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The 8th International Symposium on
Nano & Supramolecular Chemistry
In Commemoration of
Professor Leonard F. Lindoy’s 80th Birthday
13-16 July 2016
Mercure, Brisbane, Australia
WELCOME
It is a great pleasure to extend a warm welcome
to you all as ISNSC-8 participants and speakers.
Building on the success of previous ISNSC
conferences, ISNSC-8 aims to foster discussion
on developments in nano- and supramolecular
chemistry and the applications of functional
materials in diverse areas.
This conference will also be a dedication
symposium to celebrate the 80th birthday of
Prof. Leonard F. Lindoy, to commemorate his achievements in chemistry and
contribution to a broad research community.
Delegates from diverse background will have an opportunity to discuss new
scientific findings, share new knowledge, and advance interesting ideas in the
related research field. This symposium will be a great forum to renew
connections, develop collaborations and strengthen academic networks.
The Symposium will begin in the afternoon of 13th July followed by three days
scientific program. It will feature outstanding plenary lectures, invited talks,
ECR/student talks, and poster presentations. Selected full papers after review
can be published in a special issue of Aus. J. Chem.
We wish you a stimulating and productive conference as well as most enjoyable
stay in Brisbane and Australia.
With best regards,
Prof. Chengzhong Yu, Prof. Yang Kim & Prof. Gang Wei
ISNSC-8, Co-Chairs
Organising Committee
Dr. Jorge Beltramini; Prof. Jin Zou; Prof. Debra Bernhardt; Prof. Huijun Zhao;
Dr. Jack Clegg; Prof. Xiangdong Yao; Prof. Gordon Xu; Prof. Lianzhou Wang;
Dr. Feng Li; Dr. Meihua Yu; Dr. Xiaodan Huang; Dr. Hongwei Zhang.
PROGRAM
DAY 1 – 13 July 2016
Conference Registration & Welcome Reception
Cocktail
16:00-19:00
DAY 2 – 14 July 2016
08:30-09:05
09:05-09:40
09:40-10:15
10:15-10:40
10:40-11:00
11:00-11:20
11:20-11:40
11:40-12:00
12:00-12:20
12:20-12:40
12:40-13:30
13:30-13:50
13:50-14:10
14:10-14:30
14:30-14:50
14:50-15:10
15:10-15:30
15:30-15:50
15:50-16:10
16:10-16:30
16:30-16:50
16:50-17:10
17:10-17:30
17:30-17:50
18:00-19:00
19:00-22:00
Room Burke, Wills & Leichhardt
PL-01 Leonard F. Lindoy
PL-02 Peter Comba
PL-03 Hiroshi Kitagawa
Morning Refreshment
Supramolecular Chemistry
Nano-Materials
Room Burke, Chair
Room Leichhardt, Chair
IT-01 Takehiko Yamato
IT-07 Martino Di Serio
IT-02 Keisuke Ohto
IT-08 Jun Shen
IT-03 Takayoshi Nakamura
IT-09 Colin L. Raston
IT-04 Ok-Sang Jung
IT-10 Jiatao Zhang
IT-05 Kerstin Gloe
IT-11 Bin Zhang
IT-06 Valery V. Gorbatchuk
IT-12 Adrian Trinchi
Conference Working Lunch
Energy
Functional Materials
Room Burke, Chair
IT-13 Liqiang Mai
IT-19 Ying Chen
IT-14 Marlies Hankel
IT-20 David James Young
IT-15 Aijun Du
IT-21 Meihua Yu
IT-16 Sesha V. Musunuri
IT-22 Nobuto Yoshinari
IT-17 Shu-Fen Hu
IT-23 Ehsan Eftekhari
IT-18 Liang Zhou
IT-24 Hongning Wang
Afternoon Refreshment
Design Synthesis
Polymer Science
Room Burke, Chair
IT-25 Jin Zou
IT-31 Debra J. Searles
IT-26 Shinya Hayami
IT-32 Afang Zhang
IT-27 Hexiang Deng
IT-33 Venkata Chevali
IT-28 Baojian Shen
IT-34 Rahul Shukla
IT-29 Jack Clegg
IT-35 Wen Li
IT-30 Yanjun Gong
IT-36 Hongwei Zhang
Poster Presentation
Conference Banquet
PROGRAM
DAY 3 – 15 July 2016
08:30-09:05
09:05-09:40
09:40-10:15
10:15-10:40
10:40-11:00
11:00-11:20
11:20-11:40
11:40-12:00
12:00-12:20
12:20-12:40
12:40-13:30
13:30-13:50
13:50-14:10
14:10-14:30
14:30-14:50
14:50-15:10
15:10-15:30
15:30-15:50
15:50-16:10
16:10-16:30
16:30-16:50
16:50-17:10
17:10-17:30
17:30-17:50
18:30-22:00
Room Burke, Wills & Leichhardt
PL-04 Jerry L. Atwood
PL-05 Annie K. Powell
PL-06 Xuchuan Jiang
Morning Refreshment
Catalysis
Room Burke, Chair
IT-37 Karsten Gloe
IT-43 Xiangdong Yao
IT-38 Mauro Mocerino
IT-44 Wega Trisunaryanti
IT-39 Feng Li
IT-45 Pei Yuan
IT-40 Takumi Konno
IT-46 Karna Wijaya
IT-41 Yasuhiro Nakazawa
IT-47 Muxina Konarova
IT-42 Shim Sung Lee
IT-48 Ajay Kumar
Conference Working Lunch
Functional Materials
ECR & Students Session-1
Room Burke, Chair
Jun Zhang; Swathi Mukundan;
IT-49 Ru-Shi Liu
Ahmad Suseno; Yichao Zou;
IT-50 Hong-Seok Kim
Santi Nur Handayani; Min Hong;
IT-51 Kun Qian
Daniel J. Fanna; Chun Xu;
IT-52 Niloofar Mahloojia
Trisha Ghosh; Xingxing Gu;
IT-53 Zuhua Zhang
IT-54 Xiaodan Huang
Xuming Sun; Yuan Gao
Afternoon Refreshment
ECR & Students Session-2
Room Burke, Chair
Serly J. Sekewael; Chang Lei;
IT-55 Makoto Shimizu
Luxin Wang; Hao Song;
IT-56 Jan J. Weigand
Weikang Shu; Manasi J.;
IT-57 Kil Sik Min
Sai Sun; Yilun Wu;
IT-58 Yoichi Habata
Mohammad Kalantari; Bei Li;
IT-59 Ryo Ohtani
IT-60 Yingjie Zhang
Yuhan Chen; Zetao Chen.
River Cruise
DAY 4 – 16 July 2016
09:00-12:00
Round Table Discussion
Plenary Lecture Abstracts
13-16 July 2016
ISNSC-8, 13-16 July 2016, Brisbane, Australia
Metallo-Supramolecular Strategies for Assembling Nanoscale Molecular
Structures
Leonard F. Lindoy
School of Chemistry, The University of Sydney, NSW 2006, Australia
*[email protected]
Abstract
The author and his coworkers have employed a range of organic ligand derivatives
incorporating polypyridyl, β-diketonato and β,δ-triketonato ligand domains in studies leading
to the construction of a variety of metallo-supramolecular structures incorporating selected
first row transition metal ions as structural elements. In these studies the electronic and steric
nature of the metal ion and the organic component(s) employed are seen to play a crucial role
in directing the formation of the desired structural assembly.1-5
In this presentation, using representative examples
from our studies in the area the strategies underlying
the successful syntheses of a varied range of molecular
architectures exhibiting various topologies will be
presented. The design principles involved in the
construction of a such species will be discussed in
terms of the choice of metal ion and the nature of the
organic component(s) employed. Examples of
supramolecular cage assembly followed by postsynthetic modification of the assembled product to
yield fully covalent cage species will also presented.6
References
[1] J. K. Clegg, S. S. Iremonger,M. J. Hayter, P. D. Southon, R. B. Macquart, M. B.; Duriska, P. Jensen, P.
Turner, K. A. Jolliffe, C. J. Kepert, G. V. Meehan, L. F. Lindoy, Angew. Chem. Int. Ed., 2010, 49, 1075-1078.
[2] C. R. K. Glasson, J. C. McMurtrie, J. C. Meehan, J. K. Clegg, L. F. Lindoy, C. A. Motti, B. Moubaraki, K. S.
Murray, J. D. Cashion, Chem. Sci., 2011, 2, 540-543.
[3] F. Li, J. K. Clegg, P. Jensen, K. Fisher, L. F. Lindoy, G. V. Meehan, B. Moubaraki, K. S. Murray, Angew.
Chem. Intern. Ed., 2009, 48, 7059-7063.
[4] F. Li, J. K. Clegg, L. F. Lindoy, R. B. Macquart, G. V. Meehan, Nature Comm., 2011, 2:205.
[5]
H. Ju, J. K. Clegg, K.-M. Park, L. F. Lindoy, S. S. Lee, J. Am. Chem. Soc., 2015, 137, 9535-9538.
[6]
C. R. K. Glasson, G. V. Meehan, M. Davies, C. A. Motti, J. K. Clegg, L. F. Lindoy, Inorg. Chem.,
2015, 54, 6986-6992.
PL-01
Magnetic Interactions in Oligonuclear 3d-4f Complexes – Synthesis,
Magnetism Spectroscopy and Theory.
Peter Comba*
Universität Heidelberg, Anorganisch-Chemisches Institut and Interdisciplinary Center for
Scientific Computing (IWR), Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
* [email protected]
Abstract
Single-molecule magnets (SMMs) have sizable relaxation barriers between the two
degenerate states of opposite electron spin and therefore are of fundamental interest and have
also attracted attention for various possible applications. Reasons for problems to design and
prepare SMMs with accurately predicted and large relaxation barriers are that the efficient and
accurate theoretical description of the magnetic anisotropy and its dependence from structure
(magneto-structural correlations) have only recently started to become available, and the
prediction and enforcement of coordination geometries of lanthanides are much less
developed than those of transition metal ions.
On the basis of three series of complexes (see Figure), the solid state structures, magnetic and
spectroscopic properties (MCD, HF-EPR and NMR) will be discussed and used to validate a
well-established computational scheme to compute the electronic ground state, magnetic
exchange and relaxation pathways, based on broken symmetry DFT as well as on an ab initio
CASSCF wavefunction, spin-orbit coupling via the restricted active space state interaction
method (RASSI) and an analysis of the multiplet splitting derived from the Lines model and a
ligand field analysis involving extended Stevens operators.
