tsujimoto, C. Tassel, N. Hayashi, T. Watanabe, H. Kageyama, K. Yoshimura, M. Takano,
M. Ceretti, C. Ritter, W. Paulus, Nature 2007, 450, 1062-1065.
[2]
Poster 240
Saturday 9:00 - 11:30
297
Alternative synthesis of surfactant KLE by 1,3-cycloaddition
reaction
Monica Violeta Cîrcu, Frank Alain Nüesch, Dorina Maria Opriş
Functional polymers – EMPA – Ueberlandstrasse 129 – Dubendorf – SUI
[email protected]
KLE [poly(ethylene-co-butylene)-block-poly(ethylene oxide)] is an ideal surfactant for
stabilization of monomer nanodroplets in inverse miniemulsions and is commonly synthesized using Kraton liquid [polyethylene-co-butylene (PEB)] as macroinitiator in
ethylene oxide polymerization.[1] The disadvantage of this approach is that ethylene
oxide is gaseous, therefor small scale experiments are not convenient to be implemented.
We propose here an alternative route to synthesize KLE avoiding use of gaseous
ethylene oxide (Scheme 1). In the first step Kraton liquid (A), which represents the
lipophilic part of the aimed surfactant C, was esterified with 4-pentynoic acid by using
active ester chemistry. The hydrophilic part, B, of this surfactant was obtained by
using commercial hydroxyl end functionalized polyethylene oxide (Mw = 2000 g/mol
and Mw = 5000 g/mol).[2] The two building blocks A and B were covalently coupled
together by so-called “click” chemistry.
Scheme 1. Retrosynthetic scheme for obtaining KLE
[1]
[2]
A. Thomas, H. Schlaad, B. Smarsly, M. Antonietti, Langmuir 2003, 19, 4455-4459.
J. A. Opsteen, J. C. M. van Hest, Chem. Commun. 2005, 57-59.
298
Saturday 9:00 - 11:30
Poster 241
Synthesis and Electrochemical Characterization of Cp*Ir
Complexes Bearing an Unsymmetrically Substituted
Bipyridine Ligand
Fanni Sypaseuth, Christoph Tzschucke
Institut für Chemie und Biochemie - Organische Chemie – Freie Universität Berlin –
Takustr. 3 14195 Berlin – Berlin – GER
[email protected]
Bipyridines have been used as chelating ligands for a wide range of metal ions in
numerous different applications.[1] Synthesis and catalytic activity of Cp* iridium
bipyridine complexes have been studied in the context of different reactions such
as transfer hydrogenation of ketones and dehydrogenative oxidation of alcohols.[2]
However, the influence of unsymmetrical substitution patterns on the 2-,2’-bipyridine
ligand has not been described. We previously developed the synthesis of unsymmetrically substituted bipyridines by palladium catalyzed direct arylation of pyridine N -oxides.[3] These bipyridines were employed as ligands in the preparation of
[Cp*Ir(bpy)Cl]Cl complexes. The redox behaviour of these complexes was characterized by cyclic voltammetry. Initial results on their catalytic activity will be presented.
[1]
C. Kaes, A. Katz, M. W. Hosseini, Chemical reviews 2000, 100, 3553.
a) S. Ogo, N. Makihara, Y. Kaneko, Y. Watanabe, Organometallics 2001, 20, 4903; b) T.
Abura, S. Ogo, Y. Watanabe, S. Fukuzumi, Journal of the American Chemical Society 2003,
125, 4149; c) Y. Himeda, N. Onozawa-Komatsuzaki, S. Miyazawa, H. Sugihara, T. Hirose, K.
Kasuga, Chemistry 2008, 14, 11076; d) R. Kawahara, K. Fujita, R. Yamaguchi, Journal of the
American Chemical Society 2012, 134, 3643; e) R. Kawahara, K. Fujita, R. Yamaguchi, Angew.
Chem. Int. Ed. 2012, 51, 12790.
[3]
S. Duric, C. C. Tzschucke, Organic Letters 2011, 13, 2310.
[2]
Poster 242
Saturday 9:00 - 11:30
299
Synthesis of Oligomeric Lignin-Analogs
Ramona Pirwerdjan, Tillmann Kleine, Carsten Bolm
Organische Chemie – RWTH Aachen – Landoltweg 1 – Aachen – GER
[email protected]
In the last decades the valorization of lignocellulosic biomass has become a field of
increased interest due to its relevance as a potential feedstock for fuels, chemicals and
energy.[1] Lignin-valorization, in contrast to cellulose and hemicelluloses, however is
still in an initial phase.[2,3] Because of its great structural diversity, analyses of this
amorphous biopolymer and its reaction products remain rather challenging. For this
reason, model compounds that mimic the properties of native lignin are of prime interest, in order to make the studies on the lignin cleavage easier and comprehensible
on a molecular level.[4] In this context, substrates containing β-O-4 linkages are particularly relevant, as those bonds are most abundant in lignin (30-50%, depending on
the wood type).[2,5]
Recently, we described a diastereoselective preparation of dimeric β-O-4 dilignol
model compounds.[5] In 2005 and 2008, Kishimoto and coworkers developed synthetic
routes for the preparation of polymeric β-O-4 mono- and dilignol model compounds.[6]
Based on these previous findings, we now present a protocol which allows the synthesis of oligomeric lignin analogs. The chain length of these lignin related mono- and
dilignols could be controlled to bear two to four β-O-4 linkages.
[1]
a) F. Cherubini, Energy Convers. Manage. 2010, 51, 1412-1421; b) J. C. Serrano-Ruiz, R.
Luque, A. Sepúlveda-Escribano, Chem. Soc. Rev. 2011, 40, 5266-5281.
J. Zakzeski, P. C. Bruijnincx, A. L. Jongerius, B. M. Weckhuysen, Chem. Rev. 2010, 110,
3552-3599.
[3]
a) Y.-T. Cheng, J. Jae, J. Shi, W. Fan, G. W. Huber, Angew. Chem. Int. Ed. 2012, 51,
1387-1390; b) G. W. Huber, A. Corma, Angew. Chem. Int. Ed. 2007, 46, 7184-7201; c) J. B.
Binder, R. T. Raines, J. Am. Chem. Soc. 2009, 131, 1979-1985; d) A. Corma, S. Iborra, A.
Velty, Chem. Rev. 2007, 107, 2411-2502.
[4]
For a recent degradation study, see: T. Kleine, J. Buendia, C. Bolm, Green Chem. 2013, 15,
160-166.
[5]
J. Buendia, J. Mottweiler, C. Bolm, Chem. Eur. J. 2011, 17, 13877-13882.
[6]
a) T. Kishimoto, Y. Uraki, M. Ubukata, Org. Biomol. Chem. 2005, 3, 1067-1073; b) T.
Kishimoto, Y. Uraki, M. Ubukata, Org. Biomol. Chem. 2006, 4, 1343-1347; c) T. Kishimoto,
Y. Uraki, M. Ubukata, Org. Biomol. Chem. 2008, 6, 2982-2987.
[2]
300
Saturday 9:00 - 11:30
Poster 243
Efficient [5+1]-Synthesis of 4-Quinolones by Domino
Amination / Conjugate Addition Reactions of
1-(2-Fluorophenyl)prop-2-yn-1-ones with Amines
Satenik Mkrtchyan, Viktor Iaroshenko, Aleksander Villinger
Faculty of Chemistry – University Rostock – Albert Einstein str. 3a, 18059 Rostock –
Rostock – GER
[email protected]
Functionalized quinolines are attractive compounds for drug discovery since many
of them have been shown to exhibit excellent biological activities. Moreover, a
very special position among all drugs containing a quinoline core is occupied by the
fluoroquinolones.[1] Recent advances in the synthesis of pyridines, quinolines and fused
pyridines by [5+1]-cyclization strategies include several efficient methods for the constructing of such heterocyclic scaffolds.[2] Having this strategy in mind Iaroshenko’s
laboratory exanimated the cyclisation reaction of fluorinated phenylpropyn-1-one 1
with different amines 2. Compounds 1 are available from commercially available
acetylenes and fluorinated benzoylchlorides by Sonogashira reaction. Using Li2 CO3
as base in DMA, a series of tandem [5+1]-cyclizations of amines 2 with 1 was conducted, resulting the 4-quinolones 3 with 73-89 % yields (Figure 1).[3] When acetylenes
1 containing a second fluorine atom in the molecule were investigated, we have observed an interesting phenomenon. In the case when the second fluorine was located
in ortho- or para- position to the carbonyl group it was substituted by an amine to
give the amino-substituted quinolones 4. However, the substrates 1 with the second
fluorine in meta-position were not prone to react with amines and in this case the
reaction resulted in 4-quinolones 3 containing the fluorine group in the position-6.
