File - Royal Society of Chemistry Early Careers Symposium

Transcription

th
4 Royal Society of Chemistry
Early Career Symposium
23-24 June 2016
University of
Strathclyde
The ECS2016 committee would like to thank all our sponsors for their generous support.
Please share your experience on social media:
@RSC_ECS @RoySocChem #ECS2016 #Time4Chem
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PROGRAMME
Thursday 23rd June
Time
13.00
Registration with Tea/Coffee
13.45
Welcome - Room TG312
14:00
Keynote Speaker: Ricky Martin - Hyper Recruitment Solutions - Room TG312
My journey in science and thoughts on how to stand out in the scientific community
Organic & Biochemistry
Room TG312
Robert Paton – University of Oxford
15:00
15:30
15:45
16:00
16:30
17:00
17:15
Computational design of new ligands for
asymmetric transition metal catalysis
Nicholas Whiteley - Uni. of Edinburgh
The limit of cooperativity in H-bond
networks
Matthew Grayson – Uni. of Cambridge
Understanding catalytic mechanisms using
computational methods
Inorganic & Materials Chemistry
Room TG314
Richard Darton – University of Keele
Catalysis by Design: Overcoming Catalyst
Deactivation in Methane Reforming
Reactions
Joanna Aldred - Durham University
Taming pyridyl-N-phosphinoimines
Sonia Bajo - University of Strathclyde
Oxidative Addition of Aryl Halides to
[Ni(COD)(dppf)]
Physical & Analytical Chemistry
Room TG310
Karen Johnston – University of Durham
The Bigger Picture: Structural Insights into
Functional Materials using Diffraction,
Solid-State NMR and First-Principles DFT
Calculations
Gillian Carse - IOM Edinburgh
Characterisation of high aspect
nanomaterials to support hazard assessment
Damion Corrigan - Uni. of Strathclyde
Rapid electrochemical assays for biomedical
applications
Chemical Education & Outreach
TG223
Andy West - Pera Technology Solutions
Is Volunteering Good for Business?
Fraser Scott - University of Strathclyde
Simulated peer assessment as a means to
solve the ‘mathematics problem’ in science
education
Tea/Coffee and Posters
Room TG312
Nikolaos Georgakopoulos - Keregen
Non-covalent small molecule inducers of
Nrf2 for the treatment of Parkinson's
Disease
Maria Kopsida - Robert Gordon Uni.
trans,trans-BNIPDaCHM: a Novel
Bisnaphthalimidopropyl (BNIP) derivative
designed for targeting DNA in a human
breast cancer cell line
Timothy Allen - University of Cambridge
Towards an MIE atlas
Room TG314
Stuart Robertson – Uni. of Strathclyde
1,2-Dihydropyridines: from kinetic
intermediates to isolable compounds
Nicola Bell - University of Edinburgh
Controlling uranyl oxo group
interactions to group 14 elements using
polypyrrolic Schiff-base macrocyclic
ligands
Ross Davidson - Durham University
The incorporation of transition metals
into single molecule conductors
Room TG310
John Griffin - University of Lancaster
An Atom’s Eye View: Studying Structure and
Function in Materials using Nuclear
Magnetic Resonance Spectroscopy
Amit Delori - University of Strathclyde
Supramolecular hair dyes (SHDs): A
new application of co-crystallization
TG223
Heather Doran - University of Aberdeen
Combining Public Engagement and
Research
Sarah Hampson - Loughborough Uni.
3D-printed microdevices for particle
synthesis and analysis
Joy Leckie - University of Strathclyde
ReallySmallScience on Tour
Rowena Fletcher-Wood - RSC
Environmental Chemistry Group
Translating Theory to Practice
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17:30
17:45
18:00
19:30
21:00
Tilemachos Kosmidis - Uni. of Strathclyde
Defining the Structural Determinants of
Transcriptional Fidelity in an Expanded
Genetic Alphabet
Robert Edkins - University of Oxford
Tuning the optical and electronic properties
of boron-containing electron-acceptor
groups
Phil Jemmet - University of Birmingham
Understanding lipid behaviour: improving
the therapeutic potential of glycolipids
Alistair Boyer - University of Glasgow
1-Sulfonyl-1,2,3-triazoles versus sea
lampreys
Danielle Fragoso - University of Glasgow
Lignin conversion to fine chemicals
James McDonagh - Uni. of Manchester
The Generation of a Novel Force Field
for Biomolecular Simulation
Lewis Hou – Science Ceilidh
Workshop
Wine Reception, Hot Buffet and Poster Judging
Break
Science Ceilidh @ Strathclyde Union (finishes at midnight)
Friday 24th June
09:00
09:30
10:00
10:15
10:30
10:45
11:00
Tea/Coffee and Poster Viewing
Room TG312
John Bower - University of Bristol
Catalytic Chirality Generation: New
Strategies for Heterocyclic Chemistry
Room TG314
Jemma Rowlandson - University of Bath
Towards Tuneable Lignin-Derived Activated
Carbons for Energy Storage Applications
Room TG310
Marcel De Matas - Seda PDS
Transforming Molecules into Valued
Medicines: The Domain of the
Pharmaceutical Scientist
Maksim Misin - University of Strathclyde
How liquids affect solutes: Modelling
solvation using physics-based model
Neil Keddie - University of St. Andrews
All cis-1,2,3,4,5,6hexafluorocyclohexane: the most polar
aliphatic motif currently identified
Alex Cresswell - University of Edinburgh
Room temperature gold-catalysed arylation
of heteroarenes: Orthogonality to SuzukiMiyaura cross-coupling
Mustapha Garba - University of Glasgow
Carbon laydown analysis of transhydrogenation activity over CrOx/Al2O3
catalyst
Adam Hardy - Heriot-Watt University
A new approach to screening and designing
solvents for low-dimensional materials
Elizabeth Frye - Syngenta
The synthesis of Tentoxin analogues as
potential herbicides
Maria Heras Ojea - University of Glasgow
Enhancement of TbIII-CuII singlemolecule magnet performance through
structural modification
Suchanuch Sachdev - Loughborough Uni.
Synthesis and assembly of gold particles on
an emulsion droplet; nanoparticles,
nanosheets and core-shell particles
John Santos - University of Glasgow
Organic solar cells, the future:
development of DODIPY-based small
molecules for organic photovoltaics
Sebastien Rochat - University of Bath
Polymer-based porous composite
materials for hydrogen storage
applications
Anna Stradomska - University of Glasgow
Modelling excited state dynamics in
molecular aggregates: From dimers to
porphyrin nanotubes
TG223
Debra Willison - Uni. of Strathclyde
Promotion and Outreach Activities
Arno Kraft - Heriot-Watt University
Videos, apps and LEGO instruments
Marc Reid - University of Edinburgh
Capturing fast organic reactions: new
approaches to stopped flow kinetics
Menno de Waal - EYCN
EYCN - connecting chemists around Europe
Tea/Coffee and Poster Viewing
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Room TG312
Volker Engels - Cambridge NanoCat
Fully Automatic Organic Synthesis
Zoe Wilson - University of Cambridge
Flow enabled peptide synthesis
Room TG314
Nicholas Chilton - Uni. of Manchester
The Road So Far
Haralampos Miras - Uni. of Glasgow
Towards design of 2D layered materials via
a molecular assembly approach
12:15
Wen Zhu - Cardiff University
How does a metalloprotein catalyze
chemically difficult reaction: the mechanistic
study of Bacillus subtilis oxalate
decarboxylase
Tina Yu-Ting Su - University of Glasgow
Lithium hydride and organic amines for
hydrogen storage
12:30
Keynote Speaker: Dominic Tildesley - President of the Royal Society of Chemistry - Room TG312
Modelling: the adventures of a young chemist
13:15
Prize Ceremony and Closing Remarks
14:00
Buffet Lunch
11:30
12:00
Room TG310
Robert Šardzík - Syngenta
Title TBC
Pól MacFhionnghaile - Uni. of Strathclyde
Going from Product to Process Analysis:
Analysing Pharmaceutical Crystallisation
using in-situ Spectroscopy
Kirsten Gracie - University of Strathclyde
Development of Nanoparticle Based
Detection Methods
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CONTENTS
PROGRAMME ....................................................................................................................................... 3
CONTENTS............................................................................................................................................ 6
WELCOME ............................................................................................................................................ 7
ECS2016 COMMITTEE ........................................................................................................................ 8
KEYNOTE SPEAKERS ......................................................................................................................... 9
INVITED SPEAKERS ......................................................................................................................... 11
ORGANIC AND BIOCHEMISTRY ................................................................................................ 11
INORGANIC AND MATERIALS................................................................................................... 15
PHYSICAL AND ANALYTICAL................................................................................................... 18
EDUCATION AND OUTREACH ................................................................................................... 22
ORAL ABSTRACTS............................................................................................................................ 26
ORGANIC AND BIOCHEMISTRY ................................................................................................ 26
INORGANIC AND MATERIALS................................................................................................... 38
PHYSICAL AND ANALYTICAL................................................................................................... 50
EDUCATION AND OUTREACH ................................................................................................... 61
POSTER LIST ...................................................................................................................................... 64
DELEGATE LIST ................................................................................................................................ 66
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WELCOME
On behalf of the Royal Society of Chemistry’s Early Career Network, the ECS organising committee
and the University of Strathclyde, I would like to welcome you to #ECS2016.
ECS2016 is the fourth in a series of symposia designed for, and organised by, early-career chemists
from across all disciplines and sectors. The aim of this symposium is to bring early-career chemists
together – to share their research with their peers; to network across the disciplines and to learn about
the diverse career paths available to us.
As always, ECS2016 has a strong line-up of keynote and invited speakers representing the cream of
emerging talent from across the UK’s industrial and academic sectors. All of our invited speakers will
share with you not only their research, but also how they reached this point in their careers. This is a
unique opportunity for you to learn from those who have “made it” and I would strongly encourage you
to speak to our guests throughout the event.
Crucial to the success of any symposium is the quality of abstracts received for oral and poster
presentations. Once again, the committee was overwhelmed by the volume and impact of the many
abstracts we received from around the world. I would like to thank all the delegates for submitting their
abstracts for consideration. Our only regret is that there is never enough time and space to afford
everyone the opportunity to present.
Movement between seminars is strongly encouraged – speakers have been made aware of the possibility
of some disruption so please don’t feel embarrassed to switch rooms! There is also lots of time reserved
for poster viewing. This represents a great chance to meet with your peers from other disciplines, gain
new insights and form life-long collaborations and networks. You can also continue your “networking”
at our Science Ceilidh on Thursday evening.
I would like to thank all of our sponsors wholeheartedly for their support of ECS2016. I would
especially like to thank our hosts here at the University of Strathclyde for giving us access to their
facilities today.
Finally, I would like thank you for participating in #ECS2016 and hope you enjoy two days of exciting
inter-disciplinary science.
Thomas McGlone
ECS 2016 Committee Chair
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ECS2016 COMMITTEE
If you have any questions throughout the day, please speak to a committee member. We’ll have name
badges with a red stripe to help you spot us.
Thomas McGlone
Chairperson
Sian-Sloan Dennison
Secretary
Laura Yates
Treasurer
Nitika Bhalla
Paul Brack
David Foley
Alexandre Giard
Olajide Onike
Scott Sneddon
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KEYNOTE SPEAKERS
Ricky Martin - Founder, Hyper Recruitment Solutions
Ricky graduated as a Biochemist from Cardiff University in 2006. This
subsequently fuelled his passion for a career in the Life Science sector, since
then he has almost 10 years recruiting exclusively for the sciences. Ricky was
crowned winner of The UK Apprentice in June 2012 and has since successfully
set up and expanded his own specialist recruitment consultancy, Hyper
Recruitment Solutions using the investment from Lord Sugar. The business
supports the mission of wanting to help people and improve lives through
healthcare and / or new technologies. Ricky is also a member of the Royal
Society of Chemistry and the Vice Chair of the UK Life Sciences committee for the REC, sharing best
practice and helping to raise the standards in the industry.
My journey in science and thoughts on how to stand out in the scientific community
Finding your dream career within the scientific market has never been more challenging with many
large company closures and relocations, rising competition within the UK and abroad and increasingly
tighter government constraints. In general, academic training is only one aspect in which potential
employers base their decision to recruit meaning individuals must be doing more to make themselves
stand out from the crowd. The traditional model of securing that first or second job following university
and remaining loyal to a company for 20, 30, 40+ years is definitely waning, strongly suggesting that
employees should be constantly thinking about their personal and professional development and
keeping their CV’s up-to-date. In my plenary, I will discuss some of the experiences and decisions I
have made throughout my own career and why I do what I do in science. This will support some of the
key things early career researchers should be looking at to improve their employability and just as
importantly, retainability.
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Prof. Dominic Tildesley - President of the Royal Society of Chemistry
Dominic Tildesley received his BSc in Chemistry from Southampton
University in 1973 and his DPhil from Oxford University in 1977. After
postdoctoral positions at Pennsylvania State University, Cornell and Oxford,
he joined the Chemistry Department at Southampton University in 1981. He
was awarded the Chair of Theoretical Chemistry at Southampton in 1990.
In 1998 Dominic joined Unilever Research Port Sunlight as the Head of the Physical Sciences Group.
In 2003 he became Chief Scientist for Unilever’s Home and Personal Care Division. He retired from
Unilever in June 2012.
He moved to Switzerland in January 2013, to become Director of CECAM (Centre Européen de Calcul
Atomique et Moléculaire) based in Lausanne in Switzerland. He is currently Professor Titulaire at the
École Polytechnique Fédérale de Lausanne.
His research interests include the statistical mechanics of liquids, computer modelling of complex fluid,
the simulation of adsorption and the application of high performance computing to industrial problems.
He is the author of The UK e-Infrastructure Strategy for Science and Business: a roadmap for the
development and use of advanced computing, data and networks, and he co-chaired the UK Einfrastructure Leadership team with David Willetts, Minister of Science. He is currently President of
the Royal Society of Chemistry and received a CBE for services to science, technology and business in
2014.
Modelling: the adventures of a young chemist
My deep interest in computing and software in particular began in the summer of 1973. As a young
undergraduate chemist at the end of my second year at Southampton, I had the opportunity to work for
the summer with IBM, learning to program in their Development Laboratory at Hursley. My summer
holiday work was enthralling and convinced me to commit to a PhD, which would combine chemistry
and this newfound appreciation of the computer. In those days we would trek from the Chemistry
Department to the Computing Centre carrying a box of 500 punched cards. 20 minutes of run time
overnight was the state-of-the-art and, depending on the size of queue, I could perform Monte Carlo
simulations of 108 hard dumbbells as a model for liquid N2. Output was on line-printer paper, and
punched cards; there was little or no computer graphics; and a small compilation error cost a full 24
hours.
40 years later I was asked to serve as the President of the Royal Society of Chemistry. In my inaugural
speech, I suggested that, "the speed and development of computers is now so rapid, and the advances
in modelling and informatics are so dramatic that in 15 years time, no chemist will be doing any
experiment at the bench without trying to model it first". So despite the fact that chemistry is essentially
and absolutely an experimental science, from this point forward, it would always be decorated and
enhanced by modelling.
What had changed since the 70’s, when one solid gust of wind on the Banbury Road could have reduced
the universe of molecules from 108 to 107 by the loss of a single card? What developments and changes
over my career had inspired such an optimistic outburst from an ageing modeller?
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INVITED SPEAKERS
ORGANIC AND BIOCHEMISTRY
John Bower – University of Bristol
John obtained his MSci degree in Chemistry in 2003 from the University of
Bristol. He then remained at Bristol to study for his PhD degree (2007) under
the guidance of Professor Timothy Gallagher. During this time his research
focused on the development of cyclic sulfamidate based N-heterocyclic
methodologies and their application to natural product synthesis. His first
postdoctoral appointment (2007-2008) was with Professor Michael Krische
at the University of Texas at Austin where he investigated transfer
hydrogenative strategies for carbonyl addition. He then undertook a second
postdoctoral appointment with Professor Timothy Donohoe at the University of Oxford where he
focussed on the use of olefin cross metathesis for heteroaryl synthesis.
In 2010, he was awarded a Royal Society University Research Fellowship and commenced his
independent career at the University of Bristol. His group’s research interests lie broadly within the area
of asymmetric catalysis, with an emphasis on the development of green processes (atom economy, step
economy and selectivity). Current studies are directed towards (i) the development of new methodology
for heterocyclic chemistry, (ii) the application of these processes to natural product synthesis and (iii)
the evaluation of natural product analogues for medicinal purposes. The understanding of reaction
mechanism to increase the efficiency, scope and applicability of new transformations is also of
paramount interest. John has been the recipient of a number awards and fellowships, including the RSC
Harrison-Meldola Memorial Prize (2013), an ERC Starter Grant (2015), and the RSC Hickinbottom
Award (2015).
Catalytic Chirality Generation: New Strategies for Heterocyclic Chemistry
Our research programme is focussed upon the development of new catalysis platforms that enable direct
access to medicinally valuable chiral scaffolds. Recently, we outlined a metal-catalysed (3+1+2)
carbonylative cycloaddition strategy for the synthesis of complex nitrogen containing scaffolds
(Scheme 1A).1 The key metallacyclic intermediates 1 are generated by Rh-catalysed carbonylative ring
expansion of readily available amino-substituted cyclopropanes. To control the regioselectivity of this
process we have developed a directing group based strategy, which takes advantage of the N-protecting
group (Scheme 1B). This approach controls (a) the regioselectivity of oxidative addition (into the more
hindered cyclopropane C-C bond) and (b) the regioselectivity of CO insertion. Mechanistic aspects of
this process will be discussed and prototypical catalytic processes that involve trapping of the
metallacyclic intermediate with tethered alkynes or alkenes will be presented.[13]
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1.