PL-02
Dimensional Crossover in Coordination Chemstry
Hiroshi Kitagawa*
Department of Chemistry, Graduate School of Science, Kyoto University, Japan
*[email protected]
Abstract
Here, we demonstrate a bottom-up approach for the fabrication of well-defined dimensionalcrossover nano-architectures with high tunability using metal ions and organic molecules as
building blocks [1-6]. We succeeded in rationally constructing an assembly of square prismshaped metal-organic nanotubes with aside of 2 nm. A uniform 1D channel is fabricated inside
the tube, and H2O and alcohol can be selectively adsorbed. Its optical gap is about 0.76 eV of
semiconductive region, and X-ray and theoretical studies
revealed its unique electronic structure of CDW quartets. In
addition, its electronic states can be successively controlled
by exchanges of structural components and guest
molecules. The results presented here demonstrate a
rational route to the creation of nanotubes with high
tunabilities of structures and electronic states, and might
also offer valuable insights into multifunctional
nanomaterials.
References:
[1] S. Sakaida, K. Otsubo, O. Sakata, C. Song, A. Fujiwara, M. Takata,
H. Kitagawa, Nature Chemistry, 8, 377-383 (2016).
[2] G. Li, H. Kobayashi, J. M. Taylor, R. Ikeda, Y. Kubota, K. Kato, M. Takata, T. Yamamoto, S. Toh, S.
Matsumura, H. Kitagawa, Nature Materials, 13, 802 (2014).
[3] K. Otsubo, Y. Wakabayashi, J. Ohara, S. Yamamoto, H. Matsuzaki, H. Okamoto, K. Nitta, T. Uruga, H.
Kitagawa, Nature Materials, 10, 291 (2011).
[4] R. Makiura, S. Motoyama, Y. Umemura, H. Yamanaka, O. Sakata, H. Kitagawa, Nature Materials, 9, 565
(2010).
[5] R. Makiura, T. Yonemura, T. Yamada, M. Yamauchi, R. Ikeda, H. Kitagawa, K. Kato, M. Takata, Nature
Materials, 8, 467 (2009).
[6] T. Yamada, K. Otsubo, R. Makiura, H. Kitagawa, Chem. Soc. Rev., 42,6655-69 (2013).
PL-03
Metal-Seamed Organic Nanocapsules
Asanka S. Rathnayake, Joshua White, Rahul S. Patil, Harshita Kumari,
Chen Zhang, Philip H. Atwood, and Jerry L. Atwood*
Department of Chemistry, University of Missouri-Columbia,
Columbia, MO 65211, USA
*[email protected]
Abstract
We have previously reported the rapid self-assembly of six pyrogallol[4]arenes and 24 ions
(M = Zn2+, Cu2+, Ni2+, or Co2+ ions) to form metal seamed hexameric nanocapsules. Other
metal
seamed
nanocapsules
include
Ga12(pyrogallol[4]arene)6
and
dimeric
M8(pyrogallol[4]arene)2. The relationship of the dimers and hexamers has been revealed from
small angle neutron scattering studies. The Ga12(pyrogallol[4]arene)6 hexameric nanocapsules
are seamed together by a combination of Ga-O and hydrogen bonding. The
Ga12(pyrogallol[4]arene)6 nanocapsules may be further seamed by M2+ ions to form
hexameric MxGa24-x(pyrogallol[4]arene)6 nanocapsules. For potential applications, other
metal-seamed hexameric nanocapsules are needed, but thus far synthetic targets such as
M24(pyrogallol[4]arene)6 nanocapsules for M = Fe2+ or Mn2+ have not been reported. Now,
we have substantial progress to reveal on this front.
PL-04
Plenary Lecture - 05
Annie K. Powell*
Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
* [email protected]
Abstract
Ongoing core research activities in Powell group
1. Molecular Magnets: We are synthesising materials which are described as Single Molecule
Magnets or SMMs. These are molecules which show hysteresis in their magnetisation and can
be used to store or process information in future applications. We have discovered a molecule
with 19 manganese centres which has the largest ground spin state ever seen at S = 83/2. We
have also developed synthetic routes to access mixed 3d/4f systems. We find that 4f ions such
as Dy(III) are very useful for introducing anisotropy into these molecules which, along with
non-zero spin, is required for the observation of SMM behaviour . In addition, we are looking
at pure 4f systems and have several exotic systems including a triangular arrangement of
Dy(III) ions which represents the molecular archetype of the noncollinear Ising model and
offers real prospects for developing qubit design strategies. Finally, we have also begun to
explore using supramolecular effects to enhance magnetic properties.
2. MOFs and SMOFs: In addition to long-standing research interests in making the
coordination networks which have become known as MOFs we have developed design
principles to using metal coordination clusters as building units for “Super Metal Organic
Frameworks” or SMOFs. In the past we have published structures build up from Al15, Fe13
and Cu44 units and recently we have synthesised SMOFs made up from building blocks
containing large numbers of rare earth ions, such as a Dy36 and Y79 (not yet published). The
attractive thing about this approach is that even if a network becomes interpenetrating, the
building blocks are so large that there is still plenty of accessible volume for small molecules
such as water or hydrogen.
3. Biomimetics: We are currently looking at two areas, although in the past we have looked at
iron clusters as models for loaded ferritin and this is still an area of general interest. Firstly,
we have found that using Schiff-base ligands gives access to a system with 4 Mn and 1 Ca ion
which is the best model so far for the Oxygen Evolving Centre of Photosystem II. Secondly,
we have been looking at calcium carbonate biomineralisation mimics. We find that even using
relatively simple polycaboxylates we can produce complicated structures including
“microtrumpets” which are formed from the organisation of high-aspect ratio nanocrystals of
calcite.
4. Processing of Coordination Compounds: Coordination compound-based systems can be
processed, for example through thermolysis, to give materials with novel structural
characteristics. For example, a simple dinuclear iron building block can be organised into
supramolecularly connected arrays with various architectures depending on the substitution at
the ligand peripheries. Thermolysis of one such array where the space is divided into an
inorganic honeycomb structure filled with carbon atoms from phenyl rings leads to
hexagonally organised nano-bundles of sodium carbonate and iron oxide. Likewise, heating
an array of Mn21 clusters organised into a cubic structure leads to a highly porous manganese
oxide material which has potential as a battery anode material as well as showing very good
catalytic activity [submitted].
PL-05
Engineering VO2 Nanoparticles for Energy and Environmental
Applications
Xuchuan Jiang
Laboratory for Simulation and Modelling of Particulate Systems (SIMPAS)
Department of Chemical Engineering, Monash University
Melbourne, VIC 3800, Australia
*[email protected] ;[email protected]
Abstract
Energy and environment have emerged as the most critical challenges human faced to the
sustainable global developments in the 21st century. Nanomaterials have attracted much more
attention because of their unique functional properties and broad applications in energy and
environment. This presentation is going to talk about how to engineer nanoparticles for energy
and environmental applications, specifically focusing on vanadium dioxide nanoparticles for
smart window coatings. In this talk, the development of synthesis strategies of VO2
nanoparticles, film deposition, and functional evaluation will be discussed.
PL-06
Invited Talk Abstracts
13-16 July 2016
Pyrene-Cored New [n]Helicenes: Synthesis, Crystal Structures and
Photophysical Properties
Xing Feng and Takehiko Yamato
Department of Advanced Technology Fusion, Graduate School of Science and Engineering,
Saga University
* [email protected]
Abstract
For many years, helicenes were considered academic curiosity because of their twisted shape
as a result of repulsive steric overlap of the terminal aromatic nuclei. The scientific interest
revised due to the unique properties of helicenes with powerful inherently chiral chromophore
and by the possibility of electronic interaction. Consequently, there is sudden surge of interest
in helicene with unique properties and in the development of novel synthetic protocols to
access them and therefore various methods have been developed and reported for the
synthesis of these class of compounds.[1,2]
Photo-induced cyclization of 2,7-di-tert-butyl-4,9-bis(arylethenyl)pyrenes 1[3–5] in the
presence of iodine and propylene oxide led to the novel expanded -conjugated systems,
tetrabenzo[a,fg,j,op]tetracene
derivatives 2, in which the first
number
of
the
double
[4]helicene
structures
are
contained. The single X-ray
crystal study revealed that
twisting of naphthalene motifs
from the existing pyrene core of
2a is 23.04°, whereas same for
2b is 45.05°. From these data it
was
concluded
that
the
introduction of methyl group at
fjord
region
is
highly
responsible for distorted structure of compound 2b.
The photophysical properties of the double [4]helicenes 2 were also investigated in
solution, and were compared with those of phenylethenylpyrenes (1). Both the helicenes and
the phenylethenylpyrenes exhibited highly emissive emission from violet-blue to pure-blue
with high quantum yields, which makes them of potential application in optoelectronic
devices. In this presentation, we will discuss the electronic properties of [4]helicenes 2a–2c
and [5]helicenes 3, and evaluate the effects of the expanded -conjugation on the structural
properties.
Reference
[1] J.-Y. Hu, A. Paudel, N. Seto, X. Feng, M. Era, T. Matsumoto, J. Tanaka, M. R. J. Elsegood, C. Redshaw
and T. Yamato, Org. Biomol. Chem., 2013, 11, 2186–2197.
[2] J. Hu, X. Feng, A. Paudel, H. Tomiyasu, U. Rayhan, P. Thuéry, M. R. J. Elsegood, C. Redshaw and T.
Yamato, Eur. J. Org. Chem. 2013, 5829–5837.
[3] X. Feng, J-Y. Hu, H. Tomiyasu, Z. Tao, C. Redshaw, M. R. J. Elsegood, L. Horsburgh, S. J. Teat, X.-F.
Wei and T. Yamato, RSC Adv., 2015, 5, 8835–8848.
[4] X. Feng, H. Tomiyasu, J.-Y. Hu, X.-F.Wei, C. Redshaw, M. R. J. Elsegood, L. Horsburgh, S. J. Teat and T.
Yamato J. Org. Chem., 2015, 80, 10973–10978.
[5] X. Feng, J.-Y. Hu, C. Redshaw and T. Yamato, Chem.–Eur. J. in press.