Nevertheless, during this investigation we have encountered with the fact that the
double-substitution occurred only with aliphatic amines. The application of anilines
under our standard reaction conditions did not result in substitution of the second
fluoride group. However, this result provided us the possibility to use some products
3 to substitute the second activated fluorine atom by aliphatic amines to deliver different quinolones 4. Moreover, the mechanism of this transformation was investigated
and a number of intermediates was isolated and identified.[3]
Figure 1. Synthesis of functionated 4-quinolines
[1]
R. B. Silverman, The organic chemistry of drug design, and drug action (Second Edition),
Elsevier Academic Press, 2004, 617, ISBN 0-12-643732-7. [2] a) D. Craig, G. D. Henry, Tetrahedron Lett. 2005, 46, 2559-2562; b) T. Harschneck, S. F. Kirsch, J. Org. Chem. 2011, 76,
2145-2156. [3] V. O. Iaroshenko, S. Mkrtchyan, A. Villinger, Synthesis 2013, DOI: 10.1055/s0032-1316826.
Poster 244
Saturday 9:00 - 11:30
301
Alternative method for blood alcohol determination by
proton -NMR – Development and validation
Elina Zailer , Bernd Diehl
Spectral Service AG – Spectral Service AG – Emil-Hoffmann-Straße 33 – 50996 Köln –
GER
[email protected]
Aims: The 50 - year - old methods of analyzing blood alcohol (BAC) like headspace gaschromatography and the enzymatic ADH can be supplemented by the alternative
method of NMR spectroscopy using only one capillary blood drop with an equivalence
of 20 µL. The aims of this method are the keeping of the demands of the Guidelines
to determine the BAC for forensic purposes and the introduction of a fast, precise
and non - destructive BAC analysis with a minimum volume of capillary full blood.
Methods: The NMR method involves the use of a solvent of maximum 1 mL D2O
spiked with TMSP, and an internal standard in form of 20 µL DMS. The measurement
occurs with the NMR spectroscopy (600 MHz) with fixed parameters.
Results and Discussion: The volume of 20 µL capillary full blood is enough for the determination of the BAC with the same accuracy like the “old” methods. The stability
at different storage places, the repeatability, reproducibility, linearity and accuracy
confirmed by preparing calibration series with reference serum and whole blood are
analyzed. Factors like personnel, chemicals, temperature, light and air humidity do
not show any effects on the BAC results. A scientific drinking test proves that intravenous and capillary blood shows the same BAC level.
Conclusion: The drinking test proves that a single capillary blood drop is sufficient for
a BAC determination. A comparison of the BAC results of the forensic jurisprudence,
measured by GC - HS and ADH, and of the alternative NMR – method demonstrates
the accuracy of this method with real blood samples. A forensic usability with the
specified limits can be met.
Key words: blood, alcohol, BAC, NMR, spectroscopy
302
Saturday 9:00 - 11:30
Poster 245
Exploring what’s underneath Sub-Surface AFM to locate Nanoparticles within Polymer
Soft Matter
Bob-Dan Lechner ∗ , Eike-Christian Spitzner† , Adekunle Olubummo† , Matthias Schulz‡ ,
Wolfgang H. Binder‡ , Robert Magerle† , Alfred Blume∗
∗
Physikalische Chemie – Martin-Luther-Universität Halle-Wittenberg –
Von-Danckelmann-Platz 4 – Halle an der Saale – GER
†
Chemische Physik – Technische Universität Chemniz – Reichenhainer Str. 70 –
Chemnitz – GER
‡
Makromolekulare Chemie – Martin-Luther-Universität Halle-Wittenberg –
Von-Danckelmann-Platz 4 – Halle an der Saale – GER
[email protected]
The interactions of mixed systems of lipids and surface modified nanoparticles have
increased researchers interest in the past decade. Modified nanoparticles are a valuable target system for a plenty of biological, biomedical and nano-technological issues
requiring the controllability and tunability of their mixing abilities within lipid membranes with focus on adsorption, binding, dispersion and localization.[1] A powerful
mean to investigate such nanoscopic systems are amplitude modulation atomic force
microscopy (AM-AFM) techniques enabling visualization of nanostructures and characterization of key local mechanical properties, simultaneously. By indenting the soft
material of the sample with the oscillating AFM tip a depth resolved map of mechanical properties can by gained. Hard tissues like non-compressive CdSe nanoparticles
can thus be visualized underneath the respective lipid/polymer surface.[2]
The aim of this work is to gain insight in interaction principles of CdSe nanoparticles
with mixed lipid/polymer monolayers at the air water interface or transferred films
at solid Si substrates via AM-AFM. We focus on the organization and localization of
the nanoparticles within the monolayer thereby demonstrating that the nanoparticles
surface modification plays a crucial role for the respective nanoparticle location within
or at the interface.
Fig. 1. Location of functionalized CdSe nanoparticles within mixed DPPC/
PIB87-b-PEO17 monolayers; interaction cartoon for hydrophobicly modified
nanoparticles (left), AFM scan of a transferred layer at Si substrate (mid), localization of
CdSe nanoparticle clusters within polymer columns measured by AM-AFM (right).
[1]
a) A. Olubummo, M. Schulz, B.-D. Lechner, P. Scholtysek, K. Bacia, A. Blume, J. Kressler, W.
H. Binder, ACS Nano 2012, 6 (10), 8713-8727; b) M. Schulz, D. Glatte, A. Meister, P. Scholtysek,
A. Kerth, A. Blume, K. Bacia, W. H. Binder, Soft Matter 2011, 7, 8100.
[1]
E.-C. Spitzner, C. Riesch, R. Magerle, ASC Nano 2011, 5, 1, 315.
Poster 246
Saturday 9:00 - 11:30
303
Composition and Chemistry of a Pd-Ni-Co alloy studied by
HAXPES
Julius Kühn
6.8 Surface Analysis and Interfacial Chemistry – BAM – Unter den Eichen 44-46 –
Berlin – GER
[email protected]
The surface near region is very important for catalytic processes. Compositional
changes, e.g. segregation of alloy constituents in states before and after hydrogen sulfide exposure was investigated by non-destructive chemical HAXPES depth profiling.
The HAXPES data are completed by results of AES providing data characteristic of
the uppermost surface and EDX data characteristic of the bulk of the alloys.
304
Saturday 9:00 - 11:30
Poster 247
Characterizing electrostatic interactions for drug design
purposes
∗
Marta Kulik ∗ , Anna Maria Goral† , Paulina Maria Dominiak† , Joanna Trylska∗
Centre of New Technologies – University of Warsaw – Żwirki i Wigury 93 – Warsaw –
POL
†
[email protected]
Accurate tools to establish recognition patterns between small ligands and their receptor biomolecules are needed in order to improve drug design process. Electrostatic
interactions are often crucial in recognition of ligands binding to nucleic acids (for
example, in the case of aminoglycoside antibiotics targeting various RNA motifs). Reconstructing the electron density with the single point charge models, as in classical
molecular mechanics potential energy functions, lacks the accuracy of the multi-pole
expansion approaches. The methodology that accounts for other than single-point
charge terms in the description of electrostatics was applied.
The idea of University at Buffalo Databank (UBDB)[1] is based on the transferability of electron density parameters between atoms that are in chemically equivalent
vicinities. The UBDB parameters allow reconstructing the electron density from the
experimental structural data even for large systems. The UBDB and the Exact Potential Multipole Method (EPMM) developed by Volkov[2] were applied to estimate
the electrostatic energy of interactions and its per-ring contributions between RNA
and aminoglycosides as the electrostatic effects dominate the binding process.[3]
Understanding the amplitude of electrostatic interactions between aminoglycosides
and their ribosomal RNA target is necessary to introduce aminoglycoside modifications that would enhance their binding.
[1]
K.N. Jarzembska, P.M. Dominiak, Acta Cryst. 2012, A68, 139-147.
A. Volkov, T. Koritsanszky, P. Coppens, Chem. Phys. Lett. 2004, 391, 170-175.
[3]
H. Wang, Y. Tor, Angew. Chem. 1998, 37, 109-111.
[2]
The authors acknowledge support from the Foundation for Polish Science Team project (TEAM/20093/8) co-financed by European Regional Development Fund operated within Innovative Economy
Operational Programme.
Poster 248
Saturday 9:00 - 11:30
305
Coordination Behavior and Spectroscopic Studies of
Biologically Active Metal Complexes of Triterpene Acid.
Khadija Shahid
Riphah Institute of Pharmaceutical Sciences –
Riphah International University, Islamabad – 7th Avenue, G-7/4 – Islamabad – PAK
[email protected]
New metal complexes of triterpene acid were synthesized in stoichiometric ratio in
anhydrous toluene under the reflux yield the organometallic complexes[1] with general
formula R4-nMLn(R= Me, n-Bu, Ph, and n= 2, 3 where M= Zn, Fe, Sn, Cu, Sb). All
the complexes have been characterized by various spectroscopic methods (IR,1H,13C
NMR) and atomic absorption spectroscopy. These compounds have also been screened
for biological activities[2] to establish their significance.