M. H. Shaw, E. Y. Melikhova, D. P. Kloer, W. G. Whittingham and J. F. Bower, J. Am. Chem. Soc. 2013, 135, 4992-4995.
2.
M. H. Shaw, N. G. McCreanor, W. G. Whittingham and J. F. Bower, J. Am. Chem. Soc. 2015, 137, 463-468.
3.
M. H. Shaw, R. A. Croft, W. G. Whittingham and J. F. Bower, J. Am. Chem. Soc. 2015, 137, 8054-8057.
Volker Engels - Cambridge NanoCat
Volker holds a Ph.D. in catalytic nanochemistry from the Cambridge
University Department of Chemistry (Brian F. G. Johnson). Among others, he
has worked as a scientist at the Max-Planck-Institute for Coal Research,
Mülheim/Germany, and as a JSPS Research Fellow in Japan, authoring close
to 30 publications and receiving multiple prestigious awards for his work.
Prior to co-founding Cambridge NanoCat, he has also been a strategy
consultant in nanotechnology for the European Commission and scientific coadvisor to the Romanian government.
Fully Automatic Organic Synthesis
Our mission at Cambridge NanoCat is to develop a scalable solution for the fast and fully automatic
synthesis of organic small molecules. Once this development is done, we will be in the position to
deliver world’s first molecular 3D printer.
To achieve this goal, we make use of two key technologies that have gained tremendous attention over
the past years, namely microreactor systems, which offer a wide range of advantages over traditional
batch reactors in terms of facilitating and controlling the reaction process, and a novel type of
nanodimensional catalysts with as yet unachievable chemical stability. These catalysts have proven to
be an extremely potent alternative to both traditional heterogeneous catalysts and standard
nanocatalysts. Cambridge Nanocat combines these technologies with an external neuronal network into
a device for the highly predictable synthesis of organic structures. Moreover, by automatising the
traditional laboratory process, we are able to achieve improved catalytic efficiencies, as well as reduced
reaction times and waste materials.
Apart from introducing our project and some of its scientific achievements so far, the talk will give an
overview over the tech-entrepreneurial process - from a personal perspective and with valuable insights
for the entrepreneur-to-be.
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Nikolaos Georgakopoulos – Keregen Therapeutics
Nikolaos co-founded Keregen Therapeutics, a UCL start-up company
focused on the development of first generation small molecule Nrf2
inducers for diseases where there is an unmet clinical need. In 2015, he was
part of the team that won the OneStart Europe bio-entrepreneur competition
and was awarded £100k and lab space to take the company forward.
Nikolaos is due to complete his PhD in medicinal chemistry at UCL, where
he also obtained an MSc in Drug Discovery with distinction. His research
interests lie in the field of chemical biology with a current focus on the
Keap1-Nrf2 signalling pathway and its interplay with mitochondrial function and quality control.
Non-covalent small molecule inducers of Nrf2 for the treatment of Parkinson's Disease
Nuclear factor-erythroid 2-related factor 2 (Nrf2) is a transcription factor that orchestrates one of the
main cellular stress responses by regulating the expression of antioxidant, anti-inflammatory and
cytoprotective gene products. Nrf2 expression levels decline with age, leaving tissues, particularly the
CNS, vulnerable to oxidative damage. Accumulating evidence from in vitro and in vivo studies in
models of Parkinson’s Disease (PD) suggest that activation of Nrf2 could slow down or even reverse
PD progression. However, traditional Nrf2 inducers suffer from a lack of specificity in their mode of
action, compromising the Nrf2-mediated neuroprotection and limiting their clinical applicability.
Keregen’s primary drug discovery program aims to develop first-in-class non-covalent small molecule
inducers of Nrf2 for the treatment of PD, which are expected to show several advantages compared to
current therapies. This presentation will plot the journey from our discovery of the distinctive biology
of reversible Nrf2 inducers through winning OneStart Europe 2015, and beyond. In addition, the
challenges involved in setting up a biotech start-up, whilst simultaneously translating an academic
project into a viable business proposition will also be discussed.
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Robert Paton - University of Oxford
Rob Paton is an Associate Professor in Organic Chemistry at Oxford who
uses computation to understand and predict organic structure and reactivity.
In 2015 he received the RSC Harrison-Meldola Memorial Prize for
pioneering the rational design of catalysts and an Outstanding Junior
Faculty Award from the ACS Computers in Chemistry division. Rob
completed his PhD in Cambridge, followed by a Fulbright-AstraZeneca
postdoctoral fellowship at UCLA and a visiting fellowship at the Institute
of Chemical Research of Catalonia.
Computational design of new ligands for asymmetric transition metal catalysis
Computational chemistry provides unparalleled insight into the transition structures of catalytic
reactions. This delivers new understanding of the non-covalent interactions critical for reactivity and
selectivity. Alongside experimental investigatations we have explored the mode of action of asymmetric
organocatalysts, where our insights into mechanism have been used to explain unusual reactivity (such
as a formally disfavoured 5-endo-trig carbocyclization) and to design of more atom-efficient
asymmetric catalysts.
Despite the widespread adoption of computational tools across chemistry, the prediction and design of
asymmetric catalytic reactions is not yet routine. In this talk we discuss some of the inherent challenges
involved in the quantitative prediction of stereoselectivities, and our ongoing approaches to overcome
them. The development of bespoke transition state force fields is introduced as a means to accurately
describe these species accurately and efficiently, which has led to new ways of studying
conformatioanlly flexible systems in our group. We present two approaches for the design of new
ligands for asymmetric transition metal catalysis, based on a mechanistic study of competing pathways
in the cycloisomerizations of ynamides, and the development of quantitative structure-selectivity
relationships in asymmetric conjugate additions.
References:
Peng, Q.; Paton, R. S. Acc. Chem. Res. 2016, DOI: 10.1021/acs.accounts.6b00084
Madarász, A.; Berta, D.; Paton, R. S. J. Chem. Theory Comput. 2016, 12, 1833-1844.
Straker, R.; Peng, Q.; Mekareeya, A.; Paton, R. S.; Anderson, E. A. Nature Commun. 2016, 7, 10109
Gammack-Yamagata, A. D.; Datta, S.; Jackson, K. E.; Stegbauer, L.; Paton, R. S.; Dixon, D. J. Angew. Chem. Int. Ed. 2015,
127, 4981-4985.
Johnston, C. P.; Kothari, A.; Sergeieva, T.; Okovytyy, S. I.; Jackson, K. E.; Paton, R. S.; Smith, M. D. Nature. Chem. 2015,
7, 171-178.
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INVITED SPEAKERS
INORGANIC AND MATERIALS
Richard Darton - University of Keele
Richard obtained his MChem degree from the University of St Andrews
in 2001 and remained there to undertake a PhD with Prof. Russell Morris
entitled “Structural Studies of Zeolites by Solid State NMR and
Microcrystal X-ray Diffraction”. In 2005 he moved to the University of
British Columbia, Vancouver, Canada to undertake a Post Doctoral
Research Fellowship with Prof. Colin Fyfe in porous materials chemistry,
before returning to the UK in 2008 to work with Dr. Richard Walton at
the University of Warwick on the hydrothermal synthesis of complex
metal oxides. In October 2008 he was appointed as a Lecturer in Physical
and Analytical Chemistry at Keele.
Catalysis by Design: Overcoming Catalyst Deactivation in Methane Reforming Reactions
Syngas is one of the largest sources of commercial hydrogen gas and is the principal commercial source
of carbon monoxide. Research into the production of syngas has attracted more attention in recent years
due to its potential as a greener alternative to conventional fuel sources for use in solid oxide fuel cells
and also as a feedstock for the manufacture of chemicals, such as methanol and hydrocarbons.
Syngas is typically produced through the catalytic reforming of methane over a metal supported
catalyst, such as nickel on alumina. These catalysts often suffer from numerous side reactions that can
lead to significant carbon deposition, which eventually poisons the active metal surface or blocks the
flow of reactive gases causing catalyst deactivation.
In this presentation we will highlight some of the recent work from our group and explain how
hydrothermal synthesis methods combined with structural characterisation can be used in the design of
mixed metal oxides to overcome these deactivation issues, whilst retaining favourable catalytic
performances.
Stuart Robertson - University of Strathclyde
1,2-dihydropyridines: from transient intermediates to isolable compounds
Dihydropyridines are important molecules to study due to their diverse roles in pharmacology (for
example as L-type calcium channel blockers used to treat hypertension), biochemistry (for example as
reducing agents in the coenzyme NADPH, a biological reducing agent in photosynthesis) and synthetic
chemistry (for example as intermediates to substituted pyridines).1 Since simple dihydropyridines are
not potent hydride donors themselves, the acceptors often need pre-activation by a metal cation.
However, metallo-dihydropyridines can exhibit enhanced hydride transfer capability due to the extra
negative charge transferred to the heterocycle, but generally these only exist as transient intermediates
in pyridine functionalization reactions and thus have been rarely studied in their own right.
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Rather than focusing on the functionalized pyridine product, our interest lies in the metal-hydride
moiety. The key to opening up this area was to subject lithium alkyls to a stoichiometric amount of
pyridine in the absence or presence of donor solvents.2 This produced 1-lithio-2-alkyl-1,2dihydropyridines, the structures of which (and hence their organo-solubility) depend on the nature of
the alkyl (for example, n-Bu, t-Bu).
Here, I will discuss the synthetic approach to isolating and characterizing these reactive intermediates,
extension to other metallo species and their uses as metal hydride sources for functional group
transformation and in catalysis.
(1) D L Comins, K. Higuchi, D. W. Young in Advances in Heterocyclic Chemistry vol.10, ed. A. R.
Katritzky, Academic Press, 2013, chapter 6, 175.
(2) S. D. Robertson, A. R. Kennedy, J. J. Liggat, R. E. Mulvey, Chem. Commun. 2015, 51, 5452.
Jemma Rowlandson - University of Bath
Jemma Rowlandson is a second year PhD student at the Centre for
Sustainable Chemical Technologies based at the University of Bath. Her
research under Dr Valeska Ting and Professor Karen Edler focuses on the
preparation and characterisation of new activated carbon materials, made
from waste feedstocks. Jemma graduated from the University of
Southampton with a degree in chemistry, and has a keen interest in public
engagement. She won the water zone in the X-factor style online
engagement competition I’m a Scientist, Get me out of here! in 2014,
made it to the national final of the IET Present around the World competition in 2015, and has
participated in Science Show Off, FameLab, and Three Minute Thesis events.
Jemma has been invited to present at ECS2106 as an award for her presentation at the 2015 Royal
Society of Chemistry's Energy Sector Early Career Chemists Event
Towards Tuneable Lignin-Derived Activated Carbons for Energy Storage Applications
A significant shift from fossil fuels to clean technology is required to reduce carbon dioxide emissions,
and limit the effects of global warming. There is one class of materials which offers potential solutions
in many areas of energy storage, from supercapacitors to Li-battery materials, and materials for
adsorptive storage of gases, such as methane and hydrogen. These so-called nanoporous carbons have
a lot in common with Leerdammer cheese. Although these materials are neither bright yellow nor edible,
they are full of thousands of nano-scale sized pores. The performance of these carbon materials is
strongly correlated to the size and geometry of their pores.
Lignin, an integral part of lignocellulosic biomass, is produced in large quantities by the paper and
pulping industry. The wide-spread availability and low cost of lignin makes this a promising feedstock
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for industrial-scale production of activated carbons. Uniquely, the lignin structure varies depending on
the plant species it is isolated from. This leads to the exciting possibility we will be able to tune the
activated carbon structure, including the size and shape of its pores, simply by choosing the feedstock.
The structure of four lignins systematically isolated using the same method, but from different
feedstocks, was investigated. Despite a similar chemical composition, it became clear that each lignin
was composed of different numbers of aromatic units. After lignin carbonisation, only the aromatic
backbone remains, thus lignin from different feedstocks is likely to produce carbons with distinct
structures. Initial experiments support this possibility, since the lignins exhibited different behaviours
after carbonisation. This work shows promise for using selection of the biomass feedstock to tune
activated carbons porosity for different applications.
Nicholas Chilton - University of Manchester
Nick completed his undergraduate degree (BSc. Adv. Hons.) at Monash
University in 2011, under the supervision of Prof Keith S. Murray. As a
President's Doctoral Scholar, he investigated the magnetic anisotropy of
transition metal compounds during a PhD at Manchester, completed in March
2015. He is currently a Research Fellow at the University of Manchester
The Road So Far
From his time as an undergraduate at Monash University in Melbourne, Australia, to his current role as
a Research Fellow at The University of Manchester, Nick will reflect on his journey and share some
points that have helped him along the way. He will use research highlights as examples to illustrate key
moments that have shaped his short career so far, as well as provide some thoughts on how young
researchers can tackle concerns over career prospects.
17
INVITED SPEAKERS
PHYSICAL AND ANALYTICAL
Marcel de Matas - Seda Pharmaceutical Development Services
Marcel de Matas is the cofounder and Director of Product Design at Seda Pharmaceutical Development
Services, which is focussed on helping biotechnology and drug delivery companies to progress new
medicinal products into clinical development and towards commercialisation.
Marcel was formerly a Principal Scientist in Product Development at AstraZeneca where he was
focused on advancing and implementing new science and technology to improve and accelerate the
development of medicinal products.
He has a degree in chemistry and PhD in physical pharmaceutics and has spent a proportion of his career
in industry and in academia. Marcel started his industrial career as a senior scientist in the Respiratory
Technology group at Rhone-Poulenc Rorer in 1997 before moving to Zeneca, soon to become
AstraZeneca (AZ) in 1999. He initially spent 7 years at AZ, where he led teams working at the Drug
Discovery/Development interface and in Late Stage Product Development, whilst also leading specialist
drug delivery projects. As a Senior Lecturer in Clinical Pharmaceutics at the University of Bradford,
Marcel focused his research on the development and understanding of novel processing and formulation
technology, including the evaluation of new methods for manufacturing oral and inhaled dosage forms.
His activities were also centred on engineering materials and products to enable improved processing
and clinical performance which included the development of methodology for modelling in-vitro invivo correlations for inhaled medicines. He was also the Science Lead for a University start-up (Lena
Nanoceutics Ltd) which commercialised a novel processing platform for the production of
pharmaceutical nanoparticles.
Transforming Molecules into Valued Medicines: The Domain of the Pharmaceutical Scientist
Much of the focus of drug development is centred on proving the safety and efficacy of new drugs with
significant attention given during drug discovery to the design of the molecule. However, it is the
product that the patient actually receives, the regulatory authorities approve, the physician prescribes
and the payers reimburse. It is this product, which must deliver the molecule at the right time, the right
place and at the right level to deliver a health outcome, which is worthy of registration and
reimbursement.
Over the last decade there has been an evolution in the Pharmaceutical Sector focussed on accelerating
the development and launch of new medicinal products which address major unmet needs in serious
diseases. This has resulted in markedly compressed development timelines which when coupled with
substantial constraints on resources and materials puts severe pressure on, Pharmaceutical Scientists, as
they must continue to provide robust products and capable manufacturing processes to deliver medicinal
products to support clinical development and subsequent commercialisation.
Amongst other disciplines, scientists with a chemistry background play a pivotal role in the
development of these drug delivery systems, which provides strong opportunities for future career
growth.
This presentation describes some key aspects of pharmaceutical dosage form development and makes
reference to examples ranging from the design of particles with enhanced processing characteristics to
the evaluation of emerging technologies for product manufacture and the assessment of the linkages
18
between product design and in-vivo performance. Each of these examples have been pertinent to my
development as a scientists, but also important in our attempts to transform biologically active chemical
entities into products which make a meaningful difference to the health of patients.
John Griffin - University of Lancaster
John Griffin is a lecturer in Materials Chemistry at Lancaster University. His
research interests concern the development of solid-state NMR (SSNMR)
methods to solve problems in materials science, with a particular focus on
energy materials. During his PhD at the University of Warwick, he developed
high-resolution NMR methods for the study of pharmaceuticals. He then joined
the group of Prof. Sharon Ashbrook at the University of St Andrews to carry
out postdoctoral research in combining advanced NMR experiments with firstprinciples DFT calculations to characterise disorder and dynamics. This was
followed by a postdoctoral position in the group of Prof. Clare Grey, FRS, at
the University of Cambridge, where he developed in situ NMR methods for
the elucidation of supercapacitor charging mechanisms.
An Atom’s Eye View: Studying Structure and Function in Materials using Nuclear Magnetic
Resonance Spectroscopy
Solid-state nuclear magnetic resonance (NMR) is one of the most powerful probes of atomic-level
structure and is applicable to a wide range of systems across chemistry and materials science. While
this technique is most commonly applied to favourable nuclei such as 1H, and 13C, in principle almost
all of the elements in the periodic table are accessible to study by NMR, and in many cases the nuclear
spin properties of more ‘exotic’ nuclei can yield detailed information that cannot be obtained by other
analytical techniques. Recent years have seen many advances in technology and hardware, and also in
solid-state NMR methodology, meaning that experiments that were previously unfeasible can now be
routinely applied. Of great importance has also been the introduction of computational codes for the
efficient and accurate calculation of NMR parameters for periodic solids, which provide the possibility
to test and verify model structures against experimental results.