IT-01
Gas Adsorption Property of Calixarenes
Keisuke Ohto,1* Birendra Babu Adhikari,1 Hirotoshi Sadamatsu,1 Hajime Endou2
1 Saga University, Dept. Chem. & Appl. Chem., 1-Honjo, Saga 840-8502, Japan
2 Crown Research Inc., Hamasaki, Karatsu 849-5131, Japan
*[email protected]
Abstract
Calixarenes are macrocyclic oligomers providing three-dimensional site for certain guests.
The researches on metal discrimination have also been carried out by many research groups.[1]
In general, metal extraction is induced by strong electrostatic interaction due to ion-exchange
or coordination mechanism, and calixarenes are used as a platform. On the contrary, inclusion
of neutral organic molec
and London dispersion force, and they play a role as actual host molecules. The researches on
gas storage have been carried out, in particular, hydrogen storage have been focused and
carried out due to viewpoint of energy storage using various materials. Hydrogen storage
alloys and metal-organic frameworks[2] are typical examples. Some articles on gas storage
experimentally and simulationally using calixarenes were reported by Atwood et al.[3] and
Ripmeester et al.[4]
In this work, various calixarenes were prepared and sublimated for purification and
appropriate crystallization under the reduced pressure and at high temperature. Storage
behavior of carbon dioxide and hydrogen molecules onto the compounds was investigated to
compare the effect of ring size and substituents of calixarenes. Different from carbon dioxide,
hydrogen molecule is too small to be discriminated by calixarene derivatives around room
temperature. Complex stoichiometries of carbon dioxide to calixarenes were integer, while
those of hydrogen to calixarenes were less than 1. Among many compounds, calixarene resin
exhibited better hydrogen storage.
References
[1]
[2]
[3]
[4]
K. Ohto, Ion Exch. Solvent Extr. 2014, 21, 81-127;
J. Sculley, D. Yuan, H.-C. Zhou, Energy Environ. Sci. 2011, 4, 2721-2735;
S. J. Dalgarno, J. Tian, J. E. Warren, T. E. Clark, M. Makha, C. L. Rastonc, J. L. Atwood, Chem. Commun.
2007, 4848-4850;
S. Alavi, T. K. Woo, A. Sirjoosingh, S. Lang, I. Moudrakovski, J. A. Ripmeester, Chem. Eur. J. 2010, 16,
11689-11696;
IT-02
Functional Magnetic Materials based on Mn-Cr Oxalate Complexes with
Supramolecular Rotator Structure
T. Nakamura,* M. Yoshitake, K. Kubo and S. Noro
Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan
* [email protected]
Abstract
We already reported flip-flop motion of a supramolecular rotator (mfluoroanilinium+)(dibenzo[18]crown-6) in the crystal, which showed an order-disorder-type
ferroelectric transition at 348 K caused by dipole inversion [1]. In this study, we introduced
supramolecular rotator structures in the ferromagnetic [MnCr(oxalate)3]- complexes [2-4] in
order to realize novel functionality such as multiferroic properties and chiral magnetism.
Figure 1 shows the crystal structure of (m-fluoroanilinium+)(tst-DCH [18]crown6)[MnCr(oxalate)3]- (1) (tst-DCH = trans-syn-trans-dicyclohexano). Crystal system and space
group were orthorombic and P212121, respectively. In the crystal, two supramolecular cations
A and B, and two [MnIICrIII(oxalate)3]- units were asymmetric. The [MnIICrIII(oxalate)3]formed infinite two-dimensional honeycomb layers parallel to the ac-plane. Supramolecular
cations of (m-fluoroanilinium+)(tst-DCH[18]crown-6) were located between the anionic
layers. The m-fluoroanilinium cation formed a supramolecular structure with the tstDCH[18]crown-6 through hydrogen bonding. Two types of tst-DCH[18]crown-6 in the
supramolecular cations were observed forming anti-V-shaped and V-shaped conformations.
Disorder of F atom with large anisotropic thermal factors was observed at 298 K in
supramolecular cation B, suggesting molecular rotation in the solid state.
Temperature dependent magnetic susceptibilities of 1 followed the Curie-Weiss low with
the Weiss temperatures and the Curie constants of + 7.0 K and 85.6 emu K mol-1, respectively.
The in-phase and out-of-phase
AC magnetic susceptibilities
indicated
the
ferromagnetic
transition at 5.2 K. The magnetic
field
dependence
of
magnetization
in
zero-field
cooling (ZFC) processes showed
anomalies
around
the
ferromagnetic
transition
temperature in lower magnetic
fields, suggesting chiral magnetic
nature of the crystal 1.
Figure 1. Crystal structure of
1.
Reference
[1] T. Akutagawa, H. Koshinaka, D. Sato, S. Takeda, S. Noro, H. Takahashi, R. Kumai, Y. Tokura and T.
Nakamura; Nature Materials 8, 342 (2009)
[2] T. Endo, K. Kubo, M. Yoshitake, S. Noro, T. Akutagawa and T. Nakamura; Chem. Lett., 42, 137 (2013)
[3] T. Endo, K. Kubo, M. Yoshitake, S. Noro, N. Hoshino, T. Akutagawa and T. Nakamura, Crystal Growth &
Design, 15, 1186-1193 (2015)
[4] M. Yoshitake, K. Kubo, T Endo, S. Noro, T. Akutagawa and T. Nakamura, Bull. Chem. Soc. Jpn, 89, 354
(2016).
IT-03
Tailor-made Synthesis of Multilayered Trimetallocyclophanes via
Transannula Interactions
Ok-Sang Jung*
Department of Chemistry, Pusan National University, Pusan 609-735, Korea
*[email protected]
Abstract
Synthesis and operation of a nano-demension 24 × 24 × 15 Å3 “left and right ball-joint-type
host-guest system” via one π∙∙∙π interaction and three NH∙∙∙O=C hydrogen-bonds along with
the combined helicity are described. The system consists of unprecedented conglomerate
aggregates of two distinct helical metallacyclophanes, chiral isomer (P)-[Pd3X6(L1)2]@(M)[Pd3X6(L1)(L2)] and its enantiomer (M)-[Pd3X6(L1)2]@(P)- [Pd3X6(L1)(L2)] are described.
Successive reactions afford desirable four-layered metallacyclophanes via tailor-made
procedure. Synthesis and operation of a nano-demension size multilayered metallacyclophane
system via one π∙∙∙π interaction along with the combined helicity are described. A synthetic
strategy of generation of new molecular species utilizing a provision of nature has been
reported: nano-dimensional (23(2) × 21(1) × 16(1) Å3) hetero four-layered trimetallacyclophanes via the proof-of-concept experiments that utilize a suitable combination of π∙∙∙π
interactions between the central aromatic rings, tailor-made short/long spacer tridentate
donors, and the combined helicity are constructed. The unprecedented four-layered
metallacyclophane system’s behavior offers a landmark in the development of new molecular
system.
≡ [PdCl2]
≡
≡
≡
LSA
AgNO3
LLE
LSA
AgCl
2 LLE
2 LLA
LLA
LSA
41
2 LSA
+ 2 LLE
3 LLA
LLA
LLE
40
LLA
42
2 LSA
+ 2 LLA
43
1 LSA
+ 3 LLA
≡ [Pd2+](NO3)2
Scheme 1. Construction of hetero four-layered tripalladium(II)cyclophanes through
consecutive, substitution, and direct reactions.
References
[1]
Lee, H.; Noh, T. H.; Jung, O.-S.*Angew. Chem. Int. Ed. 2013, 52, 11790-11795.
[2]
Lee, H.; Noh, T. H.; Jung, O.-S.* Angew. Chem. Int. Ed. 2016, 55, 1005-1009.
IT-04
Anion Binding by Pyridinium-ß-diketone Ligands
Kerstin Gloe*, Melanie Mohn, Jan J. Weigand, Karsten Gloe
Department of Chemistry and Food Chemistry, TU Dresden,
01062 Dresden, Germany
*[email protected]
Abstract
Anion receptor design is a challenging research topic in order to find selective anion binders
for their sensing, transport and separation [1, 2]. Anions are ubiquitous in nature and play a
fundamental role in many living phenomena. Furthermore they possess also a strong impact
on the environment and in industrial processes.
During the last 20 years diverse anion receptor types were studied. Our research interest was
focused especially on tripodal amine systems [3]. As part of our ongoing studies we report
herein results of the anion binding by pyridinium-ß-diketone receptors. This ligand type we
have already used for metal ion binding and extraction [4].
Reference
[1]
N. Busschaert, C. Caltagirone, W. Van Rossom, P. A. Gale, Chem. Rev. 2015, 115, 8038-8155;
[2]
M. J. Langton, C. J. Serpell, P. D. Beer, Angew. Chem. Int. Ed. 2016, 55, 1974-1987;
[3]
K. Wichmann, B. Antonioli, T. Söhnel, M. Wenzel, K. Gloe, K. Gloe, J. R. Price, L. F. Lindoy, A. J.
Blake,
M. Schröder, Coord. Chem Rev. 2006, 250, 2987-3003;
[4]
M. Dudek, J. K. Clegg, C. R. K. Glasson, N. Kelly, K. Gloe, K. Gloe, A. Kelling, H.-J. Buschmann, K.
A.
Jolliffe, L. F. Lindoy, G. V. Meehan, Cryst. Growth Des. 2011, 11, 1697–1704.
IT-05
Smart Supramolecular Hosts
Valery V. Gorbatchuk,* Marat A. Ziganshin, Karina V. Gataullina, Askar K. Gatiatulin
Kazan Federal University, Kremlevskaya 18, 420008 Kazan, Russia
* [email protected]
Abstract
Smart properties of solid calixarenes and other hosts were observed boosting their selectivity
and clathrate stability. Absolute selectivity of host response to guest inclusion and release was
observed, which goes far beyond the capability of ordinary key-to-lock mechanism. While
current concept of molecular recognition is based on the preferential binding of
complementary species, the present work uses specific cooperative properties of host crystals
such as their memory of previously bound guest, pseudopolymorphism of host-guest
clathrates with more than one step of guest inclusion, favorable hydration effect on binding of
hydrophobic guests by hydrophilic hosts, and effect of clathrate preparation history on guest
inclusion capacity and clathrate stability. Thus, small guest molecules having no more than
one functional group capable of H-bonding or donor-acceptor interactions can be
discriminated even from their close homologues.