[1]
(a) K. Shahid, S. Ali, S. Shahzadi, J. Coord. Chem, 2009, 62 (17), 2919-2926; (b) K. Shahid,
S. Shahzadi, J. Serb. Chem. Soc. 2009, 74 (2), 141-154.
[2]
A. Rahman, M.I. Choudhary, W.J. Thomsen, Bioassay Techniques for Drug Development,
Hardward Academic Press, Amsterdam 2001.
Key words: Triterpene acid, Biological activity and Spectroscopy.
306
Saturday 9:00 - 11:30
Poster 249
Tuning Selectivity of Switchable Multicomponent
Heterocyclizations involving aminoazoles, salicylaldehydes
and pyruvic acids
Maryna Murlykina, Yana Sakhno, Valentin Chebanov
Department of Heterocyclic Compounds Chemistry –
State Scientific Institution “Institute for Single Crystals” NAS of Ukraine –
Lenin ave. / 60 – Kharkiv – UKR
[email protected]
The intense interest in multicomponent heterocyclizations of aminoazoles, aldehydes
and pyruvic acids is connected with the possibility of realization of several different reaction pathways depending on the reagents’ structure, type of solvent and catalyst.[1]
It was also shown that the introduction of OH-group in ortho-position of the aldehyde allows yielding among several types of final compounds also oxygen-bridged
structures.[2-4]
The present work is dedicated to the tuning selectivity of multicomponent reactions
of aminoazoles, salicylaldehydes and pyruvic acid derivatives.
It was shown that the control the direction of these three-component reactions can
be carried out by varying the temperature condition with the help of non-classical
activation methods (microwave and ultrasonic irradiation). It should be noted, that
in comparison with ordinary mechanical stirring, ultrasonication doesn’t influence on
the reaction mechanism and direction and its effect comes to decreasing of the reaction
time for account of the effective mass transfer and homogenization.
Scheme 1
[1]
V. A. Chebanov, K. A. Gura, S. M. Desenko, Top. Heterocycl. Chem. 2010, 23, 41-84.
Ya. I. Sakhno, S. V. Shishkina, O. V. Shishkin et al., Mol. Divers. 2010, 14, 523-531.
[3]
N. Yu. Gorobets, Y. V. Sedash, K. S. Ostras et al., Tetrahedron Lett. 2010, 51, 2095-2098.
[4]
J. Svetlik, V. Kettmann, Tetrahedron Lett. 2011, 52, 1062-1066.
[2]
Poster 250
Saturday 9:00 - 11:30
307
α, β, and ω
Marko Popovic
Faculty of chemistry, University of Belgrade – University of Belgrade – St.Trg 12 –
Belgrade – SER
[email protected]
The proposed thermodynamic model of an biological system satisfies the following
caracteristics of a living organism: the exchange of substance and energy with its
surroundings (open system); the property of growth, so that input of matter into
the system is greater than the output; the membrane is semipermeable; the analyzed
system requires energy and matter from outside for its growth; chemical reactions are
going on in the system and complex structures are formed; it continuously changes its
state; during the change of state errors happen and accumulate over time; there is a
mechanism which repairs the errors but it isn’t perfect; the living system has two (or
more) subunits; the subunits are differentiated and each has its role (which represents
the differentiation of cells in complex organisms); the function of α subsystem is
dependent on the function of β subsystem (because the catalyst DEF can be produced
only in a specialized β cell). The subsystems α and β function as one entity αβ,
surrounded by ω. Based on Schrodinger’s[1] assumption supported by Ho[2] and
Hansen[3] , as well as on the assumption of von Bertalanffy[4] that living systems act
as open thermodynamic systems, and on Prigogine’s work[5,6] , the aging of living
systems is described. Aging of biological systems is directly related to the processes
of life, and is described by thermodynamic equation which shows two tendencies: one
to increase the entropy and the other is an act of the organized biological machine
to decrease the entropy. Aging is a consequence of imbalance between these two
tendencies. It’s also concluded that because of the property of growth the input
and output of substance aren’t equal, because a part of the substance remains in
the system, as a consequence of that the system is in a quasi-steady state. This
means that pressure, temperature, molarity and mol fractions are constant; while the
quantity of substance and entropy of the system are variable.
308
Saturday 9:00 - 11:30
Poster 251
Stereoselective modifications of salen-like ligands - chiral
chelates and macrocycles
Paweł Tokarz ∗ , Jarosław Lewkowski∗ , Anna Krzyczmonik∗ , Katarzyna Ślepokura† ,
Tadeusz Lis†
∗
Department of Organic Chemistry – University of Łódź – Ul. Tamka 12 – 91-403 Łódź –
POL
†
Department of Chemistry – University of Wroclaw – Ul. F. Joliot-Curie 14 –
Wrocław – POL
[email protected]
Compounds derived from 1,2 -diaminocyclohexane (DACH ) play a crucial role in the
modern chemistry of chiral synthesis. One of the most spectacular substances, derived
from this simple amine, are macrocyclic molecules that can be obtained by so-called
cyclocondensation.[1] Such macrocycles have found numerous applications, only to
mention a few - the asymmetric catalysis or the chiral recognition of biologically
active agents.[2,3]
Until now little is known about modified structures of DACH -based macromolecules,
in particular, those containing lipophilic substituents. We have decided to provide
a simple and stereoselective method of the introduction of long carbon chains into
the macrocyclic moiety. We have used dialkyl phosphites as chain carriers. In this
way it was possible for us to introduce two chains per one azomethine bond. We
developed a novel synthetic protocol applying use of sodium hydride which gave us
diastereoisomeric ratios as high as 100:1:1 for acyclic model systems. In case of the
large, cyclic systems the problem becomes more complex due to a number of possible
isomeric products.
Synthesis of lipophilically modified DACH -based macrocycles
[1]
N. E. Borisova, M. D. Reshetova, Y. A. Ustynyuk, Chem. Rev. 2007, 107, 46-79.
G. Zhou, Y. Cheng, L. Wang, X. Jing, F. Wang Macromolecules 2005, 38, 2148.
[3]
R. D. Hancock Pure Appl. Chem. 1986, 58, 1445-1452.
[2]
Poster 252
Saturday 9:00 - 11:30
309
Dihydrogen-bonded complexes as active intermediates at
acid mediated transformations of transition metal
tetrahydroborates
Igor E. Golub ∗ , Oleg A. Filippov† , Viktor P. Dyadchenko∗ , Elena S. Shubina†
∗
Chemistry Department – M.V. Lomonosov Moscow State University –
Leninskiye Gory 1-3 – Moscow – RUS
†
A.N. Nesmeyanov Institute of Organoelement Compounds (INEOS RAS) –
Vavilov Street 28 – Moscow – RUS
[email protected]
The dihydrogen-bonded (DHB) complexes are known to form at the first step of
proton-transfer reaction. These complexes previously investigated for different types
of metal hydrides and hydrides of main group elements, but for metal tetrahydroborates study of influence intermolecular interactions on chemical properties of such
compounds.
The mechanism of acid mediated transformation of transition metal tetrahydroborates
was thoroughly studied by means of combination of experimental (IR and NMR,
190-300 K) and computational (DFT/M06) methods. Formation of DHB complexes
as the first reaction step and their thermodynamic characteristic was established
experimentally. By means of theoretical investigation possible coordination modes of
DHB complexes were revealed. Despite of existence a large number of DHB different
types (mono-, bi- and trifurcate complexes) and competition between these forms,
only one type of DHB bifurkate complex with participation of terminal and bridge
hydrides of tetrahydroborate-group is active intermediate of the reactions.
Acknowledgment: This work was supported by Russian Foundation for Basic Research (project No 13-03-00604).
310
Saturday 9:00 - 11:30
Poster 253
JungChemikerForum Aachen
Jeanne Fronert, Peter Becker, Julian Kleemann
Institutes of Chemistry – RWTH Aachen University – Landoltweg 1 – Aachen – GER
[email protected]
The JCF Aachen is a group of 18 active members, who are Bachelor-, Master- or
doctoral students. We meet regularly every four weeks to discuss new projects or
just to meet each other for exchange in a casual atmosphere. We organize lectures
that are mainly addressed to students. Furthermore we realize excursions to chemical
companies. Another special event is our beachvolleyball tournament, that takes place
every summer.
In 2012 the following events took place in Aachen:
Lecture by Prof. Dr. Klaus Roth – “Vom ersten Bier zum Kater.”:
To the “Tag der Chemie” of the RWTH Aachen University we invited Prof. Dr.
Klaus Roth to give an interesting and entertaining lecture related to the interaction
of alcohol with the human body.