This presentation will illustrate some of the structural information that can be obtained for a range of
complex materials including minerals, proton-conducting oxides and organic semiconductors. For these
systems, advanced NMR experiments performed on nuclei such as 17O, 19F and 31P combined with
theoretical calculations on model structures provide detailed pictures of atomic-level structure,
dynamics and disorder within the material. The application of NMR as an in situ approach will also be
described, whereby experiments performed on a working energy storage device enable the charging
mechanism to be fully characterised.
19
Karen Johnston - University of Durham
Karen completed her undergraduate degree in Chemistry and Mathematics at
the University of St Andrews, where she was awarded the Charles Horrex
prize for best undergraduate physical project. She then undertook her PhD
with Professors Sharon Ashbrook and Philip Lightfoot, also at the University
of St Andrews. Her thesis focused on the synthesis and structural
characterisation of novel perovskite-based materials using a combination of
powder diffraction, solid-state Nuclear Magnetic Resonance (NMR)
spectroscopy and first-principles Density Functional Theory (DFT)
calculations. Following her PhD research, she undertook post-doctoral work
with Professor Robert W. Schurko at the University of Windsor, Windsor,
Ontario, Canada. Here she focused on the development of wideline solid-state
NMR techniques for the study of quadrupolar nuclei in transition-metal organometallic complexes. She
also worked on the development of indirect detection methods for the study of nitrogen-containing
pharmaceuticals. This was completed in collaboration with Professor Marek Pruski at The Ames
Laboratory, Iowa State University. Karen then completed a second post-doctoral position in the
Advanced Lithium Storage-European Research Institute (ALISTORE-ERI) with Dr Nicolas Dupré
(Nantes, France) and Professor Clare P. Grey (Cambridge). Here she focused on the characterisation of
ternary alloys for use as negative electrode materials in lithium-ion (Li-ion) batteries.
Her current research aims to combine high-resolution powder diffraction (X-ray and neutron) with
multinuclear solid-state NMR and first-principles DFT calculations to study structure in the solid state.
We are interested in the characterisation of both ordered and disordered materials. Current areas of
interest include high temperature ceramics, e.g., perovskite-based systems. We are also interested in
conversion materials for use as negative electrodes in Li- and Na-ion batteries. One area of particular
interest is the design, synthesis and characterisation of novel solid electrolyte materials for use in both
Li- and Na-ion batteries. Understanding the local structure of these materials will provide detailed
insight into the physical properties they exhibit.
The Bigger Picture: Structural Insights into Functional Materials using Diffraction, Solid-State NMR
and First-Principles DFT Calculations
The term “functional material” has been applied to a large array of compounds, including metals, metal
oxides, semiconductors and zeolites. The range of exploitable properties available in functional
materials is substantial and includes magnetism, dielectric properties, piezoelectricity and ionic
conductivity. The range of possible application sectors is similarly large, with uses in energy generation
and storage, transport, information and technology etc. As a result, functional materials have gained
huge economic significance over the last 50 years.
Piezoelectrics and batteries are just two examples of functional materials studied extensively in recent
years. Perovskites are an important class of materials that have been studied for use in both batteries
and piezoelectrics. The alkaline niobates, NaNbO3, KNbO3 and the solid-solution KxNa1−xNbO3
(KNN) are of considerable interest owing to recent reports of exceptional piezoelectric responses,
believed to be comparable to those of the most widely used piezoelectric ceramic, Pb(ZrxTi1−x)O3
(PZT). The work presented here focuses on the room temperature phases of NaNbO3, which remain a
subject of considerable discussion. Several phases have been suggested and observed experimentally,
including the antiferroelectric Pbcm and polar P21ma polymorphs of NaNbO3. The relative quantities
of these two phases are known to vary considerably depending on the precise synthetic conditions used,
e.g., conventional solid state techniques versus softer routes such as sol-gel. X-ray diffraction and solidstate NMR data will be presented comparing different synthetic techniques.
20
The rechargeable Li-ion battery has revolutionised global communication and is now considered the
technology of choice for energy storage in portable electronic devices and zero emission vehicles.
Conversion type materials have recently been suggested as plausible alternatives to conventional
electrode materials. The ternary alloy TiSnSb was recently proposed as a possible negative electrode
material due to its excellent electrochemical performance. TiSnSb is known to undergo a conversion
reaction, leading to the simultaneous formation of Li-Sb and Li-Sn intermetallic compounds. Several
phases have been successfully identified via X-ray diffraction and 119Sn Mössbauer studies. However,
several ambiguities remain. Can 7Li solid-state NMR provide insight into the phases formed during
lithiation?
21
INVITED SPEAKERS
EDUCATION AND OUTREACH
Heather Doran - University of Aberdeen
Heather Doran is a Project Officer in Public Engagement with Research at the
University of Aberdeen. Her role is to help embed public engagement across
the university and develop opportunities for engagement. Heather is also the
Aberdeen co-ordinator for the EU NUCLEUS project focusing on the
integration of Responsible Research and Innovation.
She is the Chair of the British Science Association Branch in Aberdeen and in
2015 she was awarded a Winston Churchill Memorial Trust Travel Fellowship
to travel to the USA, Canada, China and Japan to explore how social media
can be used as a tool for public engagement with science.
Before moving to Public Engagement with Research she was a PhD student
in molecular pharmacology and co-founded and was editor for Au Science Magazine.
Arno Kraft – Heriot-Watt University
Arno Kraft studied Chemistry at the University of Würzburg in Germany
where he received his PhD degree in 1989. During a 3-year postdoctoral stay
in the group of Prof. Andrew Holmes in Cambridge he was involved in the
development of some of the first electroluminescent polymers. He then spent
7 years at the University of Düsseldorf where he completed his habilitation in
Organic Chemistry and Macromolecular Chemistry. He is currently a lecturer
at Heriot-Watt Chemistry with an interest in polymer chemistry.
Videos, apps and LEGO instruments
Times change, and so do teaching methods. Many changes in teaching Chemistry have occurred over
the last decades. The increasing use of, and reliance on, technology provides both new opportunities
and challenges for a lecturer.
The discussion of new educational resources will focus on the following topics:

Videos on Chemistry topics are abundant on the internet. However, not all of them are suitable
or helpful for teaching, and sometimes it becomes necessary to create your own teaching video.
Educational projects can allow final-year BSc students to communicate Chemistry by designing
a video from scratch. Our experiences at Heriot-Watt with home-made videos on 2D NMR
techniques and polymer chemistry will be discussed.
22


Apps for smartphones and tablets are plentiful nowadays, although apps for supporting
Chemistry teaching are still rare. The procedure for making a “lab app” for supporting
Chemistry students will be demonstrated (Figure 1).
Whereas commercial spectrophotometers tend to be black boxes to most of us, a colorimeter
can be readily and cheaply made from a handful of components. A simple colorimeter requires
just a light-emitting diode as light source, a magnifying glass to focus the light, a photosensor
to measure the light intensity, an Arduino to collect and transfer the data to a computer, and
some LEGO bricks, with total costs amounting to about £80. The construction of a LEGO
colorimeter and a LEGO filter fluorimeter will be demonstrated.
Menno de Waal - European Young Chemists Network
Menno de Waal (1985) studied chemistry at the University of Applied Sciences in Utrecht and aviation
at the University of Applied Sciences in Amsterdam. He now works as a Coordinator Analytical
Chemistry at the Regional Education Institute of Amsterdam, where he is also the International
Coordinator. Besides his job, Menno is the chairman of the Young Royal Dutch Chemical Society (Jong
KNCV) and member of the KNCV Education Board.
EYCN connecting chemists around Europe
The European Young Chemists Network aims to connect the young chemists around Europe. Founded
in 2006, EYCN organises the yearly Delegates Assembly, photography contests, and-together with
national societies- the career days, focussing on soft skills. The Highlight is the programme Young
Chemists Crossing Borders (YCCB); a collaboration between ACS and EYCN where ACS members
visit the EuCheMS Congress and EYCN members visit the ACS Conference
23
Debra Willison – University of Strathclyde
Debbie Willison is based in the Department of Pure and Applied Chemistry. During a career spanning
almost 40 years she has had a number of roles including Director of Teaching within the Department.
She is currently Vice Dean Academic for the Faculty of Science. She has a background in organic and
organometallic chemistry but current research interests lie in the area of pedagogical development.
Current projects include exploring student transitions through university, enhancing employability
skills and assessing the value of reflection in work based learning.
Championing Success: 15 years of Outreach Activities Champions at Strathclyde
The competitive nature of recruitment in Higher Education is clearly recognised. While a range of
promotion and outreach activities, such as branding and student recruitment, are organised centrally
within institutions, departments also have an important role to play in promoting themselves. To address
this, the Department of Pure and Applied Chemistry at the University of Strathclyde appointed an
Outreach Activities Champion over 15 years ago. Their task was to co-ordinate current outreach activity
while also creating new opportunities to promote the department and courses. A relatively small team
was established to implement this. A number of initiatives began to evolve through dialogue within this
team and with colleagues in the secondary education sector. Successes in this area encouraged other
colleagues to become involved in outreach activities. The department indicated further commitment
with the appointment of a marketing specialist who has taken responsibility for the design of our
publicity material and the content of the Admissions page on our website. All external communications
are produced to the highest specification to heighten the perception of the department as a professional
organisation. As an indication of our commitment to outreach and the wide ranging scope of our
activities, in 2014/15 we interacted with approximately 113 schools, 168 teachers and 2312 school
pupils. This approach is now being rolled out across the Faculty of Science. My presentation will
describe the scope, and assess the success, of our activities to delegates.
24
Andy West – Pera Technology Solutions
Volunteering is Good for Business
Andrew obtained his degree in chemistry and Ph.D. in sustainable fluorine
chemistry and synthesis of recyclable homogeneous catalysts from the
University of Leicester. After a period in Belfast, where he worked as a
postdoctoral research assistant at Queen’s University carrying out research for
BP as part of a multi-million pound project, Andrew returned to Britain in
2006 to take up a role at Crystal Faraday (which became Chemistry
Innovation KTN), a DTI-sponsored body promoting green and sustainable
chemistry in the UK. Here, Andrew was a Project Formulator and Programme
Manager for Fluorum, the network set up to promote fluorine chemistry in the UK and Europe. He also
had responsibility for helping to manage Chemistry Innovation’s portfolio of UK projects.
Missing the lab, Andrew joined Pera Technology as a chemist in the Chemistry and Biotechnology
division in 2007. Since joining the company, he has worked on the management and technical delivery
of numerous projects in a wide range of areas from food research to industrial catalysis, waste
minimisation, bio-fuels and alternative energy. He also helps to write successful bids for both TSB and
EU funding. He was promoted to Principal Chemist in 2013 and now has additional responsibility for
building industry-academia consortia in order to obtain research funding.
Andrew is a keen supporter of the Pera Foundation, a charitable trust set up by Pera to help the
development of disadvantaged and disaffected young people in local society. Part of the Foundation’s
remit is to encourage young people, through events, activities and competitions, to study STEM subjects
and the RSC is the perfect partner to help the Foundation with this aim.
Is Volunteering Good for Business?
Outreach activities are increasing being seen by businesses as a core part of their social responsibility
and an excellent way to help staff develop. However, business demands, staff awareness and finding
suitable partners can challenge the success of outreach projects and misconceptions regarding
measureable business/social impacts can deter corporations from participating. In this presentation, the
question ‘is volunteering good for business?’ is asked, and the journey of Pera Technology Solutions in
setting up the Pera Foundation is presented as a case study, describing the challenges we have faced,
the impacts we have achieved and rewards we have received.
25
ORAL ABSTRACTS
Towards an MIE atlas
T. E. H. Allen1*, S. Liggi1, J. M. Goodman1, S. Gutsell2, P. J. Russell2.
1
Centre for Molecular Informatics, Department of Chemistry, University of Cambridge, Lensfield Road,
Cambridge CB2 1EW
2
Unilever Safety and Environmental Assurance Centre, Colworth Science Park, Sharnbrook, Bedfordshire
MK44 1LQ
[email protected]
Modern humans are exposed to hundreds of chemicals in their everyday lives. In order to ensure the safety of
these chemicals toxicity risk assessment must be carried out. Historically an in vivo approach based on observation
has dominated, particularly in the pharmaceutical industry. These methods are expensive, time-consuming,
ethically unsound, and do not effectively reflect human responses. In response to this the field of toxicology is
moving away from in vivo experiments and towards in silico and in vitro alternatives based on understanding the
mechanisms behind toxicological effects. One such approach is the adverse outcome pathway (AOP) framework
for risk assessment. This approach aims to build an understanding of the effects a toxicant has across all levels of
biological organisation. [1] The molecular initiating event (MIE) can be thought of as the gateway to the AOP the initial chemical interaction. Chemistry is key to understanding the MIE. What is it about these molecules that
allow them to do this?
In this project answers to this question have been explored in a number of cases. This has included the
characterisation of a number of MIEs across several well understood toxicants using literature searches. This work
led to a greater understanding of what an MIE is and how it should be described. This was then built upon, leading
to a new unified definition of the MIE: the initial interaction between a molecule and a biomolecule or biosystem
that can be causally linked to an outcome via a pathway. [2] Principles for model construction have been
developed, linking a molecule’s properties with its activities more closely than ever before, and a manner in which
understanding gained from these models can be fed back into AOP resources has been presented. Finally a number
of models based on these principles have been developed and tested, providing a platform for the screening of
novel chemicals to establish the kind of MIEs they may be able to activate in humans, and hence the toxicities
they may elicit. [3]
This combined work represents the first steps in the development of an MIE-based approach to human safety risk
assessment. These efforts represent a foundation to develop the area of alternatives to animal based toxicity
testing.
References:
[1] G.T. Ankley, R.S. Bennett, R.J. Erickson, D.J. Hoff et al. (2007) Environ. Toxicol. Chem. 29; 730-741
[2] T.E.H Allen, J.M. Goodman, S. Gutsell, P. Russell. (2014) Chem. Res. Toxicol. 27
(12); 2100-2112
[3] T.E.H. Allen, S. Liggi, J.M. Goodman, S. Gutsell, P. Russell. (2016) Using Molecular
Initiating Events to Generate 2D Structure Activity Relationships for Toxicity Screening. Manuscript Submitted
26
ORAL ABSTRACTS
1-Sulfonyl-1,2,3-triazoles versus sea lampreys
A. Boyer*
School of Chemistry, University of Glasgow, Glasgow, UK
[email protected]
The manipulation of reactive species is an attractive strategy in chemical synthesis which can be directed to
rapid generation of molecular complexity. Recently, 1-sulfonyl-1,2,3-triazoles 1 (1-STs) have emerged as
valuable precursors to α-iminocarbenoids 2.1 In the presence of a catalyst, 1-STs 1 undergo denitrogenative
decomposition resulting in the controlled formation of a reactive carbenoid 2 (Scheme 1). The careful design
of novel reaction conditions has resulted in the ability to steer these highly reactive intermediates towards a
range of interesting products in excellent yield and with remarkable selectivity.
Scheme 1
This approach was extended to the novel stereocontrolled synthesis of substituted tetrahydrofurans
(Scheme 2).2 Rhodium(II) acetate catalyses the denitrogenative transformation of 1-STs with pendent allyl
ether motifs 3,6 to oxonium ylides that undergo [2,3]-sigmatropic rearrangement to give substituted
tetrahydrofurans 5,7 in high yield and diastereoselectivity.
Scheme 2
The utility of this method was demonstrated by the enantioselective synthesis of (+)-petromyroxol 8
(Figure 1). The petromyroxols are natural products isolated from water conditioned with larval sea lamprey. 3
However, only 3 mg of the natural product was isolated from >100 000 L. Using methodology based on
denitrogenation of 1-STs, an efficient 9-step synthesis was devised, which supplied useful quantities on this
fascinating natural compound for further evaluation.
Figure 1
[1] a) Reviews: H. M. L. Davies, J. S. Alford, Chem. Soc. Rev. 2014, 43, 5151; b) P. Anbarasan, D. Yadagiri,
S. Rajasekar, Synthesis 2014, 46, 3004; [2] a) A. Boyer, Org. Lett. 2014, 16, 1660; b) A. Boyer, Org. Lett.
2014, 16, 5878; [3] K. Li, M. Huertas, C. Brant, Y.-W. Chung-Davidson, U. Bussy, T. R. Hoye, W. Li, Org.
Lett. 2015, 17, 286.
27
ORAL ABSTRACTS
Room temperature gold-catalysed arylation of heteroarenes:
Orthogonality to Suzuki-Miyaura cross-coupling
A. J. Cresswell*1 and G. C. Lloyd-Jones1
1
School of Chemistry, University of Edinburgh, Edinburgh UK.
[email protected]
We recently reported a new route to biphenyls via oxidative cross-coupling of moderately electron-rich arenes
with aryltrimethylsilanes.1,2 This gold-catalysed reaction exploits the innate SEAr-type reactivity of the arene
partner, rather than a directing group, and proceeds under mild and convenient conditions. However, although
many substituents are tolerated, including esters, aldehydes, alcohols, and (pseudo)halides, the only
heteroarenes we were able to efficiently arylate under our original conditions were 2-bromothiophenes.