A true recognition was found in a two-step formation of benzene clathrate with tertbutylthiacalix[4]arene derivative both on vapor sorption isotherm and in kinetic response of
mass-sensitive sensor. This experiment is extremely selective being capable to detect benzene
qualitatively and quantitatively in mixtures with any other compounds. Inclusion
cooperativity of glassy calixarenes makes possible also a visual detection of organic vapors in
mixtures giving a response to a very small step in guest concentration [1].
An observed ability of several calixarenes to remember evolved guests does not have any
precedents by selectivity. This memory can be read in simultaneous TG/DSC experiment as
an exothermic effect of host collapse from loose to dense phase without mass change. The
memory parameters (enthalpy and temperature of polymorphic transition) strongly depend on
the guest structure. This smart property persists also for guest mixtures [2]. In some cases,
such memory effect can be found only after a solid-phase guest exchange in calixarene
clathrates.
The procedure of clathrate preparation by guest exchange is rather selective itself and gives
a surge in guest inclusion capacity and clathrate stability both for calixarenes and betacyclodextrin [3]. This may produce clathrates that cannot be formed by host-guest interaction
in binary systems. The highest clathrate stability was found for calixarene capable of special
anti-sieve effect, so that larger guests can be bound, while smaller ones are excluded [4].
The work was supported by RFBR (grant no. 14-03-01007-a) and by Russian Government
Program of Competitive Growth of KFU.
References
[1] K. V. Gataullina, M. A. Ziganshin, I. I. Stoikov, A. T. Gubaidullin, V. V. Gorbatchuk, Phys. Chem. Chem.
Phys. 2015, 17, 15887-15895;
[2] G. D. Safina, M. A. Ziganshin, A. T. Gubaidullin, V. V. Gorbatchuk, Org. Biomol. Chem. 2013, 11, 13181325;
[3] V. V. Gorbatchuk, A. K. Gatiatulin, M. A. Ziganshin et al, J. Phys. Chem. B 2013, 117, 14544−14556;
[4] S. F. Galyaltdinov, M. A. Ziganshin, A. T. Gubaidullin, S. G. Vyshnevsky, O. I. Kalchenko, V. V.
Gorbatchuk, CrystEngComm, 2014, 3781-3787.
IT-06
Ru/RuO2@Nb2O5-SiO2 Nanomaterials for Hydrogenation of Levulinic Acid
in the Aqueous-phase
Luciana Minieri(a) , Serena Esposito(b) , Vincenzo Russo(a) , Barbara Bonelli(c) ,
Martino Di Serio(a)* , Antonio Aronne(a), Brigida Silvestri(a)
(a)
Dip. di Ing. Chimica, dei Materiali e della Produzione Industriale e Dip. di Scienze
Chimiche, Universitàdegli Studi di Napoli Federico II, (b)Dip. di Ing. Civile e Meccanica,
Universitàdegli Studi di Cassino e del Lazio Meridionale, (c)Dip. di Scienza Applicata e
Tecnologia e UnitàINSTM del Politecnico di Torino
* [email protected]
Abstract
Ruthenium oxide-based nanomaterials are versatile and attractive candidates for various
technological applications such as electrochemical capacitors, electrodes and catalysts.
Different synthetic approaches have been explored, so far, to obtain Ru/RuO2@SiO2
nanocomposites. In this paper, a novel co-synthesis sol-gel process, fully performed at room
temperature and characterized by both easy handling of precursors and the lack of toxic or
pollutant reactants, was established to prepare Ru/RuO2@Nb2O5-SiO2 nanocomposites. The
mixed oxide matrix was selected in order to realize a material that can act as bifunctional
catalyst exhibiting both acidic and redox functionalities.
The surface area and the morphological characteristics of the catalysts were controlled by
adding different amounts of a nonionic surfactant (polyethylene glycol hexadecyl ether, BrijC10) directly in the starting solution of the precursors. By this way, the surfactant plays a
double role acting both as pore-directing agent and as oxygen-rich complexing agent of the
metallic species.
The research is inspired by the growing interest on ruthenium-based materials in view of
their ability to catalyze the green conversion of levulinic acid (LA) to γ-valerolactone (GVL).
LA is considered as one of the “top 10” most promising platform molecules derived from
biomass by the U.S. Department of Energy due to its reactive nature along with the fact that it
can be produced from lignocelluloses wastes at low cost.1
Activated carbon supported ruthenium (Ru/C) catalysts showed very high conversion and
selectivity however this catalyst suffers from continuous deactivation during recycling.
Notwithstanding, different supports have been explored to overcome such an
inconvenient ,the catalyst deactivation still remains an unresolved problem.
In this paper the structural characteristics and the catalytic performance in the
hydrogenation of LA to GVL of these new Ru@Nb2O5-SiO2 nanocomposite have been
investigated.
Reference
[1]
M. J. Climent, A. Corma, S. Iborra, Green Chem. 2014, 16, 516-547.
IT-07
Nanoporous Functional Coatings on Glass via Sol-Gel Process
Shen Jun*, Wang Xiaodong, Li Xiaoguang
Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology
Pohl Institute of Solid State Physics, Tongji University, Shanghai 200092, P. R. China
* [email protected]
Abstract
As a useful and promising technology, sol-gel derived coatings have drawn attentions for their
unusual merits, such as adjustable refractive index, controllable microstructure, low cost,
simple operation process, easy to industrial scale production and so on. In this paper,
microstructure control and performance improvement of nanoporous functional coatings on
glass via sol-gel method is introduced, and the applications in a variety of fields are discussed.
Firstly, the optical property, mechanical performance and hydrophobicity of the coating via
two-step catalysis sol-gel process are investigated. The hydrophobic AR coatings are prepared
from the sol mixed by base TEOS-derived sol and acid MTES-derived sol with different
molar ratio. Such simple sol-gel process can improve the production efficiency and reduce the
cost by eliminating the post treatment for hydrophobic. Ordered hexagonal mesoporous SiO2
coating was synthesized via evaporation induced self-assembly (EISA) process. The
mechanical performance and hydrophobicity tests proved that the coatings had excellent
scratch resistant and long-time stability. Therefore, the resulting mesoporous film has a
promising commercial value as AR coating. Also, some special AR coatings which applied in
the fields of high power laser systems are introduced, which may require a transmittance of
more than 99%, and high laser damage threshold for intense high power lasers.
Secondly, a two-step dipping process is designed for the fabrication of superhydrophobic
surface which shows the excellent water-repellence of lotus leaf. The micro-nano structure is
also formed which shows the similar surface morphology of a lotus leaf. The water contact
angle can as high as 170°. This method is also suitable for the deposition on large area as well
as non-flat substrates. And different wettabilities, different adhesive forces and different
optical properties can be integrated together at the same time.
Thirdly, aqueous droplets are successfully deformed with superhydrophobic silica coating.
The particles on the top of the superhydrophobic coating can be removed by the droplet
impact due to the weak bonding force between the silica nano-particles. Then the traditional
concept of surface tension that is determined by the homogeneous interaction of molecules at
liquid surface is not appropriate here. The water drops can be deformed in any shape. It is
even possible to get very small volume of liquid by cutting droplet, which may be meaningful
in the area of biomedicine, etc.
Reference
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
X. Wang, J. Shen, J Sol-Gel Sci Technol. 2010, 53, 322;
X. Li, J. Shen, Thin Solid Films 2011, 519, 6236;
X. Li, J. Shen, Chem. Commun. 2011, 47, 10761;
X. Wang, G. Wu, B. Zhou, J. Shen, Optics Express 2012, 20, 24482;
X. Li, M. Gross, K. Green, B. Oreb, J. Shen, Optics Letters 2012, 37, 2364
X. Li, G. Mark, O. Bob, J. Shen, Journal of Physical Chemistry C 2012, 116, 18367;
X. Li, Y Xue, P. Lv, H. Lin, F. Du, Y. Hu, J. Shen, Soft Matter 2016, 12, 1655;
X. Li, J. Shen, Chem. Commun. 2013, 49, 10016;
IT-08
Vortex Fluidic Mediated Self-Assembly and Nano-Materials Processing
Colin L. Raston
NanoScale Science and Technology, School of Chemical and Physical Sciences, Flinders
University, Bedford Park SA 5042, Australia.
*[email protected]
Abstract
The ability to carry out chemical and biochemical processing under continuous flow is
gaining prominence, where scalability is factored in at the inception of the fundamental
science. To this end we have developed a vortex fluidic device (VFD), Fig. 1,1-5 as a versatile
thin film microfluidic platform where the processing is not limited to diffusion control.
Reaction rates and yields can be dramatically increased relative to conventional batch
processing, as well as gaining access to new products and processing. This relates to the
unique conditions imparted in the dynamic thin film in the device, including a vibronic
response in the form of Faraday waves, high shear stress and micromixing, and increased heat
and mass and transfer.2
All molecules are treated in the same way in the thin film, which can be varied by varying
the VFD control parameters, including concentrations, temperature, flow rates, tilt angle θ,
rotational speed, and surface contact angle, as well as different Faraday waves and other field
effects (magnetic, pulsed laser and UV, plasma), Fig.1. The VFD is effective in controlling
the pore size and wall thickness of mesoporous materials, the phase of materials, the
formation of graphene scrolls, slicing SWCNT and MWCNT < 400 nm,5 and the exfoliation
of h-BN and graphene. Other applications abound in catalysis (including enhancing enzymatic
reactions), probing the structure of self organised systems, reactivity and selectivity (assembly
line synthesis),3 protein folding,4 and more:
Figure 1. The vortex fluidic device and some applications.