Beachvolleyball Tournament:
In July we arranged the annual beachvolleyball tournament with 20 teams and many
spectators. With perfectly sunny weather, music and cold drinks we had a great
day. After sports we enjoyed a barbecue in front of the chemistry department and
decorated the winners of the tournament.
Excursion to AIXTRON SE:
In August we had the chance to visit AIXTRON SE, which is a leading provider
of deposition equipment to the semiconductor industry and has been established in
Aachen. We listened to interesting presentations and we were given the chance to see
how the deposition equipment is built up.
Our plans for 2013:
In February a lecture will be held by Prof. Dr. Thomas Loetzbeyer – “Molekulare
Küche - Ein Experimentalvortrag über Gaudi, Genuss und Lebensfreude.”
In the end of February we are going to conduct another excursion to LANXESS AG
in Cologne.
In March we will pay a visit to the pharmaceutical company Grünenthal GmbH.
Furthermore we organize an experimental lecture in the summer term and want to
organize a spring party afterwards.
Another highlight will be the annual beachvolleyball tournament, that will take place
in summer again.
Poster 254
Saturday 9:00 - 11:30
311
JungChemikerForum Gießen
Michael Linden ∗ , Rabea Dippel†
Institute of Organic Chemistry – Justus-Liebig-University – Heinrich-Buff-Ring 58 –
Giessen – GER
†
Institute of Physical Chemistry – Justus-Liebig-University – Heinrich-Buff-Ring 58 –
Giessen – GER
∗
[email protected]
Since the foundation of the JCF Gießen in 2005, the group of members has grown
steadily with about ten of them being actively engaged. We regularly meet at the
“JCF Stammtisch”, where we plan our events and discuss current topics, problems or
just spend some quality time together.
Lectures:
Each Semester, we have the possibility to invite special guests during the ongoing
term of GDCh lectures. We highly appreciate guests who are talking about uncommon chemical topics, for example, “Supramolekulare Detektion von Sprengstoffen –
Grundlagen und Anwendungen“ (Prof. Dr. Siegfried R. Waldvogel, Johannes Gutenberg Universität Mainz); “Das Problem der nuklearen Entsorgung” (Prof. Horst Geckeis, Institut für Nukleare Entsorgung KIT).
A special lecture was given by Prof. Richard Ernst in November 2010. The noble
laureate gave the audience an extraordinary example of interdisciplinary work in his
talk entitled: “Die interkulturelle Passion eines Naturwissenschaftlers: Tibetische
Malkunst, Pigmentanalyse und Wissensvermittlung an tibetische Mönche”.
Theme nights:
Furthermore, we organize theme nights where we take a chemical view at different
topics. For example:
“Themenabend CSI: Chemiker suchen Indizien” Lecture: Dr. H. Wollersen,
Dr. P. Weis
“Berufseinstieg für Chemiker” and different lecturers from chemical companies, e. g.,
Evonik, Heraeus, VAA.
Excursions:
So far, we have organized excursions to chemical companies close to Gießen, e. g.,
Merck (Darmstadt), Seidel (Marburg/Fronhausen), ESA (Darmstadt), etc. In the
summer of 2011, we arranged a three-day trip to Leipzig, where we met the JCF
Leipzig and visited BELL and the department of chemistry at the university.
In December 2010, we organized an excursion to BASF Coatings (Münster) together
with the JCF Münster, followed by a jolly trip to the Christmas market.
Other activities:
In addition, we arrange a number seminars on different subjects (e.g., presentation
techniques, career entry), and represent the JCF/GDCh at the “Hochschulinformationstag” and the “Studieneinführungswoche”.
Together with the association “Verein der Freunde der chem. Institute e.V.” we organize a regular barbecue to celebrate the end of the summer term.
312
Saturday 9:00 - 11:30
Poster 255
Das JCF Halle
Bob-Dan Lechner , Marlou Keller, Tobias Jost, Ludwig Riedel
JungChemikerForum Halle – Martin-Luther-Universität Halle-Wittenberg –
Von-Danckelmann-Platz 4 – Halle (Saale) – GER
[email protected]
“Chemie gibt Brot, Wohlstand und Schönheit!”, so der Slogan der chemischen Industrie
der DDR. Insbesondere des Chemiedreieck unserer Region warb damit. Wir haben
uns dieses Motto zum Titel des JCFs gewählt, da auch bei uns derartige Aspekte eine
essentielle Rolle spielen.
Brot: steht für unsere intensiv gepflegte Verbindung zu den hiesigen Lebensmittelchemikern, die sich in der „AG Junge Lebensmittelchemiker“ selbst organisieren, mit
denen wir dann öfter gemeinsame Aktionen durchführen.
Wohlstand: Obgleich man einen solchen den Bewohnern der neuen Bundesländern immer abschätzig macht, weist das JCF Halle trotzdem selbiges erst kurze Zeit besteht,
eine wahre Fülle an Mitgliedern auf. Eine gute Beziehung zum Ortsverbandsvorsitzenden der GDCh erlaubt uns darüber hinaus auch größere Veranstaltungen und
GDCh/JCF Double-features zu erleben.
Schönheit: Nun, was soll man sagen. Schönheit ist ein vielberedter Begriff. Man
spricht einerseits von der Schönheit des Rotkohlsaftes, andererseits von der Schönheit
mancher gemeinsamer JCF Abende und natürlich der Schönheit der Frauen unserer
Uni. Nicht umsonst heißt es “Hier bei uns in Anhalt-Sachsen, wo die schönen Mädchen
wachsen.“.
http://jcf.chemie.uni-halle.de
Poster 256
Saturday 9:00 - 11:30
313
Index
315
Index
A
Abarca, Belen, 253
Abbasi, Muhammad S. A., 200
Abramczyk, Katarzyna, 119
Abt, Bärbel, 101
Adam, Rosa, 253
Adamczyk, Zbigniew, 90
Adaszyńska, Michalina, 184, 196
Aghatabay, Naz Mohammed, 118
Akhmadullina, Nailya, 210, 260
Albrecht, Ralf, 213
Almazahreh, Laith, 37
Alom, Shamim, 253
Alshakova, Irina, 187
Altınbaş Özpınar, Gül, 186
Altamura, Emiliano, 168
Altenburg, Horst XXX, 315
Altinbas Ozpinar, Gul
Altindal, Ahmet, 69, 153
Altun, Altan Alpay
Amakawa, Kazuhiko, 133
Amir, M. D., 118
Andrić, Jelena, 115, 122
Antonschmidt, Leif
Apfel, Ulf Peter, 37
Araqelyan, Qnar, 200
Arbuzova, Anna, 121
Arenz, Christoph, 160