By tailoring the pre-catalyst, the arylsilane, and the iodine(III) oxidant, a range of heteroarenes can now be
arylated with excellent, and in some cases unique, regioselectivity under mild conditions (Scheme 1). The
reactions proceed without the need for a protective atmosphere or directing groups and their tolerance to
halides and boronic esters, in both the heteroarene and silane partners, provides orthogonality to SuzukiMiyaura coupling.
Scheme 1 Gold-catalysed C–H arylation. tht = tetrahydrothiophene.
[1] L. T. Ball, G. C. Lloyd-Jones, C. A. Russell, Science 2012, 337, 1644–1648.
[2] L. T. Ball, G. C. Lloyd-Jones, C. A. Russell, J. Am. Chem. Soc. 2014, 136, 254–264.
28
ORAL ABSTRACTS
The limit of cooperativity in H-bond networks
N. Dominelli Whiteley*, J. J. Brown, and Scott L. Cockroft
EastCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road,
Edinburgh, EH9 3FJ, UK.
[email protected]
It is often presumed that H-bond chains are more stable than the sum of the individual H-bonds due to positive
cooperativity arising from polarisation. Here, we have examined H-bonding chains of hydroxyl groups using
synthetic molecular balances (Figure 1) and computational predictions. Surprisingly, we found that extending
the length of the chain beyond two hydrogen bonds did not increase the stability of the terminal H-bond. The
interaction trend was consistent with through-space substituent effects dominating over long-range
polarisation. The implication is that the term H-bond chain should be reserved as a structural descriptor,
without long-range cooperative energetic connotations.
ΔG1 < ΔG2 ≈ ΔG3
Figure 2: Molecular balances used for the experimental dissection of H-bond chain energies
29
ORAL ABSTRACTS
The synthesis of Tentoxin analogues as potential herbicides
E. C. Frye*1, M. McLachlan1, T. O’Riordan1, J. Delaney1, and S. Oliver1
Syngenta UK, Jealott’s Hill International Research Centre, Bracknell, UK
[email protected]
1
Tentoxin (1) is a phytotoxic natural product produced by the fungi Alternaria tenuis and Alternaria alternata.
This toxin causes chlorosis in sensitive plant species and affects the development of chloroplasts by inhibition
of chloroplast CF1ATPase. Tentoxin is a cyclic tetrapeptide containing an α,β-unsaturated amino acid unit
and partial N-methylation. These features and the significant ring strain in cyclic tetrapeptides make Tentoxin
and its analogues challenging synthetic targets.
In this presentation, we present our progress toward the design and synthesis of Tentoxin analogues as
herbicides, through a combination of solutionphase and solid-phase chemistry. The in vitro and in vivo
biological activity of these structures will be presented along with a discussion of their physical properties in
relation to uptake and distribution in plants.
1, Tentoxin
30
ORAL ABSTRACTS
Understanding catalytic mechanisms using computational methods
M. N. Grayson*1, M. J. Krische2, and K. N. Houk3
1
Centre for Molecular Informatics, Department of Chemistry, University of Cambridge, Cambridge, UK
2
Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas, USA
3
Department of Chemistry and Biochemistry, University of California, Los Angeles, California, USA
[email protected]
The rational design of new catalysts and reactions in organic chemistry is an attractive alternative to traditional
trial-and-error methods but for this, a detailed understanding of the elementary steps of existing reactions is
essential. I will described the use of molecular modelling to elucidate the mechanisms of two important organic
reactions, Krische’s butadiene hydrohydroxyalkylation and Wynberg’s asymmetric conjugate addition (Figure
1).
Krische reported that the catalyst generated in situ from RuH 2(CO)(PPh3)3, (S)-SEGPHOS, and a chiral
phosphoric acid promotes asymmetric butadiene hydrohydroxyalkylation and affords enantioenriched α-methyl
homoallylic alcohols. Our quantum mechanical calculations show why use of BINOL-derived phosphate ligands
lead to good levels of anti-diastereoselectivity and why the same enantiomer of TADDOL-derived phosphates
lead to syn-diastereoselectivity. We found that carbon–carbon bond formation occurs via a chair Zimmerman–
Traxler-type transition structure and that a formyl CH•••O hydrogen bond from the aldehyde CH to the phosphate
oxygen as well as steric interactions of the two chiral ligands control the stereoselectivity. We present a qualitative
guide to explain the experimental outcomes which will assist rational synthetic methodology design.1
Wynberg’s report from 1977 that cinchona alkaloids catalyze the asymmetric conjugate additions of aromatic
thiols to cycloalkenones is a landmark in hydrogen bonding asymmetric organocatalysis. Wynberg proposed that
this reaction proceeded via the formation of an alkylammonium ion-thiolate tight ion pair and activation of the
enone electrophile by a hydrogen bond from the catalyst’s hydroxyl group. We report quantum mechanical
calculations that show that the lowest energy pre-reaction complex is the alkylammonium ion-thiolate ion pair
that was proposed by Wynberg, but we show that the lowest energy transition state involves a different activation
mode. In our new model, the catalyst’s hydroxyl group orientates the thiolate nucleophile and the alkylammonium
ion activates the enone by Brønsted acid catalysis. The new model rationalizes the stereoselective outcome of
Wynberg’s reaction and provides a new, general model for asymmetric cinchona organocatalysis. 2
Figure 3 Krische’s butadiene hydrohydroxyalkylation (left) and Wynberg’s asymmetric conjugate addition
(right)
1.
2.
Grayson, M. N.; Krische, M. J.; Houk, K. N. J. Am. Chem. Soc. 2015, 137, 8838–8850.
Grayson, M. N.; Houk, K. N. J. Am. Chem. Soc. 2016, 138, 1170–1173.
31
ORAL ABSTRACTS
All cis-1,2,3,4,5,6-hexafluorocyclohexane: the most polar aliphatic motif currently identified
N. S. Keddie*, T. Lebl, A. M. Z. Slawin, D. Philp and D. O’Hagan
EaStCHEM School of Chemistry Biomedical Sciences Research Complex, University of St Andrews,
St Andrews, Fife, KY16 9ST, UK
[email protected]
There are a total of 9 configurational isomers of 1,2,3,4,5,6-hexafluorocyclohexane, with 15 possible
conformational isomers. The relative ground state energies of these molecules have been calculated, with one
structure (the all-cis 8) standing out above the others.1,2
F
F
F
F
F
F
F
F
F
1 + ent
F
F
F
F
F
F
F
F
2
F
F
F
F
F
F
F
F
F
F
F
9 + ent
F
F
F
10
F
F
F F
11
F
F
F
3
F
F
F
F
F
F
F
F
F
F
4
5
degenerate
ring flip to
same
conformation
ring flip to
conformational
enantiomer
F
F
F
F
F
F
F
F
F
F
F
F
6
F
F
F
7
F
F
12
FF F
F
F
F
F
F
F
8
F
F
F
F
degenerate
ring flip to
same
conformation
13
Figure 1 | Configurational and conformational isomers of 1,2,3,4,5,6-hexafluorocyclohexane.
The synthesis of the highest energy stereoisomer of 1,2,3,4,5,6-hexafluorocyclohexane (8), where all of the
fluorine atoms are ‘up’, is described in a 12-step protocol.3 The molecule adopts a classic chair conformation with
alternate C–F bonds aligned triaxial, clustering three highly electronegative fluorine atoms in close proximity.
This generates a cyclohexane with a high molecular dipole (μ = 6.2 D), unusual in an otherwise aliphatic
compound, and the highest currently identified for an aliphatic molecule in the literature.
X-ray analysis indicates that the intramolecular Fax...Fax distances (~2.77 Å) are longer than the vicinal Fax...Feq
distances (~2.73 Å) suggesting a tension stabilising the chair conformation. In the solid state the molecules pack
in an orientation consistent with electrostatic ordering.
Figure 2 | Single crystal X-Ray structure of 8 (a and b) and electrostatic surface potential map of 8 (c). 3
Our synthesis of this highest energy isomer demonstrates the properties that accompany the placement of axial
fluorines on a cyclohexane and the unusual property of a facially polarised ring in organic chemistry.3 We have
since further explored this facial polarity through computational, NMR and mass spectrometry anion- and cationcoordination studies,4,5 which will be discussed in this presentation.
Derivatives of 8 have potential as new motifs for the design of functional organic molecules or for applications in
supramolecular chemistry design.
1.
2.
3.
4.
5.
Q. Luo, K. R. Randall and H. F. Schaefer, RSC Adv., 2013, 3, 6572–6585.
Z. Zdravkovski, Bull. Chem. Technol. Macedonia, 2004, 23, 131–137.
N.S. Keddie, T. Lebl, A.M.Z. Slawin, D. Philp and D. O’Hagan, Nat. Chem., 2015, 7, 483–488.
R. A. Cormanaich, N. S. Keddie, R. Rittner, D. O’Hagan and M. Bühl, Phys. Chem. Chem. Phys., 2015, 44,
29475–29478.
B. E. Ziegler, M. Lecuors, R. A. Marta, J. Featherstone, E. Fillion, W. S. Hopkins, V. Steinmetz, N. S.
Keddie, D. O’Hagan and T. B. McMahon, J. Am. Chem. Soc., 2016, DOI: 10.1021/jacs.6b02856
32
ORAL ABSTRACTS
trans,trans-BNIPDaCHM: a Novel Bisnaphthalimidopropyl (BNIP) derivative designed for targeting
DNA in a human breast cancer cell line
M. Kopsida*1, G. A. Barron1, 2, G. Bermano2, P. Kong Thoo Lin1 and M. Goua1
1
School of Pharmacy and Life Sciences, Robert Gordon University, Garthdee Road, Aberdeen, AB10 7GJ,
Scotland, UK
2
Centre for Obesity Research and Education (CORE), Faculty of Health and Social Care, Robert Gordon
University, Garthdee Road, Aberdeen, AB10 7GJ, Scotland, UK
[email protected]
Breast cancer is the most commonly occurring cancer in women, with incidence rates approaching 1.38 million
cases per year worldwide. Over the last few decades, there have been numerous attempts to develop, synthesise
and advance into the clinic, novel and selective breast cancer therapies. As previously reported 1,
bisnaphthalimidopropyl diaminodicyclohexylmethane (BNIPDaCHM) (Figure 1) exerted potent in vitro anticancer activities and strong DNA binding properties. Here we report for the first time the synthesis,
characterisation and biological activity of the trans,trans-BNIPDaCHM isomer. 1H-NMR, 13C-NMR, MS and
melting point determination were used to confirm the structural identity of trans,trans-BNIPDaCHM derivative.
The cytotoxicity of trans,trans-BNIPDaCHM was assessed against a human breast cancer cell line (MDA-MB231) by MTT assay. In parallel, DNA binding properties of trans,trans-BNIPDaCHM were determined using
Fluorescence and UV quenching experiments. This novel compound exhibited strong cytotoxic activity against
MDA-MB-231 cells, with an IC50 value of 1.4 µM after 24 hours treatment. trans,trans-BNIPDaCHM
competitively displaced EtBr from DNA, with a C50 value of 5.6 µM and the DNA binding K constant of
trans,trans-BNIPDaCHM was 11.38 x 104. In conclusion, the above findings signify that trans,transBNIPDaCHM exhibits strong cytotoxic and DNA binding properties in vitro. Future work will study the potential
molecular targets of trans,trans-BNIPDaCHM in breast cancer cells.
Figure 1. Structure of the parental compound, BNIPDaCHM, with its three stereo isomers including
trans,trans-BNIPDaCHM.
1
Barron, G., Bermano, G., Gordon, A. and Kong Thoo Lin, P., Eur. J. Med. Chem., 2010, 45 (4), 1430-1437.
33
ORAL ABSTRACTS
Defining the Structural Determinants of Transcriptional Fidelity in an Expanded Genetic Alphabet
T. D. Kosmidis*1, A. M. Jobbins2, D. R. W. Hodgson,3 I. C. Eperon2 and G. A. Burley1
1
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, UK.
2
Department of Molecular and Cell Biology, University of Leicester, Leicester, UK.
3
Department of Chemistry, Durham University, Durham, UK.
[email protected]
Artificial base pairs represent an important class of compounds that have applications in molecular
diagnostics and synthetic biology. While some of these artificial nucleotides pair orthogonally via hydrogen
bonding, others rely on pairing by hydrophobic interactions. A pertinent example of the latter is the Pa/s pair
developed by the Hirao lab. While efforts towards enhancing transcriptional efficiency and fidelity of Pa have
been explored, little work has been published regarding the factors that control the transcriptional efficiency
and fidelity of s. A structural hallmark of s is a thiophene in the C-6 position of guanosine. Consequently,
assaying the impact of different substituents on the C-6 position of the guanosine scaffold will help us
understand the molecular determinants governing the transcriptional efficiency and fidelity of this family of
ribonucleotides. Herein we present the synthesis of two examples of C-6 substituted guanosine nucleotide
triphosphates and their evaluation in transcription opposite a Pa-containing DNA template. Our results show
that analogues 1 and 2 are incorporated into the transcript. These data suggest that further amelioration of this
scaffold could provide novel routes for the site-specific labelling of RNA.
a)
b)
N
O
N
N
N
R
O
H 2N
N
S
1
Pa
N
N
N
R
O
Pa
H 2N
N
s
N
R
O
OH
O
Pa
H 2N
OH
N
N
N
R
9P 3O
R=
N
N
N
R
4-O
N
N
R
2
Figure 4 a) Hirao’s Pa/s pair and triphosphates 1 and 2 synthesized in this study b) Schematic representation of
the transcription assay. Bent arrow marks the transcription starting point. NTPs = Nucleotide triphosphates.
34
ORAL ABSTRACTS
Organic solar cells, the future: development of DODIPY-based small molecules for organic
photovoltaics
J.M. Santos*1, G. Cooke2
Department of Nanoscience and Materials, School of Chemistry, University of Glasgow, Glasgow, UK.
[email protected]
For many years the world population has been consuming fossil fuel as a major energy supply. The
consumption of this limited form of energy has contributed to serious implications in the environment, such
as global warm and pollution. In addition, the world population is increasing through a very alarming rate
and the modern lifestyle demands more energy than before. The sun, an average star which is considered a
fusion reactor, is one of the most obvious alternative of “clean” and renewable energy source.
The covering of only 1% of the Earth`s surface with 10% efficiency solar cells would meet the global need
for energy. However, less than 1% of the electricity supply is based on solar energy, and this is due to the
poor balance between cost and efficiency achieved by the inorganic devices, such as conventional silicon
solar cells, from the first generation of solar cells. Since the first generation, different types of solar cells have
been developed and studied. The second generation, also called thin-film solar cells, are less expensive but
struggles to reach desirable power conversion efficiencies and thereby is not a cost-efficient viable
technology. Two of the most principal challenges to make solar cells affordable over fossil fuels are: the
conversion efficiency of sunlight to electric power and cost.
Devices based on organic photovoltaics (OPV) have attracted attentions, and are promising due to their low
cost, flexibility, high optical absorption coefficient, simplicity in production and the potential to undergo high
performances. Hence, this generation of solar cells can achieve the so required cos-efficiency balance to be
commercialized and make a significant contribution to the global energy production. The development of
high-efficient organic solar cells depends on the proper characteristics of the materials that composes the
device. Thus, the design and synthesis of high-performance functional dyes is a key factor for the
development of this area.
Boron-dipyrromethene (BODIPY) dyes (Figure 1) are interesting due to their outstanding chemical and
photochemical stability, redox activity, good solubility, and optical features that can easily modified. Thus,
this family of dyes, which is still poorly investigated for OPV, have all the attributes and thereby the potential
to applied in solar cells and achieve desirable power conversion efficiencies. Hence, this work concerns the
synthesis and characterization of novel BODPY derivatives functionalized in the meso and positions for
the application in bulk heterojunction (BHJ) solar cells and dye sensitized solar cells (DSSC).
Figure 1 General structure of BODIPY derivatives.
35
ORAL ABSTRACTS
Flow enabled peptide synthesis
Z. E Wilson*1 and S. V. Ley1
1
Department of Chemistry, University of Cambridge, Cambridge, UK
[email protected]
Peptides are a vital part of many of the core processes of living organisms. They act as neurotransmitters and
modulators, hormones, growth factors, ion channel ligands and anti-infectives.1 Although chemical synthesis
is generally favoured to access peptides due to its inherent flexibility, existing methods are largely highly
inefficient, suffering from poor atom economy, challenging purifications and difficulties in the scale-up of
processes. With a recent resurgence of interest in peptide pharmaceuticals, which is already resulting in drugs
making it to market, it is increasingly important that novel, efficient and scalable processes for the chemical
synthesis of peptides are developed.2
The use of flow technology enables the accurate control of reaction parameters, allows for in-line monitoring
and automation of reactions and can significantly simplify the scale-up of reactions, giving it exciting
potential to solve some of peptide syntheses inherent problems. We have recently successfully synthesised a
family of cyclooligomeric depsipeptides (1 – 6), including the bioactive natural products beauvericin 1,
bassianolide 2 and enniantin C 3, in overall yields of 32-52% through the informed application of flow
chemistry (Figure 1).3 Using flow technology, challenging inter- and intramolecular N-methylated amide
bonds were successfully formed in a highly atom efficient fashion. Subsequent work has further extended the
scope through the adaptation of complimentary mixed anhydride methodology, indicating a promising future
for flow chemistry enabled peptide synthesis.