References
[1]
L. Yasmin, X. Chen, K. A. Stubbs and C. L. Raston, Scientific Reports, 2013, 3, 2282.
[2] J. Britton, S. B. Dalziel and C. L. Raston, Green Chem. 2016, 18, DOI: 10.1039/C5GC02494C
[3]
J. Britton, J. Chalker and C. L. Raston, Chem. Eur. J., 2015, 21, 10660-10665,
[4]
T. Z. Yuan, et al., ChemBioChem, 2015, 16, 393-396.
[5]
K. Vimalanathan, et al., Scientific Reports, 2016, 6, 22865.
IT-09
Ions Exchange Reactions on Nanocrystals: Surface/Interface, Doping
Control and Applications
Jiatao Zhang*, Jiajia Liu, Meng Xu, Jia Liu
Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and
Green Applications, School of Materials Science & Engineering, Beijing Institute of
Technology, Beijing, 100081, China
* [email protected]
Abstract
The key iusses of Metal/seminconductor binary cooperative nano-system is the coherence
between near field enhancement from localized SPR effect and exciton bohr radius related
quantum confinement effect at the nanoscale. To achieve flexible coupling between Plasmon
and excition and then enhance optoelectronic applications, the synergistic tailoring of shape,
size, composition, crystallization, hetero-interface and the distance between two nanoscopic
components comparable to the characteristic length of plasmon/exciton interactions are key
materials issues. By controlling soft acid-base coordination reactions between molecular
complexes and colloidal nanostructures, we showed that: i) proposed the new synthesis
method, namely different kinds of phosphine initialized cation exchange reactions, to
precisely synthesize metal/semiconductor hetero-nanostructures and doped semiconductor
nanostructures; ii) realized synergistic tailoring on morphologies, compositions and heterointerfaces of many kinds of metal@monocrystalline semiconductor core/shell nanocrystals
and the exploration of their photochemical energy conversion applications; iii) developed the
new cation exchange strategy to realize the successive control of substitutional heterovalent
doping, surface/interface control, doped luminescence and p-/n-type electronic impurities in
semiconductor nanostructures, and explored their photoelectric conversion applications.
Reference
[1] J. Gui, J. Zhang*, et al. Angew. Chem. Int. Ed. 2015, 54, 3683.
[2] Q. Zhao, J. Zhang*, et al. Adv. Mater. 2014, 26, 1387.
[3] J. Liu, J. Zhang*, et al. Adv. Mater.2015, 27，2753-2761.
[4] H. Qian, J. Zhang*, et al. NPG Asia Mater. (2015) 7, e152; doi:10.1038/am.2014.120.
[5] M. Ji, J. Zhang*, et al. Adv. Mater.2016,10.1002/adma.201503201:1-8.
[6] M. Ji, M. Xu, J. Zhang, J. Liu. J. Zhang*, Chem. Commun. 2016, 52, 3426-3429.
[7] H. Qian, M. Xu, X. Li, M. Ji, L. Cheng, A. Shoaib, J. Liu, J. Zhang*, L. Jiang, and H.S. Zhu, Nano Res. 2016,
9(3): 876–885.
[8] J. Zhang, Y. Tang, K. Lee & M. Ouyang*, Science 2010, 327, 1634.
[9] J. Zhang, Y. Tang, K. Lee, M. Ouyang*, Nature 2010, 466, 91.
IT-10
Yolk-Shell Nanorattles Encapsulating A Movable Au Nanocore in
Eletroactive Polyaniline Shells for Flexible Memory Device
Bin Zhang, Sai Sun, Luxin Wang and Yu Chen*
Key Laboratory for Advanced Materials, Institute of Applied Chemistry, East China
University of Science and Technology, 130 Mei Long Road, Shanghai 200237, China.
* [email protected]
Abstract
Template-assisted synthesis of hairy rattle-type hybrid nanospheres, consisting of a gold
nanocore and poly(4-vinylaniline) (PVAn) shell decorated with polyaniline (PANI) brushes
(Au@air@PVAn-g-PANI hybrid nanorattles), was carried out. Initially monodispersed
Au@SiO2-MPS (MPS: 3-(trimethoxysilyl)propyl methacrylate ) core-shell nanospheres were
prepared by coating of gold nanoparticles (Au NPs) via the modified Stöber method.
Narrowly dispersed Au@SiO2@PVAn nanospheres were prepared by distillation-precipitation
polymerization of 4-vinylaniline and divinylbenzene, from the Au@SiO2-MPS-1 template
nanospheres. Surface-initiated oxidative graft copolymerization of aniline from the
Au@SiO2@PVAn nanospheres, using the aniline moieties of PVAn as the anchoring site,
produced the Au@SiO2@PVAn-g-PANI nanospheres. HF etching of the hairy
Au@SiO2@PVAn-g-PANI core-double shell nanospheres removes the inorganic silica innershell and gives rise to hairy Au@air@PVAn-g-PANI hybrid nanorattles. The hybrid
nanorattles can be integrated into an electrically insulating poly(vinyl alcohol) (PVA) matrix.
The Al/Au@air@PVAn-g-PANI+PVA/ITO-coated poly(ethylene terephthalate) (PET) flexible
device, with a turn-on voltage of – 2.0 V and an ON/OFF state current ratio of more than 104,
was fabricated. This device can be switched to the ON state under a negative electrical sweep,
and also can be reset to the initial OFF state by a reverse (positive) electrical sweep. The
memory behavors of the flexible device were almost unchanged under the bending test.
References
(1) Y.Chen, B. Zhang, G. Liu, X.D. Zhuang, E.T. Kang, Chem. Soc. Rev. 2012, 41, 4688-4707.
Y. Chen, G. Liu, C. Wang, W. Zhang, R.-W. Li, L. Wang, Mater. Horizons 2014, 1, 489-506.
.
IT-11
Functional Nanomaterials for Sensors and Coatings in the NSD team at
CSIRO
A. Trinchi*, M. Breedon, A. Bendavid, P.A. White, A.S. Best, G. Wei, I.S. Cole
CSIRO Australia, Manufacturing, Private Bag 10, Clayton South, VIC Australia 3169
* [email protected]
Abstract
Within the Nanomaterials and Surface Design (NSD) team in the Manufacturing Business
Unit at CSIRO, we are developing novel nanomaterial based solutions and applying them to
real world challenges. Our work is driven by the technological demands of industry whilst at
the same time being guided by insights discovered at the nanoscale. Our research focus is on
the development of novel materials that make use of functional nanoscale building blocks. In
recent years, we have explored different routes to materials and system design, including:
•
•
•
•
•
•
•
synthesis of novel metal, semiconductor and carbon colloidal nanoparticles
development of green organic molecules and coatings
nanostructured thin film sensors
modelling of fundamental properties of small organic molecules
ligand chemistry development for chemosensors
robotics for rapid screening and materials discovery
discovery of new battery electrolyte materials
Our team places emphasis on sensing and coatings technologies, particularly in the fields of
corrosion prevention and sensing, water quality monitoring, soil nutrient monitoring, and
novel electrodes for energy storage devices. In particular, our efforts have focused on the
development of inexpensive, flexible, robust materials embedded with nanoparticles that can
serve as sensors with, optical, electrical, and electrochemical modes of operation. Examples
include fluorescent semiconductor quantum dots (QDs) and their organic counterparts, carbon
dots (CDs). These exhibit unique optical properties and their surfaces can be tailored with
functional groups, enabling them to be tuned for compatibility in different environments and
sensitivity towards different materials. Additionally, we are developing hybrid nanostructures
which exhibit rapid and reversible electrical responses when exposed to low levels of gases,
even at room temperature. Other examples include the development of ligands and
chemosensor molecules capable of selectively binding with cations and resulting in unique
colorimentric responses. We will discuss some of our recent achievements in nanomaterials
and chemistry in the context of these above mentioned fields.
IT-12
Nanowire Devices for Electrochemical Energy Storage
Liqiang Mai
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,
Wuhan University of Technology, Wuhan, 430070, China
*[email protected]
Abstract
One-dimensional nanomaterials can offer large surface area, facile strain relaxation upon
cycling and efficient electron transport pathway to achieve high electrochemical performance.
Hence, nanowires have attracted increasing interest in energy related fields.1-3
We designed the single nanowire electrochemical device for in situ probing the direct
relationship between electrical transport, structure, and electrochemical properties of the
single nanowire electrode to understand intrinsic reason of capacity fading. The results show
that during the electrochemical reaction, conductivity of the nanowire electrode decreased,
which limits the cycle life of the devices.4 Then, the prelithiation and Langmuir-Blodgett
technique have been used to improve cycling properties of nanowire electrode. Recently, we
have fabricated hierarchical MnMoO4/CoMoO4 heterostructured nanowires by combining
"oriented attachment" and "self-assembly".5 The asymmetric supercapacitors based on the
hierarchical heterostructured nanowires show a high specific capacitance and good
reversibility with a cycling efficiency of 98% after 1,000 cycles. Furthermore, we fabricated
Li-air battery based on hierarchical mesoporous LSCO nanowires and nonaqueous
electrolytes, which exhibits ultrahigh capacity over 11000 mAh g-1.6 We also designed the
hierarchical zigzag Na1.25V3O8 nanowires with topotactically encoded superior performance
for sodium-ion battery cathodes.7 Our work presented here can inspire new thought in
constructing novel one-dimensional structures and accelerate the development of energy
storage appilications.
Reference
[1]
[2]
[3]
[4]
[5]
[6]
[7]
C. J. Niu, J. S. Meng, Nature Commun. 2015, 6, 7402;
Y. L. Zhao, J. G. Feng, Nature Commun. 2014, 5, 4565;
Q. Qing, Z. Jiang, Nature Nanotechnol. 2014, 9, 142;
L. Q. Mai, Y. J. Dong, Nano Lett. 2010, 10, 4273;
L. Q. Mai, F. Yong, Nature Commun. 2011, 2, 381;
Y. L. Zhao, L. Xu, PNAS 2012, 109, 19569;
Y. F. Dong, S. Li, Energy Environ. Sci. 2015, 8, 1267;
IT-13
Novel Lithium Ion Battery Anode Materials from 2D Graphene Like
Membranes
Marlies Hankel,1* David Ferguson,1 Debra J. Searles1, 2
Centre for Theoretical and Computational Molecular Science, Australian Institute for
Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072,
Australia
2
School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane,
QLD 4072, Australia
* [email protected]
1
Abstract
Carbon structures have been extensively studied over recent decades as energy storage
materials. One of the industry applications is as the anode of lithium (Li) ion batteries. The
lithium ion battery (LIB) is one of the essential technologies required for the development of
portable electronics. Graphite, a layered material consisting of sp2 bonded carbon sheets is
currently the predominant anode material offering a theoretical capacity of LiC6 with Li
inserted between the layers. To achieve higher storage capacity, novel anode materials such as
carbon allotropes or carbon nitrides or graphene composites, are widely being pursued. Some
materials that surpass the capacity of graphite for Li storage have been identified.
We investigate the Li storage capacity of novel porous graphene-like 2D membranes [1-3].