Arkosi, Mariann Kinga, 70
Asmis, Knut, 54
Audisio, Davide, 156
Augustin, André
Augustin, Ewa, 278
Avciata, Ulvi, 214, 235
B
Baburin, Igor A., 43
Bachl, Jürgen, 116
Baier, Susann, 199
Balabhadra, Sangeetha, 231
316
Bald, Adam, 119
Ballesteros, Rafael, 253
Banerjee, Rahul, 116
Bansen, Roman, 96
Barberá, Joaquín, 53
Barkleit, Astrid, 111
Barner, Leonie, 71
Barner-Kowollik, Christopher, 71
Barta, Christoph
Bartetzko, Max
Bartling, Christian
Barzen, Sebastian, 177
Baudequin, Christine, 117
Bauer, Ingmar, 240
Baum, Anne-Kathrin, 36
Baumann, Arne, 263
Bayraktar, Sinem, 258
Beceren-Braun, Figen, 202
Becker, J. Sabine, 28
Becker, Peter, 205, 311
Beeg, Sebastian
Begunk, Robert, 292
Behrens, Malte, 129, 150
Bei, Iryna
Beil, Sebastian
Beleboukhari, Nasser, 165
Beller, Matthias, 74, 280
Belov, Vladimir N., 220
Berger, Robert, 188
Berger, Walter, 46
Bernard, Marek, 191
Bernsdorf, Arne
Biczak, Robert, 206
Bieker, Georg
Bielska, Dorota, 170
Bilgin-Eran, Belkıs, 64, 68
Bilyachenko, Aleksey, 79
Binder, Wolfgang H., 303
Binder, Yvonne
Binsker, Florian
Birczyński, Artur, 49
Bisschops, Tom, 127
Bita, Andrei, 291
Blay, Gonzalo, 92, 197, 268
Błauż, Andrzej, 252
Blume, Alfred, 303
Blümel, Marcus, 199
Boeck, Florian, 127
Boeck, Torsten, 96
Böhm, Marvin
Böhme, Uwe, 195
Böhnert, Tim, 65
Bojarski, Andrzej, 238
Bojić, Aleksandar, 103
Bojić, Danijela, 103
Böker, Birte, 234
Bolm, Carsten, 139, 300
Borissova, Aleksandra, 210
Börner, Hans G., 85
Borriss, Rainer, 178
Bösmann, A., 112
Bouche, Léa, 202
Braun, Beatrice, 297
Braun, Thomas, 209
Bräutigam, Maximilian
Brcanović, Jelena M., 284, 296
Brela, Mateusz, 215
Brendler, Erica, 195
Brendler, Vinzenz, 73, 111
Breunig, Jens Michael
Brieger, Claudia, 138, 155
Brodersen, Nicolai, 121
Bronstein, Lyudmila M., 75
Bröring, Martin, 234
Brudzisz, Anna, 109
Brunner, Eike, 82, 111
Brzózka, Agnieszka, 109
Büchner, Christin
Bucila, Virginia Ramona, 287
Budniak, Adam, 86
Budniak, Urszula, 169
Bulearca, Anca-Mihaela, 291
Burda, Kvetoslava, 228
Butschke, Burkhard, 38
C
Cakar, Fatih, 64, 68
Cal, Dariusz, 243
Calvete, Juan J., 161
Cankurtaran, Ozlem, 64, 68
Carafa, Marianna, 247
Carl, Peter
Carrillo-Cabrera, Wilder, 43
Cativiela, Carlos, 116
Cędrowski, Jakub, 174
Çelebi, Mithat, 77, 104
Celichowski, Grzegorz, 78, 83, 136
Ceylan, Özgür, 77, 104
Chang, Kaichin, 56
Chebanov, Valentin, 307
Cherepanov, Il’ia A., 219
Cheriti, Abdelkrim, 165
Churakov, Andrei, 260
Ciejka, Justyna, 170
Cieślak, Małgorzata, 136
Cîrcu, Monica Violeta, 298
Cotta, M.A., 101
Cuñat, Ana C., 126
Cybulak, Marta, 264
Cyza, Małgorzata, 179
Czochara, Robert, 163
D
Dabrowska, Anna, 227
Dabrowska, Anna Maria, 132
Dalkowski, Radoslaw, 290
Damian, Grigore, 70
Daniliuc, Constantin, 63, 194
Dathe, Margitta, 51
Davis, Ben G., 47
De Keukeleere, Katrien, 44
De Roo, Jonathan, 44
de Souza, A.A., 101
Delso, Ignacio, 48, 131
Demeshko, Serhiy, 297
Dernedde, Jens, 202
Desenko, Sergey, 236
Díaz Díaz, David, 116
Diederichsen, Ulf, 273, 293
Diehl, Andreas
Diehl, Bernd, 302
Diehl, Claudia
Dieskau, André P., 154
Dietl, Nicolas, 54
Dincer, Hatice, 258
Dipalo, Maria Concetta, 168
Dippel, Rabea, 312
Diudea, Mircea V., 287
Djordjevic, Aleksandra , 294
317
Dlugaszewska, J., 50
Dmitriev, Aleksey, 79
Dmitrieva, Jana
Dobrowolski, Dariusz, 89
Doerfler, Denise, 162
Dominiak, Paulina Maria, 169, 305
Donten, Mikolaj, 278
Drabińska, Beata, 238
Drath, Christine
Dronova, Marina, 79
Drzymala, Sarah, 190
Düdder, Hendrik, 150
Duric, Sasa, 137, 146
Dutkiewicz, Zbigniew, 191
Düzgünes, Nejat, 50, 248, 279
Dyadchenko, Viktor P., 310
Dzieciuch, Monika, 295
E
Ebersbach, Ben
Efimenko, Inessa, 260
Ehlers, Peter, 246
Eisenblätter, Jördis, 71
Eitner, Krystian, 107
Ejsmont, Krzysztof, 286
El Fray, Mirosława, 269
El-khateeb, Mohammed, 37
Emen, Fatih Mehmet, 186
Emmerling, Franziska, 96
Enderle, Eric
Enders, Dieter, 127
Engeser, Marianne, 128
Erden, Ibrahim, 100, 256
Erdoğmuş, Ali, 100, 166, 214, 235,
256
Ernsting, Nikolaus P., 277
Erol, Ismail, 68
Escamilla, Ana, 126
Esser, Norbert, 263
Ester, Movsisyan
Eychmüller, Alexander, 43, 62, 72, 82,
110, 181, 193, 267
F
Fehrenbacher, Ulrich, 71, 241
Feist, Michael, 250
318
Fensterbank, Louis, 148
Feringán, Beatriz, 53
Feys, Jonas, 44
Fiechter, Fridolin
Filipek, Elżbieta, 249
Filippov, Oleg A., 310
Fink, Daniel, 217
Fischer, Cathleen, 82
Fischer, Franziska
Fischer, Tobias, 130
Fischer-Fodor, Eva, 70
Fita, Piotr, 228, 266
Fopp, Carolin
Ford, Leigh, 41
Fornal, Emilia, 232
Foucout, Lénaig, 262
Frei, Maren
Freytag, Matthias, 63, 194
Frings, Marcus, 139
Fritz, Maria, 56
Fronert, Jeanne, 127, 311
G
Gabriel, Stefanie, 62
Gambacorta, Augusto, 40
Gandor, Felix
Gaponik, Nikolai, 181, 267
Garcia-Gonzalez, Eva, 178
Gasiorek, Friederike
Gasperi, Tecla, 40
Gawel, Marta, 227
Gehne, Sören, 51
Genersch, Elke, 178
Gensch, Tobias, 240
Gensel, Julia
Gericke, Eike, 96
Gerigk, Melanie
Gevorgyan, Ashot, 200
Ghirardello, Mattia, 175
Ghochikyan, Tariel, 246
Girón, Rosa María, 268
Gliemann, Bettina, 211
Glitscher, Emanuel
Glöckner, Andreas, 194
Glor, Cindy , 123
Głowacki, Ireneusz, 282
Goddard, Jean Philippe, 148
Gölden, Simon
Golub, Igor E., 310
Gomollon-Bel, Fernando, 48, 175
Gooßen, Lukas J., 145
Goral, Anna Maria, 305
Górecka, Ewa, 91
Görls, Helmar, 37
Gorobets, Nikolay, 236
Goroncy, Christian, 93
Goslinski, Tomasz, 50, 143, 191, 228,
248, 272, 279
Göth, Melanie
Gracia, Ismael, 53
Graf, Christina, 93
Graf, Matthias, 72
Grela, Karol, 144
Grobelny, Jaroslaw, 78, 83
Grolik, Maria, 89
Große, Steffi
Großmann, Kay, 73
Grosu, Ion, 113, 117
Groth, Ulrich, 208
Grünert, Anna
Grunst, Michael, 211
Grześkowiak, Magdalena, 157
Grzyb, Tomasz, 76
Gschwind, Ruth M., 147
Gul, Ahmet, 214, 235
Gumrukcu, Gulsah, 214, 235
Gut, Arkadiusz, 179
H
Hakobyan, Ani, 200
Hamkalo, Michal, 266
Hann, Stephan, 46
Hanßke, Felix
Hashmi, A. Stephen K., 24
Hatami, Soheil, 267
Hathazi, Gabriela Denisa, 70, 176
Hauser, Anett