Figure 5 Recently synthesised natural and unnatural cyclooligomeric depsipeptides
References:
1.
N. Sewald and H.-D. Jakubke, Peptides : chemistry and biology, Wiley-VCH, Weinheim, 2002.
2.
K. Fosgerau and T. Hoffmann, Drug Discov. Today, 2015, 20, 122-128.
3.
D. Lücke, T. Dalton, S. V. Ley and Z. E. Wilson, Chem. Eur. J., 2016, DOI: 10.1002/chem.201504457.
36
ORAL ABSTRACTS
How does a metalloprotein catalyze chemically difficult reaction: the mechanistic study of Bacillus subtilis
oxalate decarboxylase
Wen Zhu,*1 Jarett Wilcoxen,2 Lindsey M. Easthon,3 Karen N. Allen,3 R. David Britt, 2 and Nigel G. Richards *1,
1
2
School of Chemistry, Cardiff University, Cardiff, CF10 3AT Wales UK
Department of Chemistry, University of California, Davis, CA 95616 USA
3
Department of Chemistry, Boston University, Boston, MA 02215, USA
[email protected]
The C-C bond in oxalate is chemically inert; in the absence of catalyst, the half-life of decarboxylation for
oxalate is over 3,300 years. [1] Meanwhile, many bacteria and fungi process oxalate-degrading enzymes to
overcome this obstacle. Understanding how nature utilizes such enzymes to catalyze chemically difficult
reaction are of interest in fundamental biological science and medicinal chemistry for drug design and clinical
diagnosis. Oxalate decarboxylase (OxDC) catalyzes a disproportionation of oxalic acid monoanion into carbon
dioxide and formate. [2] (Figure 1) Unlike other decarboxylases, which often requires the presence of cofactor
such as PLP, OxDC employs dioxygen and Mn to enable the reaction, although dioxygen is not consumed. [3] It
has long been hypothesized that dioxygen is needed to form Mn(III) or Mn(IV) in the active site of the enzyme,
but the direct spectroscopic detection of either of these forms of the metal has not been reported. [4] Using
parallel mode EPR spectroscopy, we now show that Mn(III) can indeed be formed in OxDC, but only in the
presence of substrate under acidic conditions during turnover. [5] The involvement of Mn(III) in the catalytic
mechanism of OxDC is consistent with experiments that find this species to be essential for the activity of
OxOx, which is a homologous enzyme that also breaks the C-C bond in oxalate. [6] Additionally, the first
substrate-bound X-ray crystal structure of an OxDC variant shows that substrate binds to the N-terminal metal
in a monodentate configuration, which is also consistent with the proposed mechanism of this enzyme. [7]
These observations therefore not only provide the first direct support for mechanistic proposals in which Mn(III)
removes an electron from the substrate to yield a radical, but also shed light on the mechanistic study of other
metalloproteins.
Figure 1 Bacillus subtilis oxalate decarboxylase catalyzes the cleavage of the C-C bond in oxalate.
[1] Wolfenden, R., Lewis, C. A. Jr., Yuan, Y. 2011, J. Am. Chem. Soc., 133, 5683–5685.
[2] Tanner, A.; Bowater, L.; Fairhurst, S. A.; Bornemann, S. 2001, J. Biol. Chem. 276, 14627-14634.
[3] Moomaw, E. W., Angerhofer, A., Moussatche, P., Ozarowski, A., Garcia-Rubio, I., Richards, N.G.J. 2009,
Biochemistry 48, 6116–6125.
[4] Chang, C. H., Svedruzic, D., Ozarowski, A., Walker, L., Yeagle, G., Britt, R. D., Angerhofer, A., Richards,
N. G. 2004, J. Biol. Chem. 279, 52840-52849.
[5] Zhu, W., Wilcoxen, J., Britt, R. D., Richards, N. G. J. 2016, Biochemistry, 55, 429–434.
[6] Whittaker, M. M., Pan, H. Y., Yukl, E. T., Whittaker, J. W. 2007, J. Biol. Chem. 282, 7011-7028.
[7] Zhu, W., Easthon, L. M., Reinhardt, L. A., Tu, C., Cohen, S. E., Silverman, D. N., Allen, K. N., Richards, N.
G. J. 2016, Biochemistry, 55, 2163–2173.
37
ORAL ABSTRACTS
Taming pyridyl-N-phosphinoimines
J. K. D. Aldred (née Prentis),* A. Batsanov, D. C. Apperley, M. A. Fox, D. A. Smith and P. W. Dyer
Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, United Kingdom
[email protected]
Previously, it has been shown that pyridyl-N-phosphinoimines exist in equilibrium between two pseudo-valence
tautomeric forms, “open” and “closed” (Figure 1).[1] In order to potentially exploit what can be regarded as a
“dynamic” Lewis pair, studies have been undertaken to explore how temperature, solvent polarity and the steric
and electronic demands of substituents R1-R6 (e.g. A-D) impact on the position of the “open”/”closed” equilibrium
and, hence, reactivity of these systems.[1],[2]
R1
(R -R = H, R6 = Ph)
Ratio of “Open” :
“Closed”
Tautomers (298 K)
A
Ph
100 : 0
B
NiPr2
5 : 95
C
½ MeNC2H4NMe
0 : 100
D
tBu
100 : 0
2
5
Figure 1 –“Open” and “closed” pseudo-valence tautomers of pyridyl-N-phosphinoimines.
Upon probing the influence of substituents at R2-R5
on the tautomeric equilibrium it was found that on the
introduction of a Me moiety at R2 (when R1 = NiPr2,
E) cyclisation was not observed.[2] The absence of
cyclisation has been attributed to the steric barrier
imposed by the Me substituent at R2. With a view to
facilitating
cyclisation
of
pyridyl-Nphosphinoimines with R2 = Me, attempts were
undertaken to synthesise F, the R1=Cl analogue of E.
Two products were found to form, the structures of which have been
Figure 2 –Structural forms of F
assigned as F-Salt and F-Cycle (Figure 2) using a combination of DFT
(B3LYP/6-31** level) and experimental studies. It is proposed that F-Salt is formed from dissociation of one
chloride anion from the transient F-Open and subsequent stabilisation of the phosphenium cation by the pyridine
nitrogen centre. The intramolecularly stabilised phosphenium salt is then postulated to undergo an intermolecular
C-H insertion and subsequent cyclisation sequence to form F-Cycle.
References:
[1] D. A. Smith, A. S. Batsanov, K. Miqueu, J. –M. Sotiropoulos, D. C. Apperley, J. A. K. Howard and P. W.
Dyer, Angew. Chem. Int. Ed., 2008, 47, 8674-8677.
[2] D. A. Smith, PhD Thesis, Durham University, 2009.
38
ORAL ABSTRACTS
Oxidative Addition of Aryl Halides to [Ni(COD)(dppf)]
S. Bajo,1 S. Sproules, 2 A. R. Kennedy, 1 and D. J. Nelson1
1
WestCHEM Department of Pure & Applied Chemistry, University of Strathclyde, 295 Cathedral Street,
Glasgow, G1 1XL, UK
2
WestCHEM School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK
[email protected]
Recently, the importance of nickel complexes as catalyst in cross-coupling reactions has been increasing due to
their potential as an alternative to more expensive palladium catalysts. However, few mechanistic studies of Nibased precatalysts have been reported.1 The propensity of Ni0 catalysts to generate NiI species, which are poorly
active in Suzuki-Miyaura cross-coupling reactions complicates reaction understanding and optimisation. We have
studied the rates of oxidative addition of different electrophiles to a relevant Ni0 complex ([Ni(COD)(dppf)] (COD
= 1,5-cyclooctadiene; dppf = 1,1´-bis (diphenylphosphino)ferrocene), as well as the selectivity of these processes
to clarify the origin of the NiI (Figure 1).
Figure 6
References
1. a) Quasdorf, K. W.; Antoft-Finch, A.; Liu, P.; Silberstein, A. L.; Komaromi, A.; Blackburn, T; Ramgren, S.
D.; Houk, K. N.; Snieckus, V.; Garg, N. K. J. Am. Chem. Soc. 2011, 133, 6352; b) Zhang, K. N.; CondaSheridan, M.; Cooke, S. R.; Louie, J. Organometallics 2011, 30, 2546; c) Christian, A. H.; Muller, P.;
Monfette, S. Organometallics 2014, 33, 2134; d) Guard, L. M.; Mohadjer Beromi, M.; Brudvig, G. W.; Hazari,
N.; Vinyard, D. J. Angew. Chem. Int. Ed. 2015, 54, 13352.
39
ORAL ABSTRACTS
Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base
macrocyclic ligands
N. L. Bell*1, P. L. Arnold1, and J. B. Love1
1
EastChem School of Chemistry, The University of Edinburgh, The Kings Buildings, Edinburgh
[email protected]
Uranyl [UVIO2]2+ is the most stable and prevalent form of uranium in the environment.1,2 The redox properties
of uranyl are of interest in order to establish chemical routes to separate and immobilise actinide radioactive
wastes.3 Reduced [UVO2]+ species are inherently unstable to disproportionation under aqueous conditions forming
[UVI] and [UIV] products, with the latter being insoluble in aqueous waste streams and therefore immobilised by
this process.4 As such, the synthesis of these motifs in molecular species bound within defined ligand
environments can improve our understanding of actinide bonding and help us to predict uranyl speciation.
We have studied extensively the reduction of uranyl incorporated within a Schiff-base macrocyclic ligand
with two aryl-linked coordination pockets (LMe, Scheme 1).2,5,6 Formation of heterobimetallic complexes of this
ligand by coordination of electropositive metals (e.g. Li, Ln) within the vacant compartment of the macrocycle
leads to activation of the U=Oendo bond which facilitates reduction to a stable UVO2 complex.6 In contrast,
incorporation of a less reducing metal (e.g. Fe(II), Mn(II)) did not promote reduction and the corresponding
uranyl(VI) UVIO2M(LMe) complexes were isolated.7 In this ligand, the proximity of the uranyl endo-oxygen to the
lower macrocyclic pocket facilitates interaction with the second metal. More recently we have developed the
chemistry of an anthracenyl-linked analogue of this ligand (LA) and synthesised mono- and dinuclear uranyl
complexes (Scheme 1).8 The anthracenyl linker enforces both a greater distance between the N4-coordination
compartments and a greater degree of coplanarity.
Scheme 1: Controlling the interaction of group 14 metals with uranyl oxo groups using ligands LA (top)
and LMe (bottom). M = Ge, Sn, Pb; N” = N(SiMe 3)2
We have now explored and compared the reactivity of the uranyl complexes of these two ligands, UO 2(H2L)
(L = LMe, LA) towards group 14 metal silylamides (M{N(SiMe 3)2}2, M = Ge, Sn, Pb).9 The interaction between
the two metal ions in the resulting complexes and any resulting activation of the UO 2 bonds has been assessed
spectroscopically, as has the reactivity of these complexes towards oxo-transfer reagents.
References
1.G. R. Choppin, J. Radioanal. Nucl. Chem., 2007, 273, 695-703; 2.P. L. Arnold, G. M. Jones, S. O. Odoh, G. Schreckenbach, N. Magnani
and J. B. Love, Nat. Chem., 2012, 4, 221-227; 3.J. N. Mathur, M. S. Murali and K. L. Nash, Solvent Extr. Ion Exch., 2001, 19, 357-390; E. P.
Horwitz, R. Chiarizia, M. L. Dietz and H. Diamond, Anal. Chim. Acta, 1993, 281, 361-372; Y. Sakamura, T. Hijikata, K. Kinoshita, T. Inoue,
T. S. Storvick, C. L. Krueger, J. J. Roy, D. L. Grimmett, S. P. Fusselman and R. L. Gay, J. Alloys Compd., 1998, 271, 592-596; 4.P. L. Arnold,
J. B. Love and D. Patel, Coord. Chem. Rev., 2009, 253, 1973-1978; J. C. Renshaw, L. J. C. Butchins, F. R. Livens, I. May, J. M. Charnock
and J. R. Lloyd, Environ. Sci. Technol., 2005, 39, 5657-5660; 5.P. L. Arnold, A. F. Pecharman and J. B. Love, Angew. Chem.-Int. Edit., 2011,
50, 9456-9458; P. L. Arnold, E. Hollis, F. J. White, N. Magnani, R. Caciuffo and J. B. Love, Angew. Chem.-Int. Edit., 2011, 50, 887-890; G.
M. Jones, P. L. Arnold and J. B. Love, Chem. Eur. J., 2013, 19, 10287-10294; 6. P. L. Arnold, A.-F. Pecharman, E. Hollis, A. Yahia, L.
Maron, S. Parsons and J. B. Love, Nat. Chem., 2010, 2, 1056-1061; P. L. Arnold, A.-F. Pécharman, R. M. Lord, G. M. Jones, E. Hollis, G. S.
Nichol, L. Maron, J. Fang, T. Davin and J. B. Love, Inorg. Chem., 2015, 54, 3702-3710; 7. P. L. Arnold, D. Patel, A. J. Blake, C. Wilson and
J. B. Love, J. Am. Chem. Soc., 2006, 128, 9610-9611; 8.P. L. Arnold, G. M. Jones, Q.-J. Pan, G. Schreckenbach and J. B. Love, Dalton Trans.,
2012, 41, 6595-6597; X. J. Zheng, N. L. Bell, C. J. Stevens, Y. X. Zhong, G. Schreckenbach, P. L. Arnold, J. B. Love and Q. J. Pan, Submitted,
2016; 9.N. L. Bell, P. L. Arnold and J. B. Love, Submitted, 2016
The incorporation of transition metals into single molecule conductors
40
ORAL ABSTRACTS
R. J. Davidson,1* D. Costa-Milan,2 J. Liang, R. J. Nichols,2 S. J. Higgins,2 D. S. Yufit,1 A. Beeby,1 P. J.
Low.3
1
Department of Chemistry, Durham University, South Rd, Durham, DH1 3LE, UK
Department of Chemistry, University of Liverpool, Crown St, Liverpool, L69 7ZD, UK
3
School of Chemistry and Biochemistry, University of Western Australia, Stirling Highway, Perth, WA
6009, Australia
[email protected]
2
With conventional silicon-based electronics nearing their size and therefore power limits, there has been a
drive to develop molecular electronics, whereby individual molecules act as the electronic components.
Although it is an active field of research, there still remain a great number of questions about the factors
affecting single-molecule conductance. A convenient method for probing this is to incorporate a metal centres
into molecular wires (a highly π-conjugated system), allowing the electron properties of the molecule to be
modified without significantly altering the geometry.
4-substituted bis-2,2′:6′,2″-terpyridine (tpy) metal complexes provide a distinct advantage existing
organometallic systems as the metal, linker and binding site are able to be modified in a modular fashion
without requiring significantly different synthetic approaches. In this project we examined a series of monoand bi-metallic of iron(II), cobalt(II) and ruthenium(II) complexes based on combinations of 2,3,5,6tetra(pyridine-2-yl)pyrazine and methyl-sulfane or trimethylsilylacetylene substituted 2,2′:6′,2″-terpyridine
ligands. Using conductance STM we explored how the single molecule conductance of metal complexes can
be significantly affected by the combination of metal and surface binding group, much more so than the their
pure organic molecule analogues.
Figure 1 Bimetallic ruthenium complex in an conductive STM junction
41
ORAL ABSTRACTS
Tuning the optical and electronic properties of boron-containing electron-acceptor groups
R. M. Edkins,*1,2 Z. Zhang,2,3 T. B. Marder2
1
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford OX1 3TA,
United Kingdom
2
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97078
Würzburg, Germany
3
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University,
Changchun 130012, P. R. China
E-mail: [email protected]
The strong π-electron-accepting ability of three-coordinate boron is exemplified by the BMes2 (Mes = mesityl)
group,1 wherein steric crowding by the two mesityl moieties prevents hydrolysis, affording air-stable compounds.
Following our predictions,2a work by Yamaguchi2b,c and our earlier collaboration with Jäkle,3 we report herein the
chemistry and photophysics of boron compounds containing FMes groups (FMes = fluoromesityl = 2,4,6(CF3)3C6H2). Using the B(FMes)2 group, we have observed large reduction-potential shifts of up to 1 V, relative
to B(Mes)2 analogues, and have synthesized donor-acceptor compounds exhibiting aggregation-induced emission,
turn-on fluoride sensing, and large Stokes shifts of over 10,000 cm1.4 Furthermore, dual fluorescence and longlived phosphorescence (τ = 2.47 s) of one derivative was observed at low temperature, which was studied using
time-gated spectroscopy.
However, the emission of these compounds is strongly quenched in polar solvents, which led us to develop
alternative boron-containing groups that allow finer electronic tuning while maintaining strong emission. 5
Emission maxima spanning a ca. 150 nm range highlight the effect of careful modulation of the electron-density
at the boron center. With photoluminescence quantum yields of up to 0.96, these compounds are some of the most
efficient red-emitting organoboron chromophores to-date. An understanding of the requirements for organoboron
compounds to show efficient far-red and even near-infrared emission has been developed. The observed emission
properties are rationalized based on a combined spectroscopic and theoretical study, including a TD-DFT study
of the twisted-intramolecular charge-transfer (TICT) excited-states of some archetypal B(FMes)2-containing
compounds. Furthermore, we report the use of the FMes group to stabilize anti-aromatic boroles,6 giving insight
into the electronic structure of these compounds, which may find use as electron-transporting materials in
optoelectronic devices.