These include porous graphitic carbon nitrides, g-C3N4 [1], g-CN [2] and hC2N, and 2D
carbon only membranes, graphenylene [2] and biphenylene [3]. Density functional theory
(DFT) calculations are employed to obtain the maximum Li loading of such membranes. We
also, in some cases, calculate diffusion barriers for the Li movement from one site to another.
Transition state theory can then be used to determine the mobility of the Li atoms within the
material. In addition to this we also show how the Li binds to the membrane by consideration
of the charge density distribution and the charge transfer from the Li to the membrane. The
volume change of the material on the insertion of lithium is determined by employing a
bilayer or bulk configuration of the material.
Reference
[1]
[2]
[3]
M. Hankel, D. Ye, L. Wang, D. J. Searles, J. Phys. Chem. C 2015, 119, 21921
M. Hankel, D. J. Searles, Phys. Chem. Chem. Phys. 2016 DOI: 10.1039/C5CP07356A
D. Ferguson, D. J. Searles, M. Hankel (unpublished material)
IT-14
Computational Exploration New 2D Materials for Electronics and Energy
Conversion
Fengxian Ma, Guoping Gao, Yalong Jiao and Aijun Du*
School of Chemistry, Physics and Mechanical Engineering Faculty, Queensland University of
Technology, Garden Point Campus, QLD 4001, Brisbane, Australia
*[email protected]
Abstract
Graphene-based research has progressed quickly following its epoch-making discovery in
2004, but only a handful of realistic applications are available off the shelf due to its inability
to act as a semiconductor. Now more attentions have been focused on studying other new
two-dimensional (2D) atomic crystals including hexagonal boron nitride, metal
dichalcogenides and phosphorene. Our recent research mainly focuses on (i) predicting
stability, electronic, mechanical and optical properties in experimentally less-explored 2D
materials [1-2]; (ii) exploring new structural phases and the phase transition in metal
dichalchogenides [3]; (iii) the use of 2D materials for hydrogen evolution reaction and carbon
dioxide conversion [4-5]. In this presentation, I will share our research progress in relation to
the above topics.
Reference
[1] Fengxian Ma, Yalong Jiao, Guoping Gao, YuanTong Gu…..Aijun Du, Nano Letters, 2016, published online,
DOI: 10.1021/acs.nanolett.5b05292.
[2] Yalong Jiao, Fengxian Ma, Guoping Gao, John Bell, Thomas Frauenheim, Aijun Du, Journal of Physics
Chemistry Letters 6 (2015) 2682.
[3] Fengxian Ma, Guoping Gao, Yalong Jiao….Aijun Du, Nanoscale, 8 (2016) 4969, cover image.
[4] Guoping Gao, Fengxian Ma, Yalong Jiao….and Aijun Du, Journal of Catalysis 332 (2015) 149.
IT-15
TNANO POWER HOUSE – A Futuristic Concept
Dr. Sesha V. Musunuri,
General Manager, Ramagundam Area-3,
Singareni Collieries Company Limited,
Centenary Colony – 505 212, India.
* [email protected]
Abstract
Nano Technology will optimize the use of limited non-renewable energy resources and save
them for future generations. It provides new methods for effective utilization of resources by
avoiding wastage and unnecessary processes. Coal which is currently the source of cheapest
thermal energy is finding alternatives with renewable energies. Renewable energy sources are
becoming economical with application of Nano Technology and its application. Energy cost
is an important constituent of mining costs estimated to be about 5 – 8% of production cost.
Coal mining especially Opencast needs a review in view of its enormous effect on the
environment, which has become the main source of opposition by the people around it and
environmentalists. Coal mining needs to be reviewed in view of the energy consumption
during production, and losses in utilization for power generation and transmission. Coal is
mined by Underground and Opencast methods, transported large distances and similarly
energy generated is transmitted to distances with some losses during the processes. Nano
Technology will enable to establish a Nano Power House which can directly installed in a
Mine or Coal seam for generation of energy. Underground gasification of Coal can be made
economical with application of Nano Technology. Further a day is not far off we purchase
clean Coal powder in packed form from a shop as rice / wheat to feed into a Nano Power
House of the size of present Air Conditioner to produce the necessary energy for households,
especially where Solar energy is also not possible. We produced heat and energy by burning
Coal in buckets with high pollution levels, however, Nano Science & Technology has to be
applied to utilize all the components of the chemical reaction of Coal burning including its
ash, gases in our court yard for better gardening, possibly with application of
phytoremediation and CO2 absorbing Nano material. This paper presents a futuristic concept
for use and generation of thermal energy with a Nano Power House.
IT-16
Non-noble Metal Catalyst Sensitized Si Nanowires-array Photoelectrodes
for Water Splitting
Shu-Fen Hu*
Department of Physics, National Taiwan Normal University, Taipei, 116, Taiwan
* [email protected]
Abstract
Development of a solar water splitting device requires design of a low-cost, efficient, and
non-noble metal compound as alternative to noble metals. In our study, we showed that CoSe2,
CoS2 can function as co-catalyst in phototoelectrochemical hydrogen. We designed
heterostructures of Si@CoS2 and Si@CoSe2 microwires for solar-driven hydrogen production.
CoSe2 and CoS2 successively coupled with p-Si can act as a superior photocathode in solardriven water splitting reaction. Photocurrents up to 9 mA/cm2 were achieved at 0 V vs.
reversible hydrogen electrode. Electrochemical impedance spectroscopy showed that the high
photocurrents can be attributed to low charge transfer resistance between the Si and CoSe 2,
CoS2 interfaces and that between the CoSe2, CoS2 and electrolyte interfaces. Our results
suggest that this CoSe2, CoS2 are promising alternative co-catalyst for hydrogen evolution.
References
[1] M. Basu, Z. W. Zhang, C. J. Chen, P. T. Chen, K. C. Yang, C. G. Ma, C. C. Lin, S. F. Hu and R. S. Liu,
Angew. Chem. Int. Ed. 2015, 54, 1-7.
[2] C. J. Chen, K. C. Yang, M. Basu, T. H. Lu, Y. R Lu, C. L. Dong, S. F. Hu, and R. S. Liu, ACS Appl. Mater.
Interfaces 2016, 8, 5400-5407.
Heterostructure of semi-metallic CoSe2 nanorods and p-Si MWs behave as an efficient photocathode
for solar driven hydrogen evolution reaction.
IT-17
Rational Design of High-Performance Electrode Materials for Lithium Ion
Batteries
Liang Zhou* and Liqiang Mai*
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,
Wuhan University of Technology
*[email protected]; [email protected]
Abstract
The development of high-energy lithium-ion batteries (LIBs) is an ongoing challenge. In this
talk, I will focus on our recent developments in rational design of high-performance electrode
materials for LIBs. I will start with how to design 5V LiNi0.5Mn1.5O4 hollow microspheres
and microcubes with excellent rate capability and cyclability. After that, I will move to
transition metal oxide based anode materials. Take iron oxide (FeOx) as an example, I will
show how hollow structuring, nanocompositing, and the combination of hollow structuring
and nanocompositing boost the lithium storage properties of transition metal oxides. Finally, I
will report our progress on Li3VO4, a less well studied anode material with outstanding
electrochemical performance.
Reference
[1]
L. Zhou; D. Y. Zhao; X. W. Lou, Angew. Chem. Int. Ed. 2012, 51, 239;
[2]
L. Zhou; H. Y. Xu; H. W. Zhang; J. Yang; S. B. Hartono; K. Qian; J. Zou; C. Z. Yu, Chem. Commun.
2013, 49, 8695;
[3]
H. W. Zhang; X. R. Sun; X. D. Huang; L. Zhou, Nanoscale, 2015, 7, 3270;
[4] H. W. Zhang; L. Zhou; O. Noonan; D. J. Martin; A. K. Whittaker; C. Z. Yu, Adv. Funct. Mater. 2014, 24,
4337;
[5] Q. D. Li; Q. L, Wei; J. Z. Sheng; M. Y. Yan; L. Zhou; W. Luo; R. M. Sun; L. Q. Mai, Adv. Sci. 2015, 2,
1500284
IT-18
White Graphene for Environmental and Energy Applications
Ying Chen
Institute for Frontier Materials, Deakin University, Waurn Ponds, Vic 3216, Australia
* [email protected]
Abstract
Boron nitride (BN) nanosheets are an important member of two-dimensional (2D)
nanomaterials and have a hexagonal structure similar to graphene. Because of its white color,
they are also called “white graphene”. White graphene has many properties distinct to
graphene and unique applications not available to graphene. Our current research interests
focus on BN nanosheet synthesis, new property exploration and their applications on
environmental protection and energy storage. This presentation reports our recent research in
porous white graphene for efficient oil-water separation [1], strong resistance to oxidation and
applications in protecting metals from oxidation and corrosion [2], and excellent dielectric
screening properties of BN nanosheets [3], preparation of BN colloid solution, free-standing
membranes and ultralight aerogels from functionalized BN nanosheets [4] as well as
substantial improvement for surface enhanced Raman spectroscopy (SERS) using BN
nanosheets as substrates. Further information can be found at our website at
http://www.deakin.edu.au/profiles/ying-(ian)-chen.
[1]. Weiwei Lei, David Portehault, Dan Liu, Si Qin and Ying Chen, "Porous Boron Nitride Nanosheets for
Effective Water Cleaning", Nature Communications, 4 （2013）1777
[2]. Lu Hua Li, Jiri Cervenka, Kenji Watanabe, Takashi Taniguchi, and Ying Chen#, “Strong Oxidation
Resistance of Atomically Thin Boron Nitride Nanosheets”, ACS Nano. 8 (2) (2014) 1457–1462
[3]. Lu Hua Li, Elton J. G. Santos, Tan Xing, Emmanuele Cappelluti, Rafael Roldán, Ying Chen, “Dielectric
Screening in Atomically Thin Boron Nitride Nanosheets”, Nano Letters, 15 (1) (2015) 218–223
[4]. Weiwei Lei, Vadym Mochalin, Dan Liu, Si QIn, Yury Gogotsi, and Ying Chen, “Boron Nitride Colloidal
Solutions, Ultralight Aerogels and Freestanding Membranes through One-step Exfoliation and
Functionalization” Nature Communications, 2015 DOI: 10.1038/ncomms9849.
[5]. Cai Q, Mateti S, Yang W, Jones R, Watanabe K, Taniguchi T, Huang S, Chen Y, Li LH “Boron Nitride
Nanosheets Improve Sensitivity and Reusability of Surface Enhanced Raman Spectroscopy”, Angew.