Heck, Jürgen, 36, 134, 229, 237
Heffeter, Petra, 46
Heinze, Katja, 225
Heislbetz, Sandra, 180
Hell, Stefan W., 220
Hendel, Thomas
Hennig, Andreas, 159
Hens, Zeger, 44
Hermann, Gerrit, 46
Hermes, Michael
Herrmann, Andreas, 121
Herrmann, Anne-Kristin, 181
Herrmann, Roy, 209
Herwig, Christian, 250
Hey-Hawkins, Evamarie, 204
Hickey, Stephen G., 43, 62, 110, 193
Hnida, Katarzyna, 65
Hochkirch, Ulrike, 173
Hoffmann, Martin, 234
Hofmann, Anna
Hofmann, Bettina, 177
Hofmann, Johanna, 173
Holyst, Robert, 45
Holzweber, Markus, 162
Horeglad, Pawel, 132
Horn, Bettina, 250
Huang, Xueliang , 141
Huh, Joonsuk, 188
Hurtado-Guerrero, Ramon, 48
Hussner, Janine, 292
Huster, Daniel, 121
Hüttenhain, Stefan H., 161
Hutter, Herbert, 162
Huzar, Elżbieta , 189
I
Iannone, Francesco, 247
Iaroshenko, Viktor O., 198, 200, 223,
292, 301
Iglesias, Álvaro, 205
Ilic, Marija, 98, 294
Imhof, Wolfgang, 37
Intelmann, Matthias
Ivanov, Anton, 198
J
Jähnigen, Sandra, 195
Janissen, R., 101
Janoschka, Tobias
Jantschke, Anne, 82
Janus, Ewa, 261
Jarosz, Magdalena, 58
Jarzebinska, Anita, 278
Jarzembska, Katarzyna N., 169
Jarzynski, Szymon, 233
319
Jasiński, Marcin, 251
Jaskuła, Marian, 58, 65, 80, 84
Jemielity, Jacek, 239
Jevric, Lidija, 274, 281
Jones, Peter G., 63, 194
Jost, Tobias, 313
Joswig, Jan-Ole, 267
Jovanović, Ljiljana, 222
Jovanovic, Olga, 294
Jovanovic, Snezana, 98, 294
Jóźwiak, Andrzej, 243
Jung, Jarosław, 282
Junge, Henrik, 74
Junge, Kathrin, 280
K
Käbisch, Bert, 241
Kaczor-Kamińska, Marta, 99
Kähler, Kevin, 150
Kahraman, Gizem, 88
Kaiser, Selina
Kalajdzija, Natasa, 274, 281
Kalevaru, Narayana, 124, 275
Kalinichenko, Kira
Kalinin, Valery N., 219
Kalwarczyk, Tomasz, 45
Kaminski, Kamil, 170
Kandemir, Timur
Kapoor, Iti, 116
Kapusta-Kołodziej, Joanna, 80
Karaagac, Erdal
Karaman, Ferdane, 64, 68
Karaoglan, Gulnur Keser, 214
Karavelioğlu, Selvi
Karewicz, Anna, 170
Kastner, Katharina, 226
Katona, Jaroslav, 265
Kaya, Mehmet Arif, 69, 77, 104, 166
Keßler, Eva
Keller, Marlou, 313
Kępczyński, Mariusz, 171, 179, 295
Keser Karaoglan, Gulnur, 235
Keshavarz, Elahe
Keskin, Bahadir, 153
Kettemann, Frieder
Kierys, Agnieszka, 227
Kılıçarslan, Fatma Aytan, 256
Kırbac, Erkan, 100
320
Kirilin, Aleksey, 79
Kittler, Katrin, 283
Kittler, Susann, 110
Kivala, Milan, 211
Kjaer Nielsen, Pia, 133
Klaper, Matthias, 125
Kleemann, Julian, 311
Kleine, Tillmann, 300
Klimczak, Anna Agnieszka, 206
Klimczyk, Sebastian , 141
Klos, Manuel Rudolf
Klucznik, Tomasz, 221
Kluza, Rafal, 218
Knar, Arakelyan
Knölker, Hans-Joachim, 240
Knyazyan, Aram
Kobin, Björn
Koch, Gregor, 55, 142
Koch, Matthias, 190, 271, 283
Köckert, Hansjochen
Koczorowski, Tomasz, 228
Koel, Mihkel, 162
Koellensperger, Gunda, 46
Kollmorgen, Patrick, 124
Konopka, Krystyna, 50, 248, 279
Koplak, Oksana, 79
Körber, Wieland
Kotus, Joanna
Kovacevic, Strahinja, 274, 281
Kowalczyk, Agata, 278
Kowalkiewicz, Zuzanna, 97, 106, 183
Kowalska, Joanna, 239
Kowalski, Marcin, 259
Kowollik, Sandro
Kranz, C., 101
Krause, Norbert, 130
Kraushaar, Konstantin
Krawczyk, Barbara, 290
Kretzschmar, Jérôme, 111
Kreye, Markus, 194
Krich, Christopher, 263
Krogul, Agnieszka
Kroke, Edwin, 195, 241
Krówczyński, Adam, 91
Krstić, Nenad, 103
Kruk, Danuta, 49
Krumbein, Angelika, 283
Kryjewski, Michal, 143
Krysinski, Pawel, 278
Krzyżanowska, Anna, 289
Krzyczmonik, Anna, 309
Kuźmicz, Danuta, 89
Kubiak, Katarzyna, 90
Kubica, Aleksandra, 49
Kubicka, Aleksandra, 232
Küchenthal, Christian
Kuchkina, Nina V., 75
Kucinska, M., 50
Kuckling, Dirk, 67
Kühbeck, Dennis, 116
Kühl, Stefanie, 150
Kühn, Julius, 304
Kuhrt, Patrick, 123
Kujawski, Jacek, 191, 238
Külcü, Nevzat, 186
Kulik, Marta, 305
Kumke, Michael U., 51
Kurczab, Rafal, 238
Kurowska, Elżbieta, 84
Kuryltso, Vladyslav, 95
Kwiecień, Halina, 189, 196, 224
Kwolek, Urszula, 171
L
Lalović, Mirjana, 222, 245
Landschulze, Dirk
Lang, Heinrich, 257
Langer, Peter, 198, 223, 246
Łapok, Łukasz, 179
Lar, Claudia, 113
Lechner, Bob-Dan, 303, 313
Lee, Michael, 279
Lempke, Linda, 130
Lentz, Dieter, 146
Leovac, Vukadin, 222, 245
Lesniak, Anna, 244
Lesniak, Stanislaw, 233
Leubner, Susanne, 267
Levacher, Vincent, 262
Levitsky, Mikhail, 79
Lewandrowska, Anna, 285
Lewkowski, Jarosław, 206, 309
Li, Yuehui, 280
Liebscher, Jürgen, 121
Liebscher, Lydia, 43, 62
Lijewski, Sebastian, 279
Lill, Andreas, 177
Limberg, Christian, 201, 230, 250, 297
Lindel, Thomas, 39
Linden, Michael, 312
Lindermayr, Katharina
Linert, Wolfgang, 162
Linke, Vanessa
Linker, Torsten, 125
Linscheid, Michael W., 173
Lipiecka, Sylwia, 97, 106, 183
Lips, Katrin Susanne, 202
Lis, Stefan, 61, 231
Lis, Tadeusz, 309
Litwinienko, Grzegorz, 163, 174
Litwinska, Anna, 132
Liu, Shanshan, 276
Loew, Martin, 121
Löhmann, Oliver
Lojovic, Maja, 281
Lommens, Petra, 44
Loncar, Eva, 274
Lorenz, Tommy, 267
Loreto, Maria Antonietta, 40
Lorite, G.S., 101
Losensky, Louisa, 121
Loth, Sebastian, 26
Lu, Liang-Qiu, 280
Ludwig, Ralf, 277, 288
Lukomska, Marlena, 286
Lükermann, Daniel, 263
Lungwitz, Ralf, 162
Lupan, Iulia, 70
Luparia, Marco, 156
Lyczkowska, Patrycja, 136
M
Maaß, Sebastian
Maekawa, Miyuki, 63
Magerle, Robert, 303
Mahrwald, Rainer, 207
Mahut, Sonia, 176
Majcher, Aldona, 285
Makowska, Katarzyna, 97, 106, 183
Makuch, Edyta, 151
Malec, Katarzyna, 58
Mandel, Miles
Mandić, Emanuela
Mansuy, Virginie, 148
Marca, Eduardo, 48
Marcinkowska, Magdalena, 254
Märker, Björn
321
Marosanovic, Biljana , 281
Marrero-Tellado, José Juan, 116
Marten, Silvia, 190
Martin, Andreas, 124, 275
Martina, Miceli
Matusiak, Agnieszka, 206
Matviitsuk, Anastassia, 207
Maul, Ronald, 271, 283
Maulide, Nuno, 141, 156
Mavelli, Fabio, 168
Mazerska, Zofia, 278
Mazur, Maciej, 86
Mazziotta, Andrea, 40
McDonough, Michael, 47
Mebs, Stefan, 250
Meißler, Maria, 85
Meißner, Gisa, 123
Meier, Patrick, 188
Meineck, Myriam
Mele, Valentina, 247
Mellmann, Dörthe, 74
Merino, Pedro, 48, 131, 175, 216
Mert Balaban, Humeyra, 258
Mette, Katharina, 150