[1] Entwistle, C. D.; Marder, T. B. Angew. Chem. Int. Ed. 2002, 41, 2927-2931
[2] (a) Weber, L.; Werner, V.; Fox, M. A.; Marder, T. B.; Schwedler, S.; Brockhinke, A.; Stammler, H.-G.;
Neumann, B. Dalton Trans. 2009, 1339-1351; (b) Wang, J.; Wang, Y.; Taniguchi, T.; Yamaguchi, S.; Irle, S. J.
Phys. Chem. A 2012, 116, 1151-1158; (c) Taniguchi, T.; Wang, J.; Irle S.; Yamaguchi, S. Dalton Trans. 2013,
42, 620-624
[3] Yin, X. D.; Chen, J. W.; Lalancette, R. A.; Marder, T. B.; Jäkle, F. Angew. Chem. Int. Ed. 2014, 53, 97619765
[4] Zhang, Z.; Edkins, R. M.; Nitsch, J.; Fucke, K.; Steffen, A.; Longobardi, L. E.; Stephan, D. W.; Lambert, C.;
Marder, T. B. Chem. Sci. 2015, 6, 177-190
[5] Zhang, Z.; Edkins, R. M.; Nitsch, J.; Fucke, K.; Eichhorn, A.; Steffen, A.; Meier, M.; Wang, Y.; Marder, T.
B. Chem. Eur. J. 2015, 21, 5922-5927
[6] Zhang, Z.; Edkins, R. M.; Haehnel, M.; Wehner, M.; Eichhorn, A.; Mailänder, L.; Meier, M.; Brand, J.; Brede,
F.; Müller-Buschbaum, K.; Braunschweig, H.; Marder, T. B. Chem. Sci. 2015, 6, 5922-5927
42
ORAL ABSTRACTS
Lignin conversion to fine chemcials
D. Fragoso*1, S. D. Jackson
1
Center for Catalysis Research
[email protected]
The production of fuels and chemicals from biomass is one of the great challenges of this century and several
methods of transforming biomass into useful products have been studied over the past few years. Lignocellulosic
materials represent one of the biggest renewable natural reserves and the biorefinery has an important role
contributing to the environment along with biomass conversion to multiple products such as fuel and fine
chemicals. Kraft lignin is obtained from the most dominant process (Kraft process) and it is produced
commercially. Currently this lignin is seen as a waste product and is mainly used as a fuel. The challenge of
studying lignin conversion is significant because of its complex structure that varies with plant source and
pretreatment, however it is promising try to find more useful applications for lignin such as the generation of very
high-quality aromatic products that can be obtained by depolymerisation. Since it is a polymeric material (high
molecular weight) the use of heterogeneous catalysts has been applied in this area. From previous studies it is
known the efficiency of catalysts based on Pt in C-O bond breakage; a key bond in the lignin polymer.
Primarily for this work, the reactions were done in order to study what effect different solvent solutions had on
Kraft lignin depolymerisation in the absence and presence of the Pt/alumina catalyst. The solvents used were
methanol, ethanol, isopropanol and acetone in a 50/50 v/v ratio with water. The reactions studied were conducted
in a 300 mL Parr batch autoclave reactor at 300 0C for 3 hours.
With the purpose of analysing the reaction products and obtaining an overview of the mass distribution, Gel
Permeation Chromatograph was carried out. From the GPC analysis could be observed a difference in product
distribution for the blank (reaction without catalyst) and the catalytic reaction compared to the Kraft lignin for all
the solutions used. There is a clear change indicating a shift to lower molecular monomeric products when the
solvent solutions and catalyst were added, therefore can be assumed that some depolymerisation occurred at Kraft
Lignin.
It can be considered from previous studies that the possibility of lignin be deposited and charred onto the catalyst
surface during the reaction as well as some of the higher molecular weight product species. With the aim of
investigating this carbonaceous material, the post reaction catalyst were properly collected and the samples were
analysed using the CHN (Elemental Analysis), Raman, BET (Surface Area and Pore Volume Determination),
XRD (X-Ray Diffraction) and TGA (thermogravimetric analysis).
43
ORAL ABSTRACTS
Carbon laydown analysis of trans-hydrogenation activity over CrOx/Al2O3 catalyst
M.D. Garba*; S David Jackson
Centre for Catalysis Research, WestCHEM, Dept of Chemistry, University of Glasgow, Glasgow G12 8QQ, UK.
[email protected];
Introduction
The primary purpose of the trans-hydrogenation process historically has been to convert low-value
cracked hydrocarbons into valued distillate products. Although trans-hydrogenation is not a new technology for
production of olefins there is scant scientific attention toward the invention. 1-3 Trans-hydrogenation combines
two processes, dehydrogenation & hydrogenation, together over a catalyst to form two alkenes. Alkane
dehydrogenation is endothermic (~124 kJ.mol-1) which has an equilibrium limitation where typical temperatures
≥ 550 oC are required for reasonable conversion. On the other hand, alkyne/alkadiene hydrogenation is exothermic
(~-157 kJ.mol-1) and produces significant amount of heat which can be utilized in the dehydrogenation process.
At higher temperatures however secondary reactions such as cracking and carbon deposition are also favoured. In
this study we have examined the carbon deposition associated with trans-hydrogenation.
Experimental
A 4% CrOx/alumina catalyst was prepared using incipient wetness. The catalyst 0.5g was reduced in
pure hydrogen (40cm3min-1) for 2 hr at 600oC. Pentane, hexyne and 1,5-hexadiene were fed using argon as carrier
gas, individually and as a mixed (alkane/alkyne or alkadiene) in the ratio 1:5 and a GSHV 2250 h -1 over the
temperature range 250-500 oC. The reactor eluent were analysed by GC and the post reaction catalyst analysed
by TPO, BET, Raman and XRD to analyse the carbon laydown on the catalyst
Ion Current (nA)
Deriv. Weight (%/°C)
Result and discussion
Trans-hydrogenation activity was observed, however carbon laydown analysis revealed an appreciable
amount of carbonaceous material on the post reaction catalyst. TPO revealed a single broad evolution of CO 2
(TGA/MS) as shown in figure 2. While analysis by Raman spectroscopy revealed the presence of D and G bands
associated with graphitic carbon. The extent and nature of the carbon
0.05
5.00E-03
deposit was associated with the reactant and reaction temperature
used. A loss in surface was also evident from the BET surface area
4.00E-03
0.04
analysis (table 1). No sintering of the support was detected by XRD
3.00E-03
0.03
analysis suggesting the loss in area was due to carbon blocking pores.
2.00E-03
0.02
The full evaluation will be presented in the paper.
1.00E-03
0.01
0
0.00E+00
References.
1. Jackson SD, Matheson IM, Webb G (2005) Appl Catal 289:16–21
2. Jackson SD, Matheson IM, Webb G (2004) Preprints. Div Pet
Chem ACS 49:50–53
3. Wigzell FA, Rugmini S, Jackson SD (2015) Appl Pet Res 5:199-205
0
200
-1.00E-03
400 600 800 1000 1200
Temperature (°C)
driv weight loss
Table 1: BET surface area for various reactions conducted compared to the fresh
catalyst
Reactant
Pentane
Reactant
Hexyne
Pent/hex
BET
surface
area
(m2g-1)
BET
surface
area
(m2g-1)
Fresh
catalyst
Fresh
203
catalyst
Post reaction catalyst
500C
177
155
165
500C
400C
350C
184
191
Post
154reaction catalyst
152
163
159
400C
350C
300C
195
151
300C152
Pentane only
177
184
191
195
200
Hexyne only
155
154
152
151
Pent/hex mix
165
163
159
152
Table 1: BET surface area for various reactions conducted compared to the fresh
catalyst
44
ORAL ABSTRACTS
A new approach to screening and designing solvents for low-dimensional materials
A. Hardy1*, H. Bock1
1
Institute of Chemical Sciences, Heriot Watt University, Edinburgh, UK
[email protected]
Despite more than 25 years of intensive research, we are still lacking solvents for many 1D and 2D nanomaterials
such as carbon nanotubes (CNT) and graphene, that are good enough for industrial processing, not to mention
solvents that are also environmentally friendly, non-toxic and generally safe to use.
Intriguingly, a molecule (cyclohexyl-pyrrolidinone, CHP 1) has recently been discovered that is at least 5 times
better at dissolving CNTs than all other tested substances. This has raised confidence that even better solvents can
be discovered in the future. However, experimental testing is time-consuming, costly, limited to immediately
available substances and potentially unsafe.
We propose to use computational screening instead. A new technique will be presented, the Theory of
Corresponding Distances, which increases the computational speed for a potential of mean force (PMF)
calculation by up to 20x compared to current methods, and requires just one simulation to obtain the entire PMF
curve. A comparison to current techniques is shown in Figure 1; agreement is excellent between the two.
The improved computational speed and reduced overheads of performing a PMF calculation in this way should
allow the rapid screening of potential solvent molecules and exploration of these systems in ways that previously
may have been regarded as too costly or too complex.
1
2
Figure 1 Main: Potential of mean force calculation for CBrCl3 2 from a simulation using the theory of
corresponding distances (lines) and a series of independent simulations using conventional techniques (squares).
Inset: raw force data from the same simulations. The distance, d, on the x-axis corresponds to the tube-tube
surface distance. T = 300K.
45
ORAL ABSTRACTS
Enhancement of TbIII-CuII single-molecule magnet performance through structural modification
M. Heras Ojea*1, V. A. Milway1, L. H. Thomas2, S. J. Coles3, C. Wilson1, W. Wernsdorfer4 and Mark
Murrie1
1
WestCHEM, School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK.
2
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
3
Department of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK.
4
Institut Neel, CNRS, Nanosciences Department, BP 166, 25 rue des Martyrs, 38042 Grenoble Cedex 9,
France
[email protected]
The development of new synthetic methodologies towards the assembly of 4f-based complexes has attracted
considerable interest in molecular magnetism, due to the high-spin ground state and large magnetic anisotropy
characteristics of the lanthanide ions.[1-3] Recent studies reveal how subtle modifications of the environment
around 4f ions can cause dramatic changes in the overall magnetic properties of the complex.[4,5]
Here we present a series of 3d-4f complexes using the bis-tris propane (H6L) pro-ligand {Ln2Cu3(H3L)2Xn}
(when X = OAc−, Ln = Gd, Tb or when X = NO3−, Ln = Gd, Tb, Dy, Ho, Er). All complexes, except where
Ln = Gd, show slow magnetic relaxation in zero applied dc field. A remarkable improvement of the energy
barrier to reorientation of the magnetisation in the {Tb2Cu3(H3L)2Xn} complexes is seen by using a strategy
based on the replacement of the auxiliary ligands (X = OAc −, NO3−). This leads to the largest reported
relaxation barrier in zero applied dc field for a Tb/Cu-based single-molecule magnet.
[1] L. Rosado Piquer and E. C. Sanudo, Dalton Trans., 44, 8771 (2015).
[2] D. N. Woodruff, R. E. P. Winpenny and R. A. Layfield, Chem. Rev., 113, 5110 (2013).
[3] J. Luzon and R. Sessoli, Dalton Trans., 41, 13556 (2012).
[4] J. Zhu, C. Wang, F. Luan, T. Liu, P. Yan and G. Li, Inorg. Chem., 53, 8895 (2014).
[5] W.-B. Sun, P.-F. Yan, S.-D. Jiang, B.-W. Wang, Y.-Q. Zhang, H.-F. Li, P. Chen, Z.-M. Wang and S. Gao,
Chem. Sci., 7, 684 (2016).
46
ORAL ABSTRACTS
Towards design of 2D layered materials via a molecular assembly approach
H. N. Miras,* H.-Y. Zang, J. Purcell, J. McAllister, D.-L. Long and L. Cronin
[email protected]
Polyoxometalates (POMs) and polyoxo(thio)metalates have been the subject of a large number of studies due to
their nanoscale size, versatile architectures and tuneable electronic and physical properties, 1 as well as
fundamental investigations of their supramolecular self-assembly.2 Previous studies showed that the dimeric
[Mo2O2S2]2+ cationic species is a very useful building block, due to inherent stability over a wide range of pH
values. This is because interactions with ligands of the appropriate rigidity, charge and geometry can lead to
gigantic structures. Herein we report the directed assembly of the [Mo2S2O2]2+ / XO32- (X = Se, Te) system, (Figure
1) leading to the isolation of a range of nanoscale structures ranging from “endo” {Mo 16Se20} and “exo”
{Mo28Se17}, to ring-shaped {Mo16Se8}, {Mo8Te} topologies. Additionally, we explored the possibility of using
molecular chalcoxides (ChalcoPOMs) as progenitors for the manufacturing of layered chalcogen-doped materials
and interesting optical properties, Figure 2.
Figure 1 Ball-and-stick representation of the clusters “endo” {Mo16Se20}, “exo” {Mo28Se17} and {Mo16Se8}. The
gradual increase of Se concentration in the reaction mixture was reflected by the increased Se content in the
isolated architectures as revealed by the X-ray diffraction analyses. Colour code: Mo, light grey; S, Yellow; Se,
Blue; O, Red.
Figure 2 (LEFT) Optical photograph displaying blue emission of the layered materials; (RIGHT) SEM images of
Te-doped MoS2
References
1. H. N. Miras, J. Yan, D.-L. Long and L. Cronin, Chem. Soc. Rev., 2012, 41, 7403–7430;
2. H. Y. Zang, J. J. Chen, D. L. Long, L. Cronin and H. N. Miras, Adv. Mater., 2013, 25, 6245-6249
47
ORAL ABSTRACTS
Polymer-based porous composite materials for hydrogen storage applications
S. Rochat1*, A. D. Burrows1
1
Department of Chemistry, University of Bath, Bath, UK
[email protected]
Solid-state hydrogen storage promises to significantly improve upon the conventional forms of storage
technologies such as liquid or compressed gas. In recent years a significant research effort has been devoted
to the development of adsorbents with very high surface areas, such as metal-organic frameworks (MOFs),
covalent organic frameworks (COFs) and amorphous organic polymers. 1 A frequent drawback of these
materials is their usual powdery form, which limits their processability and mechanical properties. In this
context, materials combining solution-based processability, strong mechanical properties and high hydrogen
adsorption capacity are highly desirable.
We investigated the use of a polymer, PIM-1, as a supporting matrix for high surface area adsorbents. PIM-1
is a microporous material itself (albeit with a relatively limited surface area), and also possesses the ability of
forming robust, flexible films and membranes by simple solvent casting procedures. 2 We studied membranes
made of PIM-1 to which various amounts of highly porous organic frameworks were added. The combination
of high-surface area additives with the polymeric nature of PIM-1 afforded composite materials possessing
significant hydrogen adsorption properties while maintaining the advantageous mechanical properties and
processability of membranes.
The results presented here provide a significant basis towards the development of new composite materials
for hydrogen storage applications. Further, the nearly limitless number of potential materials combinations
provides a strong incentive to further investigate such systems in the broader context of gas storage and
separation.
Figure 1: a) Structure of PIM1, b) Scheme showing its contorted, porous nature, and c) A transparent, solventcast membrane made of PIM1 over the logo of the University of Bath.
References:
[1] D. P. Broom, C. J. Webb, K. E. Hurst, P. A. Parilla, T. Gennett, C. M. Brown, R. Zacharia, E. Tylianakis,
E. Klontzas, G. E. Froudakis, Th. A. Steriotis, P. N. Trikalitis, D. L. Anton, B. Hardy, D. Tamburello, C.
Corgnale, B. A. van Hassel, D. Cossement, R. Chahine, M. Hirscher, Appl. Phys. A 2016, 122:151;
[2] P. M. Budd, E. S. Elabas, B. S. Ghanem, S. Makhseed, N. B. McKeown, K. J. Msayib, C. E. Tattershall,
D. Wang, Adv. Mater. 2004, 16, 456.
48
ORAL ABSTRACTS
Lithium hydride and organic amines for hydrogen storage
T. Y. Su and D. H. Gregory
School of Chemistry, University of Glasgow
[email protected]
Dehydrogenation reactions between amides/imides and light metal hydrides have instigated a decade-long
discussion within the hydrogen storage community. The main debate centres on the nature of the hydrogen
release process; whether a direct Hδ+ … Hxδ- interaction is operative in the solid state or if an ammoniamediated route is the preferred mechanism. Recent publications on urea-LiBH4 complex materials and LiHLiNH2 non-stoichiometric product formation in the solid state have made valuable contributions to the
fundamental understanding of these solid state reactions.
In contrast to the vast array of inorganic N-H systems and ammonia borane materials reported in literature,
organic amines have received little attention for use in hydrogen storage despite a wealth of documented
amine deprotonation studies. Common amine compounds, such as urea, are well known to deprotonate readily
in the presence of strong bases. Herein we report an account of dehydrogenation in the lithium hydride-urea
system (eq. 1). Our experimental evidence suggests that the system dehydrogenates via a mechanism,
invoking both solid state and ammonia-mediated reaction steps. A strategy to regenerate the starting urea ex
situ from the reaction product Li2NCN has also been developed.