Chem. Int Ed, published online on 26 Apr 2016, doi: 10.1002/anie.201600517
IT-19
Catch Release Catalysis using Supramolecular Assembly
Zhang Zhong-Xinga, Shi-Qiang Baia, David James Younga, b, T. S. Andy Hora, c
Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology
and Research), 2 Fusionopolis Way, #08-03, Innovis, Singapore 138634, Republic of
Singapore
b
Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast,
Maroochydore DC, Queensland, 4558, Australia
c
The University of Hong Kong, President’s Office, Pokfulam Road, Hong Kong.
a
Abstract
Homogeneous catalysts generally demonstrate better selectivity and reactivity under milder
reaction conditions than their heterogeneous counterparts because of increased accessibility to
well-defined reactive sites. Nevertheless, homogeneous catalysis accounts for less than 20%
of all industrial processes because, in large part, of the difficulty in separating a homogeneous
catalyst from the reaction product. This presentation will discuss our recent progress tuning
heterogeneous catalysts by etching Cu2O cubes with Transition Metal and Lanthanide salts
and also the use of non-bonded interactions for the development of a Catch-Release catalysis
system that combines the catalytic efficiency of homogeneous catalysis with the ease of
separation of a heterogeneous catalyst.
Figure. A catch release catalysis system
Reference
[1]
Qi, M.; Tan, P. Z.; Xue, F.; Malhi, H. S.; Zhang, Z. –X.; Young, D. J.; Hor, T. S. A. “A supramolecular
recyclable catalyst for aqueous Suzuki – Miyaura coupling” RSC Adv., 2015, 5, 3590 - 3596. [2] A. B. Author
1, C. D. Author 2, Journal name Year, volume, pages;
IT-20
Size-Dependent Gene Delivery of Amine Modified Silica Nanoparticles
Meihua Yu, Yuting Niu, Chengzhong Yu*
Australian Institute for Bioengineering and Nanotechnology, The University of Queensland,
Brisbane, QLD 4072, Australia
*[email protected]
Abstract
Gene therapy is a promising treatment where foreign genetic molecules (nucleic acids) are introduced
into living cells to supplement or alter genes to treat various diseases.[1] Naked nucleic acids
themselves cannot enter into cells and are easily degraded by nucleases, therefore efficient carriers are
needed to deliver nucleic acids (DNA or RNA) into cells. Silica-based nanocarriers have attracted
increasing attention for gene delivery because of their unique properties such as tunable particle/pore
size, biocompatibility and low cost.[2] In order to gain insight into the role of particle size on gene
transfection efficiency, amine modified monodisperse Stöber spheres (NH2-SS) with various diameters
of 125, 230, 330, 440 and 570 nm were synthesized.[3] The in vitro transfection efficiencies of NH2SS were studied in HEK293T cells by delivering plasmid DNA encoding green fluorescent protein
(GFP) (pcDNA3-EGFP, abbreviated as pcDNA, 6.1 kbp). NH2-SS with a diameter of 330 nm (NH2SS330) showed the highest GFP transfection level compared to NH2-SS particles with other sizes. The
transfection efficiency was found as a compromise between the binding capacity and cellular uptake
performance of NH2-SS330 and pcDNA conjugates. NH2-SS330 also demonstrated the highest
transfection efficiency for another plasmid DNA with a bigger size of 8.9 kbp. This work
demonstrates for the first time the significance of particle size on gene transfection efficiency in silicabased gene delivery systems. Our findings are crucial to the rational design of synthetic vectors for
gene therapy.
Figure 1. GFP expression levels in HEK 293T cells by flow cytometry, after treated with pcDNA,
NH2-SS125/pcDNA, NH2-SS230/pcDNA, NH2-SS330/pcDNA, NH2-SS440/pcDNA and NH2SS570/pcDNA at different weight ratios of NH2-SS to pcDNA
Reference
[1]
Roy, K.; Mao, H. Q.; Huang, S. K.; Leong, K. W., Nat. Med. 1999, 5, 387-391.
[2]
Kim, M. H.; Na, H. K.; Kim, Y. K.; Ryoo, S. R.; Cho, H. S.; Lee, K. E.; Jeon, H.; Ryoo, R.; Min, D. H.,
ACS Nano 2011, 5, 3568-3576.
[3] Yu, M. H.; Niu, Y. T.; Zhang, J.; Zhang, H. W.; Yang, Y. N., Taran, E.; Jambhrunkarar, S.; Gu, W. Y.;
Thorn, P.; Yu, C. Z., Nano Research 2016, 9, 291-305
IT-21
Reversible Turn-On Type Luminescence Triggered by Methanol Vapor in
Platinum(II) and Palladium(II) Complexes with Mixed 1,3Bis(diphenylphosphino)propane and L-Cysteinate
Nobuto Yoshinari,1* Tsutomu Shimizu,1 Koichi Nozaki,2 Takumi Konno1*
1
Department of Chemistry, Graduate School of Science, Osaka University, Japan
2
Graduate School of Science and Engineering, University of Toyama, Japan
* [email protected], [email protected]
Abstract
Luminescent coordination compounds are potential chemical sensors for the detection of
volatile organic compounds (VOCs) in working environments due to their property of being
detectable by the naked eye.[1] Methanol detection is especially important because it is highly
toxic in the human body. In recent years, a number of luminescent metal complexes that can
detect methanol vapor have been developed. However, almost all reported methanol detection
compounds are based on luminescence color change or luminescence turn-off. In addition,
they often respond to VOCs other than methanol. Thus, the creation of coordination
compounds that show turn-on type luminescence triggered selectively by methanol vapor
under environmental conditions is a great demand in this research area.
In this presentation, a reversible, turn-on-type photoluminescence triggered by methanol
vapor in square-planar palladium(II) and platinum(II) complexes, [M(dppp)(L-cys)] (M = PdII,
PtII), is reported.[2] Both the ‘turn-on’ and ‘turn-off’ states of the complexes were
crystallographically characterized, which revealed the presence of intermolecular OH···O and
CH···π interactions between methanol and the complex molecules in the ‘turn-on’ state.
These interactions prevent the vibrational quenching of the luminescence, leading to the turnon-type luminescence in this system.
Reference
[1]
O. S. Wenger, Chem. Rev. 2013, 113, 3686-3733; A. Kobayashi, M. Kato, Eur. J. Inorg. Chem. 2014,
4469-4483.
[2]
N. Yoshinari, T. Shimizu, K. Nozaki & T. Konno, Inorg. Chem. 2016, 55, 2030-2036.
IT-22
Anomalous Fluorescence Enhancement from Double Heterostructure 3D
Colloidal Photonic Crystals–A Multifunctional Fluorescence- Based Sensor
Platform
Ehsan Eftekhari1, Xiang Li1, Tak H. Kim1, Zongsong Gan5, Ivan S. Cole2, Dongyuan Zhao3,
Dave Kielpinski4, Min Gu5 & Qin Li1*
1.
Queensland Micro- and Nanotechnology Centre & School of Engineering, Griffith
University, Nathan, QLD 4111, Australia
2.
CSIRO Materials Science and Engineering, Clayton, VIC 3168, Australia
3.
Department of Chemistry & Laboratory of Advanced Materials, Fudan University,
Shanghai, 200433, P.R. China
4.
Centre for Quantum Dynamics, Griffith University, Nathan, QLD 4111, Australia
5.
Centre for Micro-Photonics and CUDOS, Faculty of Science, Engineering and
Technology, Swinburne University of Technology, Hawthorn, VIC 3122, Australia
* [email protected]
Abstract
Augmenting fluorescence intensity is of vital importance to the development of chemical and
biochemical sensing, imaging and miniature light sources. Here we report an unprecedented
fluorescence enhancement with a novel architecture of multilayer three-dimensional colloidal
photonic crystals self-assembled from polystyrene spheres. The new technique uses a double
heterostructure, which comprises a top and a bottom layer with a periodicity overlapping the
excitation wavelength (E) of the emitters, and a middle layer with a periodicity matching the
fluorescence wavelength (F) and a thickness that supports constructive interference for the
excitation wavelength. This E-F-E double heterostructure displays direction-dependent light
trapping for both excitation and fluorescence, coupling the modes of photonic crystal with
multiple-beam interference. The E-F-E double heterostructure renders an additional 5-fold
enhancement to the extraordinary FL amplification of Rhodamine B in monolithic E CPhCs,
and 4.3-fold acceleration of emission dynamics. Such a self-assembled double heterostructue
CPhCs may find significant applications in illumination, laser, chemical/biochemical sensing,
and solar energy harvesting. We further demonstrate the multi- functionality of the E-F-E
double heterostructure CPhCs in Hg (II) sensing.
Left: Schematic of the coupling of photonic crystal effect and multiple-beam interference in
the CPhCs E-F-E double heterostructure; Middle and Right: Illustration and SEM image of
an E-F-E double heterostructure (Scale bar is 1 μm). Insets: top-view photo images of each
layer.
IT-23
Mesoporous hollow organosiliceous spheres for VOCs removal with high
efficiency and stability
Hongning Wang*
School of Petrochemical Engineering, Changzhou University, Changzhou,Jiangsu,213164,
P.R. China
* [email protected]
Abstract
The emissions of volatile organic compounds (VOCs) have become one of the most stringent
environmental challenges. Adsorption is a reliable method and widely used among a number
of technologies available for VOC abatement because of the flexibility of the system, low
energy and cheap operation costs. Hydrophobicity, VOCs adsorption capacity and stability
are three major parameters to evaluating adsorption performance of adsorbents. Mesoporous
hollow organosiliceous spheres have been prepared by surface modification with
trimethylchlorosilane (TMCS) and condensation with tetraethylorthosilicate (TEOS) and 1,2Bis(triethoxysilyl) ethane (BTSE) under acidic conditions with F108 as surfactant, for the
removal of VOCs. The resultant hollow organosiliceous spheres possesses a uniform and
well-dispersed hollow spherical structure (25-30 nm), high surface area, large total pore
volume, high VOCs adsorption capacity, and small water vapor adsorption capacity. The
adsorption and desorption performance of hollow organosiliceous spheres under static (nhexane and 93# gasoline) and dynamic (n-hexane) conditions was investigated. Compared
with commercial silica gel (SG) and activated car-bon (AC), hollow organosiliceous spheres
show higher capacity of adsorbing n-hexane and 93# gasoline with good stability and low
water vapor adsorption capacity under static adsorption conditions, higher dynamic
adsorption capacity and stable breakthrough time under dynamic adsorption conditions. The
high efficiency and stability of hollow organosiliceous spheres are associated with their
unique hollow morphology and structure parameters. The designed hollow organosiliceous
spheres with high VOCs removal capacity and recyclability are promising candidates for the
treatment of air pollution.