Metz, Peter, 199
Meyer zu Schwabedissen, Henriette, 292
Meyer, Franc, 297
Miceli, Martina, 40
Michel, Kathrin
Middel, Stephen, 293
Mielcarek, Jadwiga, 50, 143, 228, 248,
272, 279
Milchert, Eugeniusz, 289
Milewska, Aleksandra, 170
Miliutina, Mariia, 198
Milovanović, Milan, 115
Misini, Majda, 115
Misztal, Krzysztof
Mitić, Milan N., 284
Mitić, Snežana S., 284
Mitic, Violeta, 98, 294
Mitrović, Jelena, 103
Mizaikoff, B., 101
Mkrtchyan, Satenik, 200, 301
Mlostoń, Grzegorz, 203, 218, 255, 259
Mohamed Saied Mostafa, Essa
Monleón, Alicia, 92
Montesinos Magraner, Marc, 268
Morawski, Antoni W., 157
Mot, Augustin Catalin, 70
Muhler, Martin, 150
322
Müller, Fabian
Müller, Jens, 120
Müller, Sebastian, 178
Muñiz, Kilian, 205
Münzel, Martin, 47
Murias, M., 50
Murillo Munar, D.M., 101
Murlykina, Maryna, 307
Myka, Anna, 238
N
Nalivayko, Peter, 185, 187
Narozny, Maciej, 107
Naurecka, Magdalena Ligia, 285
Nechifor, Gheorghe, 105
Neda, Ion, 113
Neff, Michael, 182
Neidlinger, Andreas, 225
Neumann, Mike, 102
Neumann, Wilma, 204
Nielsch, Kornelius, 65
Niemczyk, Agata, 269
Nikolić, Ružica, 103
Nikolic-Mandic, Snezana, 98
Ninković, Dragan, 115, 122
Ninnemann, Nina M., 146
Niyomchon, Supaporn, 156
Niza Silva, B.C., 101
Nizamov, Shamil, 220
Njaradi, Sandra , 265
Njie, Abdoulie
Nojoumi, Saba
Nowak, Michal, 143
Nowakowska, Maria, 59, 87, 89, 170,
171, 179, 295
Nowicka, Anna Maria, 278
Nüesch, Frank Alain, 298
O
Obesser, Katharina, 112
Obijalska, Emilia, 203, 218, 255, 259
Ocak, Hale, 64, 68
Olubummo, Adekunle, 303
Omenat, Ana, 53
Oppermann, Alex
Opriş, Dorina Maria, 298
Orbeci, Cristina, 105
Orzechowska, Aleksandra, 228
Oschetzki, Dominik, 182
Osipov, Alexander P., 164
Ossowicz, Paula, 261
Ostrovskyi, Dmitro, 200
Oudeyer, Sylvain, 262
Owińska, Maria, 215
Özdemir, Merve, 256
Ozdemir, Zafer Omer, 158
Ozkal, Selma, 64
Özpınar, Celal, 186
Ozturkcan, S. Arda, 108, 153
P
Pacześna, Agnieszka, 249
Palumbo, Chiara, 40
Palusiak, Marcin, 286
Panse, Cornelia H., 293
Papamicaël, Cyril, 262
Paunovic, Dusan Ð., 296
Pavlović, Aleksandra N., 284, 296
Pavlović, Jovana Lj., 284
Pedersen, Kasper
Pedro, José Ramón, 92, 197, 268
Pescador, Paula, 121
Petersen, Diana, 273
Petit, Sylvain, 262
Petkova, Nadezhda
Petran, Anca, 121
Petras, Daniel, 161
Petrosyan, Andranik, 246
Petrovic, Goran, 294
Pfeffer, Inga, 47
Pfeiffer, Florian, 180
Pfister, Andrea
Pfister, Kai, 145
Pilawka, Ryszard, 261
Pinkert, Denise, 297
Pinkert, Thomas, 160
Pirovano, Claudio, 275
Pirwerdjan, Ramona, 300
Piskorz, Jaroslaw, 248
Piskorz, Tomasz, 140
Plachetta, Silke, 123
Plażuk, Damian, 252
Plietker, Bernd, 154
Płotka, Mieczysław W., 243
Podunavac Kuzmanovic, Sanja, 274,
281
Polte, Jörg, 42
Polupanow, Tatjana, 273
Popielarska, Hanna, 238
Popovic, Marko, 308
Poppe, Jan, 62, 110
Porshneva, Ksenia, 167
Pospiech, Steffen
Potempa, Jan, 170
Povie, Guillaume, 41
Pozzi, Davide, 41
Proserpio, Davide M., 287
Proske, Matthias, 271
Prymak, Iuliia, 124
Przepiórski, Jacek, 157
Przybylska, Dominika, 94
Puchala, Agnieszka, 244
Puciul-Malinowska, Agnieszka, 95
Purtak, Katarzyna, 91
Pyrc, Krzysztof, 170
Q
Quaranta, Eugenio, 247
R
Rachwalski, Michal, 233
Rademann, Klaus, 42, 96
Radović, Miljana, 103
Raimer, Björn, 39
Ramondenc, Yvan, 117
Rasala, Danuta, 254
Räthel, Jochen, 263
Rauhut, Guntram, 180, 182, 188
Reimann, Sebastian, 277, 288
Reinhardt, Ulrike
Reissig, Hans-Ulrich, 202
Reitz, Annika, 67
Renaud, Philippe, 41
Resch-Genger, Ute, 159, 267
Ressler, Thorsten, 55, 135, 142
Reznikov, Ivan
Richter, Constanze, 73
Riedel, Ludwig, 313
Riemer, Martin, 149
Risch, Stefan, 190
323
Roca-López, David, 216
Rodić, Marko, 222, 245
Rödl, Carmen B., 177
Roelens, Stefano, 116
Rohn, Sascha, 283
Röhr, Merle Insa Silja
Romanova, Natalia A., 56
Romański, Jarosław, 251
Rommel, Susanne, 154
Rosenow, Phil, 270
Rosowski, Marcin, 78, 83
Rosseeva, Elena, 43
Rossow, Torsten, 52
Roth, Christian, 288
Roth, Christina, 138, 155
Roth, Klaus, 32
Rozwadowski, Zbigniew, 261
Rudolf, Bogna, 232
Rudolph, Manfred, 37
Ruhe, Lena, 173
Runowski, Marcin, 231
Rurack, Knut, 130
Rybarczyk-Pirek, Agnieszka, 286
Rychlik, Błażej, 252
Rychter, Piotr, 206
Rys, Barbara, 215
Rząd, Ewa, 171
S
Sachs, Anne, 134
Sadaba, David, 131, 175
Saghyan, Ashot, 246
Saha, Subhadeep, 116
Şahin, Gizem
Sakhno, Yana, 307
Sallmann, Madleen, 201
Samarskaya, Alina S., 219
Samojłlowicz, Cezary
Samsonova, Janna V., 164
Sanz, Juan F., 126
Sanz-Marco, Amparo, 197
Savych, Iryna, 223
Sawoszczuk, Tomasz, 58
Scharf, Daniel
Scharf, Philipp, 120
Schaumberg, Christian
Schax, Fabian, 297
Scheer, Elke, 208
324
Scheidt, Holger, 121
Schendzielorz, Florian
Scheunemann, Jana
Schilde, Uwe, 102
Schlangen, Maria, 54
Schlecht, Sabine, 202
Schlögl, Robert, 129, 133, 150
Schloß, Svenja, 271
Schmidt, Bernd, 149
Schmidt, Bernd M., 146
Schmidt, Lena, 142
Schmidt, Martin, 128
Schmode, Stella, 277, 288
Schmudde, Madlen, 93
Schober, Katrin, 147
Schofield, Christopher J., 47
Schökel, Alexander, 138, 155
Schollmeyer, Martin
Scholz, Juliane, 135
Schön, Eva-Maria, 116
Schönborn, Enno, 275
Schreiner, Monika, 283
Schreiner, Peter R., 30
Schröder, Felix, 148
Schulz, Christian
Schulz, Matthias, 303
Schumann, Julia, 129
Schütz, Denise
Schwarz, Helmut, 38, 54
Scorei, Romulus Ion, 291
Sednev, Maksim V., 220
Seidt, Britta
Seiffert, Sebastian, 52
Sekkoum, Khaled, 165
Sen, Betul Nur, 258
Sener, Muhammet Kasim, 69
Senf, Antti
Serrano, Jose Luis, 53
Sevim, Ilhan, 114
Shahid, Khadija, 306
Shifrina, Zinaida B., 75
Shishilov, Oleg, 210, 260
Shubina, Elena S., 79, 310
Shyichuk, Andrii, 61
Sieredzinska, Bianka, 285
Sikorski, Andrzej, 140
Silaghi-Dumitrescu, Radu, 70, 176
Simon, Paul, 43
Simonovic, Strahinja, 98
Six, Alice, 255
Skupin-Mrugalska, P., 50
Ślepokura, Katarzyna, 309
Sloniec, Jagoda, 159
Smirnova, Daria V., 164
Śmist, Małgorzata, 184, 196
Smolan, Willi
Smusz, Sabina, 238
Sobczak, Justyna, 189
Sobotta, Lukasz, 50, 228, 272, 279
Sobottka, Sebastian