4 LiH + CO(NH2)2 → Li2NCN + Li2O + 4 H2
H2
wt = 8.78 %
(1)
The onset of dehydrogenation was detected at temperatures as low as 60 °C (Fig.1), although the system
behaves differently thereafter depending on whether high energy ball milled LiH or untreated, as-received
LiH is employed: the former interacts with evolved ammonia to release hydrogen, whereas the latter remains
relatively inert..
Figure 7 TG/DTA (left) and MS (right) of ball mill activated LiH and urea.
References
[1] P. Chen, Z. T. Xiong, J. Z. Luo, J. Y. Lin, K. I. Tan, Nature 2002, 420, 302-304
[2] D. I. F. William, M. O. Jones, D. H. Gregory, C. M. Jewell, S. R. Johnson, A. Walton, P. P. Edwards,
JACS 2007, 129, 1594-1601
[3] L. Liu, G. Wu, W. Chen, Z. Xiong, T. He, P. Chen, Int. J. Hydrogen Energy 2015, 40, 429-434
[4] A. D. Sutton, A. K. Burrell, D. A. Dixon, E. B. Garner III, J. C. Gordon, T. Nakagawa, K. C. Ott, J. P.
Robinson, M. Vasiliu, Science 2011, 331, 1426-1429
49
ORAL ABSTRACTS
Characterisation of high aspect nanomaterials to support hazard assessment
G. Carse1, G. Fern1, S. Billett1, C.A. Poland1, S.M. Hankin1
1
Institute of Occupational Medicine, Edinburgh, UK
[email protected]
High aspect ratio nanomaterials such as nanoplatelets (e.g. graphene-family nanomaterials) and nanofibers (e.g.
carbon nanofibers), are of interest to hazard assessment as a result of their aerodynamic properties. Due to their
aspect ratio, physically large platelets and fibres can behave in a comparable way to significantly smaller particles
when airborne, potentially resulting in deposition in and problematic clearance from the deep lung. Detailed
characterisation is required in order to fully inform the hazard assessment of these types of materials.
A multi-instrumental approach and particle classification technique is utilised to provide a detailed
characterisation of materials. Separation of the respirable fraction from bulk powders, based on aerodynamic size,
can be performed to enable a detailed characterisation to support hazard assessment. Information on the particle
size distribution of the aerosolised and classified respirable fraction is obtained in situ utilising a selection of
direct-reading, real-time instruments covering a size range from 5 nm- 20 µm. Mapping of aerodynamic to
physical size of high aspect ratio particles is carried out using size selective particle samplers combined with offline microscopy (scanning electron microscopy) to complement direct-reading instrumental information.
The adoption of a multi-instrumental and particle classification approach allows for a detailed characterisation of
high aspect ratio nanomaterials which is integral to a robust material hazard assessment.
50
ORAL ABSTRACTS
Rapid electrochemical assays for biomedical applications
Damion K Corrigan1&2, Holger Schulze3, Grace Henihan3, Ilenia Ciani3, Andrew R Mount2, Till Bachmann3.
1
Department of Biomedical Engineering, University of Strathclyde, UK
2
School of Chemistry, University of Edinburgh, UK
3
Division of Pathway Medicine, University of Edinburgh, UK
[email protected]
The rapid diagnosis of infection, determination of antibiotic resistance and accurate measurement of biomarkers
is an analytical challenge which if met successfully promises to have significant benefits for public health.
Electrochemical techniques have the advantage of being sensitive, simple and label free which makes
electrochemical detection an ideal candidate technology for “point of care testing” applications. This talk will
cover various aspects of the development of such assays using electrochemical impedance spectroscopy (EIS)
including surface probe choice, spacer chemistry, electrode fabrication, assay conditions and sample preparation.
An important outcome of this work is the development of a sensitive test for the antibiotic resistant bacterium
MRSA which no longer requires the time consuming PCR step, thus leading to faster results (< 15 mins) and a
dramatically simplified measurement protocol leading to the prospect of rapid infection and antibiotic resistance
measurements in hospital settings and out in the community.
Summary of the assay principle and procedure
References
1)
2)
3)
4)
5)
Henihan, G., Schulze, H., Corrigan, D.K., Giraud, G., Terry, J.G., Hardie, A., Campbell, C.J., Walton, A.J., Crain, J., Pethig, R.,
Templeton, K.E., Mount A.R. and Bachmann T.T. (2016) Label and amplification-free electrochemical detection of bacterial
ribosomal RNA. Biosensors & Bioelectronics, 81, 487-94
Corrigan, D.K., Schulze, H., McDermott, R., Schmüser, I., Henihan, G., Henry, J.B., Bachmann, T.T., Mount, A.R. (2014)
Improving electrochemical biosensor performance by understanding the influence of target DNA length on assay sensitivity.
Journal of Electroanalytical Chemistry, 723, 25-29.
Corrigan, D.K., Schulze, H., Henihan, G., Hardie, A., Ciani, I., Giraud, G., Terry, J.G., Walton, A.J., Pethig, R., Ghazal P., Crain,
J., Campbell, C.J., Templeton, K.E., Mount, A.R., and Bachmann T.T. (2013) A PCR-free electrochemical point of care test for
clinical detection of methicillin resistant Staphylococcus aureus (MRSA). Analyst. 138 (22), 6997 – 7005
Corrigan, D.K., Schulze, H., Henihan, G., Ciani, I., Giraud, G., Terry, J.G., Walton, A.J., Pethig, R., Ghazal, P., Crain, J., Campbell,
C.J., Mount A.R., Bachmann, T.T. (2012). Impedimetric detection of PCR products derived from MRSA clinical isolates.
Biosensors & Bioelectronics. 34, 178-184.
Ciani, I., Schulze, H., Corrigan, D.K., Henihan, G., Giraud, G., Terry, J.G., Walton, A.J., Pethig, R., Ghazal, P., Crain, J., Campbell,
C.J., Bachmann, T.T. & Mount, A.R. (2012). Rapid detection of infection biomarkers in mock wound fluid using electrochemical
impedance spectroscopy. Biosensors & Bioelectronics, 31, 413-418
51
ORAL ABSTRACTS
Supramolecular hair dyes (SHDs): A new application of co-crystallization
A. Delori,*1, A. J. Urquhart 2 and I. D. H. Oswald1
1
Strathclyde Institute of Pharmacy and Biomedical Sciences, University of Strathclyde, 161 Cathedral
Street, Glasgow, G4 0RE, UK. E-mail [email protected] (AD), [email protected] (IO),
2
Technical University of Denmark, Department of Micro- and Nanotechnology, Ørsteds Plads, Building
345Ø, 2800 Kgs. Lyngby, Denmark, [email protected] (AJU).
Permanent hair dyes hold a dominant (70-80%) share of the multi-billion dollar hair dye industry.1 These
hairs dyes have been linked with immature greying of hairs, increase in hair porosity and hair fall, which is
due to presence of harsh chemicals such as NH3 and H2O2. Hairs dyed with NH3 containing hair dyes require
further conditioning, which adds to the cost. The research over the last 2-3 decades has also raised serious
concerns about the safety of these hair dyes, as many of these hair dyes have been found to be carcinogenic. 2,
3
We have developed a new type of hair dye product to address these issues. Unlike the commercial hair
dyes, which are formed by synthetic procedures, this new product is formed by the non-synthetic route. This
route is more economical and avoids the use of harsh chemicals like NH 3 and H2O2. All our dyes are well
characterized using diffraction, thermal and other techniques such as UV, IR etc. Hairs dyed with these new
SHDs were tested for colour fastness, which was found to be excellent. Surface analysis of hairs, using SEM,
confirmed that these dyes are not harsh on hairs.
(1) Freeman, H. S.; Peters, A. T., Colorants for Non-Textile Applications. ed.; Elsevier: 2000.
(2) http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_o_094.pdf.
(3) http://www.rsc.org/chemistryworld/2012/09/hair-dye-ppd-allergen-regulation.
52
ORAL ABSTRACTS
3D-printed microdevices for particle synthesis and analysis
S. M. Hampson*1, T. Monaghan2, S. D. R. Christie1 and M. Platt1
1
2
Department of Chemistry, Loughborough University, Loughborough, UK
Wolfson School of Mechanical & Manufacturing Engineering, Loughborough University, Loughborough, UK
[email protected]
Microfluidics, the use of liquid flows on the micrometre scale, is the driving force behind innumerous LOC
(lab-on-a-chip) innovations. These range from handheld devices for analysis (such as disease diagnostics or
environmental monitoring), to miniaturised reactors for chemical synthesis1 or material assembly. LOC
devices are also gaining increasing attention as platforms for particle handling: both in particle synthesis, and
in carrying out particle-based assays. However, key factors hindering the widespread use of these, and other,
LOC microfluidic systems is the fact that the majority are still being fabricated via time-consuming and/or
expensive methods, as well as being limited in material choice.
One possible solution is additive manufacturing, more commonly known as 3D printing. Over the last few
years its popularity has skyrocketed, with its industry now exceeding $5 billion. In this family of processes,
layers of material are successively built up under computer control to form a three-dimensional object. Its
rapid production speed, wide material variety, and its digital, easily sharable and editable file format give it
the power to revolutionise traditional manufacturing processes.
Here we present two printed microdevices for performing particle-by-particle analysis: a flow cytometer with
integrated UV/visible optical detection as shown in Figure 1, and an electrochemical micropore sensor based
on resistive pulse sensing (RPS). These widgets cost between £3.50 and £10 to print (in contrast to £15,000
to £30,000 commercial instruments), and are smaller than a match box. The characterisation and development
of these devices, along with the use of a genetic algorithm for measurement optimisation, will be discussed,
as well as both the perks and pitfalls of printing on this tiny scale.
Figure 1 3D printed flow cytometer at work: a) demonstration of hydrodynamic focusing power, by use of
water sheath flows alongside methylene blue core stream, and b) monitoring of polystyrene particle stream
at 650 nm by use of built-in optical fiber system
1. A.J. Capel, S. Edmondson, S.D.R.Christie, R.D. Goodridge, R.J. Bibb and M.Thurstans, Lab Chip, 2013, 13,
4583-4590.
53
ORAL ABSTRACTS
Understanding lipid behaviour: improving the therapeutic potential of glycolipids
P.N. Jemmett,*1 L.R. Cox1 and S.L. Horswell1
1
School of Chemistry, University of Birmingham, Birmingham, UK
[email protected]
Glycosyl ceramide derivatives (Fig. 1) within cell membranes have been observed to have therapeutic effects
either by enhancing or supressing the immune response in vivo, with the precise response varying according to
the glycolipid structure. The derivatives of these lipds are present in various regions of antigen-presenting cell
membranes (e.g. cholesterol-rich rafts or non-raft regions) but with limited established literature on the rationale
for the localisation.. It is crucial to understand the organisation of such glycolipids within biomimetic model lipid
bilayers composed of typical membrane lipids and how the addition of glycolipids changes the physical properties
of the whole lipid layer.
Figure 8: KRN7000, or α-galactosyl ceramide, the prototypical immune-related glycolipid
A model system for investigating glycolipids has been established, utilising lipid monolayers (based on
phospholipids, sphingolipids and cholesterol) formed at the air|water interface. These monolayers have been
investigated by surface pressure-area isotherms. Langmuir-Blodgett and Langmuir-Schaeffer deposition
techniques have been used to transfer lipid bilayers onto gold substrates, allowing polarisation-modulated infrared
reflection-absorption spectroscopy (PM-IRRAS) and electrochemistry (differential capacitance and
chronocoulometry) to be used to characterise the impacts of lipid structural parameters, such as alkyl chain length,
and head group structure, upon the structure and behaviour of model cell membranes.
It is anticipated that the results of such a biophysical study will shed light on the relationship between glycolipid
molecular structure and resulting immune response and help devise novel glycolipids with modified
physicochemical properties that lead to tailored immune responses for specific therapeutic applications such as
vaccinations, auto-immune disease or cancer.
54
ORAL ABSTRACTS
Going from Product to Process Analysis: Analysing Pharmaceutical Crystallisation using in-situ
Spectroscopy
P. MacFhionnghaile
EPSRC Centre for Innovative Manufacturing in Continuous Manufacturing and Crystallisation, University of
Strathclyde, Glasgow, UK
[email protected]
Traditionally analysis is focused on end product analysis. Advances in analytical and probe technology have
made real-time analysis of reactions and crystallisation possible. Process analysis has been shown to optimise
manufacturing techniques, improve process robustness, and remove the need for off-line analysis. By coupling
spectroscopic methods with a variety of probe technologies Ultra-Violent, Infrared, Near Infrared, and Raman
spectroscopy is used for in-situ monitoring, and measuring solutions, slurries, and solids. In continuous
manufacturing process analysis is essential, as continuous manufacturing requires a method of continuous
analysis. The Centre of Continuous Manufacturing and Crystallisation (CMAC) has embraced process analysis
technologies (PATs) to monitor the crystallisation of many pharmaceuticals and materials. These methods have
been integrated with control systems allowing for intelligent control of particle size and solid state production.
55
ORAL ABSTRACTS
The Generation of a Novel Force Field for Biomolecular Simulation
J. L. McDonagh, M. A. Vincent, P. L. A. Popelier
1 Manchester Institute of Biotechnology, The University of Manchester, 131 Princess Street, Manchester,
M1 7DN, UK
2 School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK
[email protected]
We present the latest advances in the generation of the novel force field FFLUX (previously known as QCTFF) 1.
This force field has been conceived and built from a bottom up approach. This approach leads to the following
workflow (Figure 1): Firstly, we generate an ensemble of distorted structures using normal modes distortion; we
follow this with a quantum mechanical calculation of each structure using ab initio computational chemistry.
Secondly, we apply topological energy partitioning in order to distribute and isolate molecular energy into atomic
basins. Through the interactions of these basins we can reconstruct the molecular energy to a very high precision
(within a few kJ mol-1). Thirdly, we apply the machine learning method kriging2 to these energetic terms, this
enables a knowledge based approached to force field design, in which the models are not fixed mathematical
forms as are found in classical force fields, but knowledgeable models that can accurately estimate energy terms
based upon molecular geometry alone.
Figure 1. Model preparation workflow in FFLUX
There are already proof-of-concept results for this approach accounting for electrostatic and exchange
interactions.3 Until recently a final important energy contribution, the dispersion energy, 4 was not available
to the energetic partitioning method. We have recently remedied this. We present proof of concept results
from the workflow laid out above along with the initial results of dispersion energy partitioning via our new
methodology. We will soon be able to directly incorporate the dispersion energy term into the machine
learning process and model generation.
1
2
3
4
P. L. A. Popelier, Phys. Scr., 2016, 91, 033007.
M. J. L. Mills and P. L. A. Popelier, Theor. Chem. Acc., 2012, 131, 1137.
Y. Yuan, M. J. L. Mills and P. L. A. Popelier, J. Comput. Chem., 2014, 35, 343–59.
J. L. McDonagh, M. A. Vincent and P. L. A. Popelier, Phys. Rev. Lett., Pending submission.
56
ORAL ABSTRACTS
How liquids affect solutes: Modelling solvation using physics-based model
M. Misin*1, M. V. Fedorov1, and D. S. Palmer2
1
Department of Physics, SUPA, University of Strathclyde, 107 Rottenrow, Glasgow, G4 0NG, UK
2
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral
Street, Glasgow, G1 1XL, UK
[email protected]
The majority of chemical reactions and processes take place in the liquid phase. Due to this reason, one of
the major goals of computational chemistry is accurate (and fast) modelling of solvation effects. Despite
many efforts, the state of the art techniques still require improvement, as the majority of existing models fail
to incorporate effects of temperature and cosolvents, and are not easily extendable to new types of solvents.
In my talk, I will demonstrate how a statistical mechanics based model, called 3D-RISM (three-dimensional
reference interaction site model), can be used to model solvation of molecules in a number of liquids and
mixtures [1]. Unlike many existing techniques, such as Poisson-Boltzmann or polarizable continuum models,
3D-RISM naturally incorporates effects of solvent structure and composition without a need for long
molecular dynamics simulations. Utilizing a recently developed correction, the model is successfully applied
to systems such as mixtures, solutions of salts and water at a non-standard temperature [2,3]. The present
limitations and the scope of the model are also discussed.
[1] Ratkova, E. L., Palmer, D. S. & Fedorov, M. V. Solvation Thermodynamics of Organic Molecules by the
Molecular Integral Equation Theory: Approaching Chemical Accuracy. Chem. Rev. 115, 6312–6356 (2015).
[2] Misin, M., Fedorov, M. V. & Palmer, D. S. Communication: Accurate Hydration Free Energies at a Wide
Range of Temperatures from 3D-RISM. J. Chem. Phys. 142, 091105 (2015).
[3] Misin, M., Fedorov, M. V. & Palmer, D. S. Hydration Free Energies of Molecular Ions from Theory and
Simulation. J. Phys. Chem. B 120, 975–983 (2016).
Figure 9 Distribution of water density around propyl ammonium predicted by 3D-RISM
Capturing fast organic reactions: new approaches to stopped flow kinetics
57
ORAL ABSTRACTS
M. Reid, *1 P. Cox,1 T. King,2 A. D. Campbell,3 and G. C. Lloyd-Jones1
1
School of Chemistry, University of Edinburgh, Scotland, UK
2
TgK Scientific, Ltd., Bradford-on-Avon, England, UK
3
AstraZeneca, Macclesfield, England, UK
[email protected]
A mechanistic understanding of chemistry fosters more efficient reaction design and improvement. So what
happens when a reaction is too fast to monitor by traditional means? How can we hope to understand a
reaction that reaches completion in the blink of an eye? In this talk, we divulge our novel and evolving
approaches to stopped flow kinetics, focusing on problematic protodeboronation processes.
Instrument Design
Reaction Kinetics
Computational Chemistry
Figure 10 Multidisciplinary study of fast protodeboronation reactions.
58
ORAL ABSTRACTS
Synthesis and assembly of gold particles on an emulsion droplet; nanoparticles, nanosheets and core-shell
particles
S. Sachdeva*, R. Maugia, C. Kirka, Z. Zhoub, S. D. R. Christiea and M. Platta
a
Department of Chemistry, Loughborough University, Loughborough, LE11 3TU, UK
b
Materials Engineering, Loughborough University, Loughborough, LE11 3TU, UK
[email protected]
The synthesis and assembly of materials at the interface between two immiscible liquids is an area of growing
interest. A variety of experimental setups from Pickering emulsions1, electro and electro less deposition2,3 allow
materials to be assembled and synthesised with relative ease. Here we report the rapid, controlled and facile
synthesis of gold (Au) nanomaterials with varying aspect ratios using emulsions droplets, figure 1a.
By placing the Au salt in the aqueous phase (P2) and by varying the concentration of decamethylferrocene within
a sodium dodecyl sulfate stabilised hexane droplet (P1), Au nanoparticles (NP) or nanosheets (NS) were formed
instantly, figure 1c. The addition of Magnetite (Fe3O4) NP into P1, produces a shell of Fe3O4 particles around the
as formed AuNP. As a comparison, AuNP’s that were first synthesized and placed into P2 allowed emulsion
droplets to be formed without the need for a surfactant and in the presence of Fe 3O4 NP’s in P1 formed Au shell
around the Fe3O4 core. This simple method of tuning the particle shape and core@shell synthesis is the first
reported using emulsion droplets, and we present X-ray powder diffraction (XRD), transmission electron
microscopy (TEM) and scanning electron microscopy (SEM) analysis of the products.
Figure 1 a) schematic of the experimental setup, hexane (P1) droplets are made via the fluidic chip, dispersed in an aqueous
solution (P2). b) Schematic of the droplet and possible reactions and additives in solutions. c) i Gold nanosheet produced when
AuCl4- 0.005 M in P2, Decamethylferrocene at 0.001 M in P1. c) ii Spherical gold particles when AuCl 4- at 0.01 M in P2,
Decamethylferrocene at 0.01 M in P1. Scale bar = 1 μm d) i Fe304@Au particle using 5 nm Au particles as NP2 in P2, and
NP1 is Fe3O4 at 3 mg/ml. d) ii Au@Fe304 particle AuCl4- at 0.01 M in P2, Decamethylferrocene at 0.01 M in P and NP1 is
Fe3O4 at 3 mg/ml. Scale Bar = 200 nm
1
2
3
S. Sihler, A. Schrade, Z. Cao and U. Ziener, Langmuir, 2015, 31, 10392–10401.
M. Platt, R. A. W. Dryfe and E. P. L. Roberts, Chem. Commun., 2002, 20, 2324–2325.
R. A. W. Dryfe, A. O. Simm and B. Kralj, J. Am. Chem. Soc., 2003, 125, 13014–13015.
59
ORAL ABSTRACTS
Modelling excited state dynamics in molecular aggregates: From dimers to porphyrin nanotubes
A. Stradomska*1, and J. Knoester2
2
Zernike Institute for Advanced Materials, University of Groningen, Groningen, The Netherlands
[email protected]
1
Self-assembled aggregates of synthetic organic dyes are of fundamental interest as models for understanding
the photophysical processes occurring in natural light harvesting systems. Collective nature of their excited
states leads to unique linear and non-linear optical properties, as well as to effective excitation energy
transport. This makes the molecular aggregates promising building blocks for functional materials with
potential applications in artificial light harvesting, lasing, and energy transport at a nanoscale.
In this contribution I will present the challenges faced by the theoretical modeling of excited state dynamics
in self-assembled system composed of a large number of molecules and present our approach for dealing with
them. This approach combines several methods rooted in exciton theory and allows to account for (i) the
intermolecular resonance interactions between the molecules in the aggregate, (ii) the influence of the static
disorder, and (iii) the interactions with the continuum degrees of freedom in the environment (the thermal
bath).
I will present two applications of our approach. The first system is the self-assembled single-walled TPPS4
porphyrin nanotubes (see Figure 1), quasi-one dimensional aggregates composed of thousands of porphyrin
molecules that mimic the structure of the chlorosomes - natural light harvesting antennae of green sulphur
bacteria. Based on phenomenological parametrization of our theoretical model, we obtain a good agreement
between the theory and experimental data, including both the optical spectra and exciton diffusion
measurement, which allows us to show how a local two-dimensional molecular arrangement influences the
spectra and energy transport properties.
Figure 11 The monomer and the aggregate of TPPS4 porphyrine
The second system are the dimers of a pseudo-isocyanine (PIC) dye, for which we employed first-principles
approach for the parametrization of the theoretical model. We started with the molecular dynamics (MD)
simulations of the self-aggregation process. The structural information provided by those simulations was
combined with quantum-chemical calculations to provide the time-dependent exciton-phonon Hamiltonians
for PIC monomers, dimers and trimers, which were subsequently used to evaluate the absorption spectra of
these systems. Very good fit of the calculated dimer spectrum to the experimental results for the initial stage
of the PIC aggregation validates the face-to-face stacked dimer arrangement found in our MD simulations.
On the other hand, the comparison of the simulated trimer spectrum to the experimental results suggests that
oligomers larger than the dimers are not abundant at the onset of aggregate formation.
60
ORAL ABSTRACTS
Translating Theory to Practice
R. L. Fletcher-Wood*1 and Z. L.Fleming1
1
Environmental Chemistry Group of the Royal Society of Chemistry, Burlington House, London, UK
[email protected]
The Environmental Chemistry Group (ECG) of the Royal Society of Chemistry reports on some of its outreach
activities, including an atmospheric chemistry “Chemistry for All” initiative with low-cost air quality sensors that
are installed in school playgrounds with tutorials where pupils download data from the nearest official monitoring
station. The resulting discussions have made the children think about the impact and implications of traffic on the
air they breathe and contributed to real research.
Issues discussed will include the challenges of translating theory into practical engagement, and the need to
balance resources, ideas, and feet on the ground. This session will include an open call for outreach collaborators
to initiative outreach projects in contaminated land and water in their geographical region.
Fig 1.Live data from the AQMesh web site, used to input the school's pollution data into a case.
Fig 2.School demonstration and outreach activities in atmospheric chemistry and air pollution
61
ORAL ABSTRACTS
ReallySmallScience on Tour
J.S. Leckie*1, and M. Haw1
1
Department of Chemical & Process Engineering, University of Strathclyde, Glasgow, UK
[email protected]
The ReallySmallScience group is a unique interdisciplinary outreach group led by Dr Mark Haw and Dr Joy
Leckie from the Department of Chemical and Process Engineering at the University of Strathclyde. Our aim
is to make scientific research more accessible and fun for all ages, through interactive hands-on activities.
The group were awarded Royal Society of Chemistry Outreach funding for a project called
‘ReallySmallScience on Tour’ in which we toured schools and science festival around Scotland.
The project objective was to reveal how the chemistry of nanosized objects underpins a lot of everyday life,
from technology and health (washing powders, targeted drugs) to nature (enzymes and proteins keeping us
alive, versus viruses making us ill).
We ran a number of nano-themed workshops including: nanojelly, nanodirt, nanoglow which illustrated the
nanochemistry involved in everyday items such as food, clean water and glowing technology.
The group visited 7 primary schools, 1 afterschool club, 1 early year’s centre, as well as 6 public events
(running activities on multiple dates for each event). We engaged with 609 school pupils in total and a further
80 from after school and early year’s clubs. Through public events we engaged with 1247 people including
children and adults. Overall during the ReallySmallScience on Tour event we engaged with 1936 people. We
also had a strong online presence through social media and engaged with many more people online throughout
the lifetime of the project.
To celebrate the end of the project we hosted a prize-giving and celebration event at the University of
Strathclyde, where schools were invited to submit images and videos for our ‘science in everyday life’
competition. Forty shortlisted pupils from four schools were invited to attend the event at Strathclyde along
with teachers and parents. At the event we showcased all of the entries to the competition before children
took part in 4 interactive workshops
Figure 12 Children attended a celebration and prize giving event at the University of Strathclyde.
62
ORAL ABSTRACTS
Simulated peer assessment as a means to solve the ‘mathematics problem’ in science education
F. J. Scott
WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, UK.
[email protected]
The ‘mathematics problem’ is a well-known source of difficulty for students attempting numerical problem
solving questions in the context of science education. This research illuminates the problem by invoking
Hogan’s numeracy framework and in doing so, reveals that the contextualisation of mathematics within the
domain of science is not the main source of difficulty for students but rather more fundamental mathematical
skills.
Having highlighted the problem, simulated peer-assessment is investigated as a method to improve student
performance in numerical problem solving questions in a science education context. Additionally, the benefits
of using simulated, rather than real, students’ answers in peer-assessment is discussed. The results demonstrate
that a simulated peer-assessment activity is suitable as a replacement for standard peer-assessment and that
students’ attitudes favour the simulated approach.
63
LIST OF POSTERS
Presenter
Alexandra Costa
Title
Engaging with children and young adults – making polymer bouncing balls
Session
Poster
No.
EO
1
Calum Williams
Nanomove: A physically interactive thermodynamics workshop
EO
2
Alexander Browne
Structural and orbital orders in Ga-V oxide spinels
IM
3
Ruth Daniels
Highly luminescent dinuclear iridium(III) complexes
IM
4
Femi Oloye
The influence of carburisation temperature on the carbide surface and their catalytic activity
IM
5
Giuditta Perversi
Perturbation of orbital molecules in the Verwey phase of Fe3O4
IM
6
Alison Savage
Early investigation of the stabilization effects of polymer and surfactant combinations in the formulation of solid
drug nanoparticles
IM
7
Adele Gabba
Structure reactivity study in glycosylation and anomerisation reactions
OB
8
Marine Hatit
Chemoselective sequential click ligations directed by enhanced reactivity of an aromatic ynamine
OB
9
Natalia Herrero Alvarez
Proteasome inhibition by new dual warhead containing peptido vinyl sulfonyl fluorides
OB
10
Alaa Kadhim
Copolymer of star poly(e-caprolactone) and polyglycidols for drug delivery systems
OB
11
Verena Klaus
Novel reaction for the formation of highly functionalized furans
OB
12
Kirsten McAulay
Towards the total synthesis of pukalide
OB
13
James McIntyre
A reactivity scale for directing group power in ruthenium-catalysed C-H functionalisation
OB
14
Oluwarotimi Stephen Ojo
Synthesis of Unnatural Amino Acids and Descurainolide A from Lignin Phenolic Monomer
OB
15
Linus Reichenbach
Defining the Structural Determinants for Fidelity in an Expanded Genetic Alphabet
OB
16
Matteo Scipioni
Synthesis and biological activity of novel anti-oxidants based on natural products
OB
17
Fraser Scott
Minor Groove Binders (MGBs): From Anti-Gram-Positives to Anti-Gram-Negatives
OB
18
Devanshi Singh
PAMAM dendrimers for target specific drug delivery systems
OB
19
64
LIST OF POSTERS
Presenter
Title
Session
Poster
No.
Tze Han Sum
Synthesis of novel hybrid flavones for chemotherapeutic applications
OB
20
Tze Jing Sum
Synthesis of naturally occurring flavonoids and novel biflavonoids for medicinal applications
OB
21
Hannah Sykes
Development of novel fluorescent heterocycles for the detection, identification and differentiation of clinically
important microorganisms
OB
22
Stacey Webster
Development of gold(I) and indium(III) catalysed reactions
OB
23
Rachael Cameron
SERS assessment of anti-cancer drug-nanoparticle conjugates
PA
24
Charlotte Carr
Thermal techniques for characterisation and problem solving in the pharmaceutical industry
PA
25
Chrysantus Chikere
Novel graphene-based electrode materials for selective electrochemical determination of antioxidants
PA
26
Laura Frame
Development of a label-free Raman imaging technique for differentiation of infected & non-infected malaria
tissue
PA
27
Yu-Ting Hsu
Small molecule biosensor development and alternative sensing material
PA
28
Cynthia Ibeto
Emission potentials and Fuel properties of Torrefied Lignite and its Blends with Biowaste
PA
29
Fay Nicolson
Development and Applications of Surface Enhanced Spatially Offset Raman Spectroscopy
PA
30
Craig Ward
Towards a rapid and selective solution assay for biopharmaceutical glycosylation analysis using lectin-coated
nanoparticles and SERS
PA
31
65
DELEGATE LIST
Adewale Adetutu
Joanna Aldred
Sam Alexander
Timothy Allen
Sondos Almahmoud
Jawza Alnawmasi
Sonia Bajo
Nicola Bell
Nitika Bhalla
John F Bower
Alistair Boyer
Paul Brack
Danielle Bradshaw
Alexander Browne
Rachael Cameron
Charlotte Carr
Gillian Carse
Chris Chapman
Chrysantus Chikere
Nicholas Chilton
David Cole-Hamilton
Damion Corrigan
Alexandra Costa
Alex Cresswell
Ruth Daniels
Richard Darton
Ross Davidson
Marcel de Matas
Menno de Waal
Amit Delori
Nicholas Dominelli Whiteley
John Marques dos Santos
Robert Edkins
Rowena Fletcher-Wood
David Foley
Clarissa Forbes
Lautech
Durham University
University of Glasgow
University of Cambridge
The University of Glasgow
Glasgow university
University of Strathclyde
University of Edinburgh
Walgreens Boots Alliance
University of Bristol
Loughborough University
Fluorochem
Pfizer Ltd
Institute of Occupational Medicine
Royal Society of Chemistry
Robert Gordon University Aberdeen
The University of Manchester
Dalton President
Northumbria University
Keele University
Durham University
Seda Pharmaceutical Development Services
European Young Chemists' Network
University of Oxford
RSC Environmental Chemistry Group
University of Dundee
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
Laura Frame
Elizabeth Frye
Adele Gabba
Mustapha Garba
Nikolaos Georgakopoulos
Alexandre Girard
Matthew Grayson
John Griffin
Jing Han
Adam Hardy
Dritan Hasa
Marine Hatit
Maria Jose Heras Ojea
Natalia Herrero Alvarez
Lewis Hou
Yu-Ting Hsu
Thomas Humberstone
Cynthia Ibeto
Jinju James
Phil Jemmett
Karen Johnston
Alaa Kadhim
Neil Keddie
Maisie Keogh
Verena Klaus
Maria Kopsida
Tilemachos Kosmidis
Arno Kraft
Ana Maria Leal Sousa
Joy Leckie
Helen Le-Mar
Pól MacFhionnghaile
Kirsten McAulay
Hollie McCarron
Liam McCarron
James McDonagh
Syngenta
NUIG Galway
Umiversity of Glasgow
Keregen Therapeutics
Lancaster University
Heriot Watt University
Strathclyde University
Umiversity of Glasgow
Glasgow University
Science Ceilidh/University of Edinburgh
Durham University
Loughborough university
Lancaster Environment Centre
University College Dublin
University of Birmingham
Durham University
University of Sheffield
University of St Andrews
Robert Gordon University
Heriot-Watt University
Science Ceilidh
Cancer Research Technology
University of Manchester
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
66
DELEGATE LIST
Thomas McGlone
Iain McLellan
Gregor Meier
Samantha Moreton
Fay Nicolson
Numrah Nisar
Oluwarotimi Stephen Ojo
Femi Oloye
Olajide Onike
David Palmer
Robert Paton
Francesca Perciballi
Giuditta Perversi
Michael Popadynec
Linus Reichenbach
Marc Reid
Sebastien Rochat
Kirsty Ross
Jemma Rowlandson
Jamie Rowney
Suchanuch Sachdev
James Sanderson
Alison Savage
Matteo Scipioni
Fraser Scott
Bunian Shareef
Jamie Sheerin
Devanshi Singh
Sian Sloan-Dennison
Scott Sneddon
Andrew Stark
University of the West of Scotland
EPP Ltd
Lahore College for WomenUniversity
University of Aberdeen
Lonza biologics
University of Oxford
University of Bath
University of Bath
Boots
Loughborough University
University of Strathclyde / GSK
University of Liverpool
Robert Gordon University
QinetiQ
Astrazeneca
Anna Stradomska-Szymczak
Tina Yu-Ting Su
Tze Jing Sum
Tze Han Sum
Luke Sutherland
Hannah Sykes
Northumbria University
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
Patrick Thomson
Dominic Tildesley
Sarah Walker
James Walker
Stephen Wallace
Stefan Warrington
Monika Warzecha
Stacey Webster
Calum Williams
Zoe Wilson
Sarahjane Wood
Laura Yates
Wen Zhu
Katie Springham
EPFL - CECAM
University of Birmingham
Heriot-Watt University
Quadralene Ltd
Cardiff University School of Chemistry
RSC
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
67
The ECS2016 committee would like to thank all our sponsors for their generous support.

File - Royal Society of Chemistry Early Careers Symposium

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