Sokolowski, Anja, 152
Soliwoda, Katarzyna, 78, 83
Sośnicki, Jacek G., 192
Sosnovskikh, Vyacheslav, 223
Souto, José A., 205
Söyler, Zafer, 118
Sozanski, Krzysztof, 45
Spange, Stefan , 162
Speck, Matthäus, 257
Speiser, Eugen, 263
Spitzner, Eike-Christian, 303
Sponholz, Peter, 74
Srivastava, Vishnu P., 242
Stachniuk, Justyna, 290
Stachowski, Gordon M., 193
Stange, Uta Corinna
Staniszewski, Zygmunt, 269
Stankov-Jovanovic, Vesna, 98, 294
Stanković, Maja, 103
Stano, Pasquale, 168
Stark, Holger, 177
Stefaniak, Monika, 251
Stefaniuk, Anna, 282
Steinhilber, Dieter, 177
Steinkamp, Anne-Dorothee, 139
Sternberg, Katrin, 292
Stockmann, Madlen, 73
Stojanovic, Branka T., 296
Stojanovic, Gordana, 294
Stojek, Zbigniew, 278
Stojkovic, Milan M., 296
Strauch, Peter, 102
Streb, Carsten, 226
Struk, Łukasz, 192
Stuckmann, Alexandra
Stutz, Christian
Su, Meng, 172
Sulka, Grzegorz D., 58, 65, 80, 84, 109
Supe, Linda, 292, 200
Süßmuth, Roderich, 178
Süssmuth, Roderich D., 161
Svensson, Emma, 137
Swarcewicz, Maria, 184
Sydow, Karl, 51
Sygula-Cholewinska, Justyna, 58
Symonowicz, Michał, 163
Sypaseuth, Fanni, 299
Sysoiev, Dmytro, 208
Szafraniec, Joanna, 87
Szczepaniak, Grzegorz, 144
Szczolko, W., 50
Szczolko, Wojciech, 191, 228
Szczubiałka, Krzysztof, 89, 170
Szczukocki, Dominik , 290
Szemraj, Janusz, 206
Szewczyk, Grzegorz, 179
Szpak, Agnieszka, 59
Szuwarzyński, Michał, 66
Szydłowska, Natalia, 295
T
Taden, Andreas, 85
Talantsev, Artem, 79
Taleb, Safia, 165
Tamm, Matthias, 194
Tamm, Nadezhda B., 56
Tarasov, Andrey, 129
Tatev, Grigoryan
Tavernaro, Isabella, 202
Tegenkamp, Christoph, 263
Tejero, Tomás, 48, 131, 175, 216
Teng, Heidi
Terec, Anamaria, 113, 117
Thiedemann, Birk
Thomale, Jürgen, 173
Thomas, Nygil, 129
Tikhonova, Julia
Ţînţaş, Mihaela-Liliana, 262
Tkacz-Szczesna, Beata, 78, 83
Tokarz, Paweł, 309
Töllner, William, 65
Tomsik, Alena, 265
Tonner, Ralf, 270
Tosic, Snezana B., 296
Tosun, Ece, 81
Trinkaus, Katja, 202
Troyanov, Sergey I., 56
Trunschke, Annette, 133
Trützschler, Anne-Kristin
Trylska, Joanna, 305
325
Tschersich, Carolin, 230
Tugcu, Fatma Tülay, 60, 81, 88
Turgut, Zuhal, 108
Turhan, Kadir, 108
Tykarska, Ewa, 50, 279
Tzschucke, C. Christoph, 123, 137, 146,
152, 213, 276, 299
U
Uebele, Katharina
Ugarova, Natalia N., 164
Uğur, Ahmet Lütfi, 100, 166
Untea, Ion, 105
Urbaniak, Alicja
Urbaniak, Włodzimierz, 97, 106, 107,
183
Utecht, Greta, 203
V
Van Driessche, Isabel, 44
Vasilkevich, Alexey
Veiros, Luis F., 141
Veljković, Jovana N., 284, 296
Viehoff, Maria
Viktor, Iaroshenko
Vilches-Herrera, Marcelo, 200
Villa, Giorgio, 41
Villinger, Alexander, 223, 301
Vishchuk , Olesya S., 167
Vlad, Miranda Petronella, 287
Vodolazhenko, Mariia, 236
Voigt, Benjamin, 207
Vojinović-Ješić, Ljiljana, 222, 245
von Kiedrowski, Gunter, 114
von Rekowski, Felicitas, 147
Vondung, Lisa
Warncke, Gisela, 212
Wasserscheid, P., 112
Watal, Geeta, 242
Węcławiak, Mariusz
Weidemann, Stefan, 96
Weigand, Wolfgang, 37
Wendt, Robert
Wiebalck, Swantje, 123
Wieczorek, Anna, 252
Wieczorek, Sebastian
Wierzchowski, Marcin, 50, 228, 272,
279
Wiglusz, Rafał, 94
Wildenhof, Thomas
Wilhelm, René, 67
Wind, Marie-Louise
Winkler, Helmut
Winkler, Rajko
Winter, Rainer, 217
Wohlrab, Sebastian, 124, 275
Woiczechowski-Pop, Adrian, 117
Wojtczak, Błażej, 239
Wolfram, Benedikt, 234
Wolski, Karol, 66
Wolter, Anne, 229
Wolter, Klaus-Jürgen, 72
Wolters, Daniel
Wolz, André, 155
Wowra, Bogumił , 89
Wozniak, Martin
Wróblewska, Agnieszka, 151
Wrona, Ewa, 215
Wrześniewska, Agata, 224
Wuithschick, Maria, 42
Wuttke, Evelyn, 217
Wybranska, Iwona, 58
Wylęgała, Edward, 89
Y
W
Wagler, Jörg, 212
Wahl, Sebastian
Walczak, Aleksandra, 254
Walczak, Sylwia, 239
Wallis, Philipp, 275
Walter, Marc D., 63, 194
326
Yadav, Arvind K., 242
Yadav, Deepak K., 242
Yadav, L. D. S., 242
Yasa, Göknur, 100, 256
Yıldırım, Hüseyin, 77, 104
Yurtseven, Hilal, 69
Yuzik-Klimova, Ekaterina Yu., 75
Z
Zagórski, Piotr, 243
Zailer, Elina, 302
Zakrzewski, Janusz , 252
Zakrzewski, Robert, 290
Zapotoczny, Szczepan, 59, 66, 87, 95
Zarić, Snežana, 115, 122
Zaspel, Irmtraut, 271
Zeuschner, Janek
Zhikol, Oleg, 236
Zielinski, Adam, 144
Ziemann, Elisabeth, 237
Zitterbart, Robert
Zlatkovic, Bojan, 294
Zorlu, Yunus
Zucker, Sina P., 146, 137
Zühlke, Martin
Zvyagintseva, Tatiana N., 167
327
328
Sudoku
329
C
O
F
O
Li
B
He C
N
H
F
He
H Be
Li
H
N
Be He
C
B
He N
F
Be
He
B
330
Be Li
Li
F
N
N
Li
C
Mg
Mg P Na Ne
S
Al Mg Si
S
Mg
Ne
Si
Mg S
Cl Ne P
Ar
Na
Cl
Al Mg S
Cl
Ne Al Ar
S
Na
Na
331
Ga
Kr
Kr
Se Ca
Ca As
Rb
Rb As
Se Ge
As
K
Ca K
Ga Kr
Kr
Se Br
K Ga
Ge
K
332
Rb
I
Cs Sn
Sb
Sb Sn
In
Xe
I
Sn
Te
Cs
Ba
Sb
Te
Ba
Sr
In
I
Sr
Ba
I
Ba Xe
Xe
Sn
333
S u p p o rt e rs
Wednesday Thursday
March 6 th March 7 th
8:50-9:30
Plenary Lecture
Prof. Dr. S. Hashmi
1 0:00
Plenary Lecture
Dr. habil. J. S. Becker
9:1 0-1 0:1 0
9:30-1 0:30
Break
Break
1 0 min Poster Talks
1 0 min Poster Talks 4x 20 min Oral
3x 20 min Oral
Presentations
Presentations
1 0:30-1 2:00
1 1 :00
1 0:50-1 2:00
1 2:00
Lunch Break
9:00-1 1 :30
Closing Lecture
Prof. Dr. K. Roth
Lunch Break
Closing Ceremony
1 2:30-1 3:30
Registration
1 2:00-20:00
1 5:00
3x 20 min Oral
Presentations
3x 20 min Oral
Presentations
Break
Break
1 3:30-1 4:30
Plenary Lecture
1 6:00
Social Activities
Plenary Lecture
Prof. Dr. P. R. Schreiner
Break
Break
1 4:50-1 5:50
1 0 min Poster Talks 1 0 min Poster Talks
4x 20 min Oral
4x 20 min Oral
Presentations
Presentations
1 6:1 0-1 7:40
1 6:1 0-1 7:40
1 6:00-1 9:00
1 8:00
Poster Session
and Champagne
Reception
1 9:00
Break
1 7:40-20:1 0
Conference Dinner
1 9:00-21 :30
Welcome Reception
20:00
Break
1 3:30-1 4:30
Dr. S. Loth
1 4:50-1 5:50
20:00
Poster Session
and
"Frühschoppen"
1 1 :30-1 2:30
1 3:00
1 7:00
Saturday
March 9 th
Opening Ceremony
9:00
1 4:00
Friday
March 8 th
Conference Party
22:00
Social Activities
1 4:00-1 9:00

- JCF Berlin

Transcription

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