IT-24
Epitaxial Growth of III-V Semiconductor Nanowires
Jin Zou *
Materials Engineering and Centre for Microscopy and Microanalysis, University of
Queensland, Brisbane, QLD 4072, Australia
* [email protected]
Abstract
Epitaxial III-V semiconductor nanowires and their heterostructures have been paid
extraordinary attention in the recent decade due to their unique structural and chemical
characteristics and in turn potential properties in optoelectronic, nanoelectronic, and sensing
developments. In general, semiconductor nanowires are induced by catalysts, which mediates
the one-dimensional growth. However, since the complications of catalysts in inducing the
nanowire growth, many nanowires induced by the catalysts have their own structural
characteristics. In this presentation, I shall summarize our discoveries of impact of catalysts in
the growth of epitaxial III-V semiconductor nanowires for the past decade [1-9].
Reference
[1] YN Guo, J Zou, M Paladugu, H Wang, Q Gao, HH Tan, C Jagadish; Appl. Phys. Lett. 2006, 89, 231917.
[2] J Zou et al.; Small 2007, 3, 389.
[3] M Paladugu, J Zou, YN Guo, GJ Auchterlonie, HJ Joyce, Q Gao, HH Tan, C Jagadish, Y Kim; Small 2007, 3,
1873.
[4] M Paladugu, J Zou, YN Guo, X. Zhang, HJ Joyce, Q Gao, HH Tan, C Jagadish, Y Kim; Angew. Chem. Inter.
Ed. 2009, 48, 780.
[4] X. Zhang, J Zou, M Paladugu, YN Guo, Y. Wang, Y. Kim, HJ Joyce, Q Gao, HH Tan, C Jagadish; Small
2009, 5, 336.
[5] HY Xu, Y Wang, YN Guo, ZM Liao, Q Gao, HH Tan, C Jagadish, J Zou; Nano Lett. 2012, 12, 5744.
[6] YN Guo, HY Xu, GJ Auchterlonie, T Burgess, HJ Joyce, Q Gao, HH Tan, C Jagadish, HB Shu, XS Chen, W
Lu, Y Kim, J Zou; Nano Lett. 2013, 13, 643.
[6] YN Guo, T Burgess, Q Gao, HH Tan, C Jagadish, J Zou; Nano Lett. 2013, 13, 5085.
[7] Z. Zhang, ZY Lu, PP Chen, W. Lu, J. Zou; Nanoscale 2015, 7, 12592.
[8] Z. Zhang, K. Zheng, ZY Lu, PP Chen, W. Lu, J. Zou; Nano Lett. 2015, 15, 876.
[9] Z. Zhang, PP Chen, W. Lu, J. Zou; Nanoscale 2016, 8, 1401.
IT-25
Graphene Oxide and Reduced Graphene Oxide Hybrids
with Spin Crossover Materials
Shinya Hayami1,2*, Yusuke Sekimoto1, Hiroshi Takehira1, Takeshi Matsui1, Masaaki
Nakamura1, Michio Koinuma1, Ryo Ohtani1
1
Department of Chemistry, Faculty of Advanced Science and Technology, Kumamoto
University, 2Institute of Pulsed Power Science (IPPS), Kumamoto University, 2-39-1
Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
*[email protected]
Abstract
Graphene oxide (GO) is 2D nanosheet, and has many functionality, for example, proton
conductivity.[1] The GO has negative charge because
GO has many oxygen functional groups such as epoxide
group, carboxyl group, hydroxyl group and so on.
Therefore, GO is able to combine with positive charge
cations such as proton, metal ions, complexes and so on.
Furthermore the hybrids can be prepared by not only
electrostatic interaction but also π-π stacking or
chemical bonding between epoxy and amine groups.[2]
After reduction of GO by hydrazine, UV irradiation or
annealing, reduced GO (rGO) can be produced, which Figure 1 Structure of GO and SCO
shows electrical conduction. After reduction of GO hybrids.
hybrids, rGO hybrids also can be produced. In this
2.2x10
study, we focus on GO and rGO hybrids with spin
crossover (SCO) cation [FeIII(qnal)2]+ (1) and
2.0
[FeII(Htrz)2(trz)](BF4) (2). The complexes exhibit a
unique SCO behavior depending on counter anions, GO
1.8
and rGO. GO-SCO hybrids (1-GO and 2-GO) and rGOSCO hybrids (1-rGO and 2-rGO) were synthesized
(Figure 1). 1-GO and 1-rGO exhibited gradual SCO
1.6
behavior, 2-GO and 2-rGO exhibited abrupt SCO
behavior with hysteresis. Moreover, a light-induced
1.4
20
40
60
80 100 120 140
excited-spin-state trapping (LIESST) effect for 1-rGO
Temperature // K
K
Temperature
was observed (Figure 2), and the increase of Tc was
also observed for 2-rGO. After reduction of GO hybrids, Figure 2 χgT vs T plots for 1-GO
rGO hybrids also showed electrical conduction. and 1-rGO before and after light
Graphene-based materials with multi-functionality are
irradiation at 800 nm.
presented here for the first time. We succeeded to
control the domain size of the SCO complexes on the graphene nano sheet or chemical
pressure of the interlayers.
g-1
χgT /
-1
cm3 K
gT / cm K g
3
-3
References
[1] S. Hayami et al., Chem. Commun., 2014, 50, 14527. Chem. Mater., 2014, 26, 5598. Angew. Chem., Int. Ed.,
2014, 53, 6997. J. Am. Chem. Soc., 2013, 135, 8097.
[2] S. Hayami et al., Adv. Funct. Mater., 2013, 23, 323. Dalton Trans., 2015, 44, 5049. Inorg. Chem. Front.,
2015, 2, 886.
IT-26
Metal-Organic Frameworks with Mesopore
Hexiang Deng*
College of Chemistry & Molecular Sciences, Institute of Advanced Studies, Wuhan University,
Wuhan, 40072, China
* [email protected]
Abstract
Metal-Organic Frameworks (MOFs) are useful due to their application potentials in gas
storage, separation and catalysis. The pore aperture and pore size are two critical parameters
of these porous materials because they dictate the size and capacity of the guest molecules
accessing pore environments. Usually, the pore apertures of MOFs are confined within the
micropore region, and MOFs with pores larger than 20 Å are rare. Larger pore sizes are
highly sought after for applications such as inclusion and separation of large molecules. Here
we show that through topological design and modular synthesis of organic links, traditional
challenges such as interpenetration and pore collapse upon guest removal can be overcome. In
this, way, the pore size of MOFs can be expended into a previously unattained regime, the
largest of which can now reach nearly 10nm. Their pores are large enough to let interesting
biomolecules such as myoglobin and green fluorescent proteins (GFPs) to pass through, and
the natural folding of these proteins remains unaltered in the pores. Furthermore, these
mesoporous materials with atomic thin walls are also suitable for the study of gas adsorption
in their pores with high precision. Extra gas adsorption with the presence of superlattice of the
gas molecules in the pores was observed for the first time to reveal the collective behavior of
gases during the pore filling process.
Reference
[1]
H. Deng, S. Grunder, K. E. Cordova, C. Valente, H. Furukawa, M. Hmadeh, F. Gándara, A. C. Whalley,
Z. Liu, S. Asahina, H. Kazumori, M. O'Keeffe, O. Terasaki, J. F. Stoddart & O. M. Yaghi, Science, 2012, 336,
1018-1023.
[2]
H. S. Cho, H. Deng, K. Miyasaka, Z. Dong, M. Cho, A. V. Neimark, J. K. Kang, O. M. Yaghi, O.
Terasaki, Nature, 2015, 527, 503-507.
IT-27
Strategy for the Preparation of Low Cost Hierarchical Porous Y Zeolite
with Nanoscale Channel System
Baojian Shen,* Shuo Mi, Tao Wei, Qiaoxia Guo
State Key Laboratory of Heavy Oil Processing; the Key Laboratory of Catalysis of CNPC;
College of Chemical Engineering, China University of Petroleum, Beijing, 102249, China
* The Corresponding Author’s email address: [email protected]
Abstract
The demand for nanoscale channel system of bulky molecules is a challenge for the zeolite,
which usually have microporous system.[1] Therefore, different strategies have been
developed, such as steaming and acid leaching, alkaline leaching, carbon templating, or
mesopore structure-directing agents. Our previous work showed that a mesoporous ultrastable Y (USY) zeolite could be prepared through the sequential desilication dealumination
process by using a high silica NaY zeolite as the starting material[2,3] or incorporating Fe
atoms into the framework of NaY by a hydrothermal synthesis process, followed by
deferrization–dealumination via steaming[4,5]. However, it is still a challenge to form better
interconnected mesopores in micropores zeolite system in an economic way. Here, we would
like to show a novel low cost strategy to generate mesopores by adding B atoms into
framework of NaY during hydrothermal synthesis process, to obtain the B-NaY zeolite as the
starting material, and then deboron-dealumination via steaming, an ultra stable Y zeolite with
rich interconnected mesoporosity and suitable acid sites was obtained by using this
methodology. As a result, compared with the ordinary USY, the mesopore volume of the new
method zeolite is increased by over 46%, and the enriched nanoscale channel-like mesopores
are obtained. Catalytic cracking catalysts prepared from the upgraded mesoporous zeolites
showed an increase in gasoline and light cycle oil selectivity when the conversion of a
vacuum gas oil was compared.
Reference
[1] A. Corma, M.J. Díaz-Cabañas, J. Martí
nez-Triguero, F. Rey, J. Rius, Nature, 2002, 418, 514
[2] Z.X. Qin, B.J. Shen, X.H. Gao, F. Lin, B. J. Wang, C.M. Xu, J. Catal., 2011, 278, 266.
[3] Zh.X. Qin, B.J. Shen, Zh.W. Yu, F. Deng, L. Zhao, Sh.G. Zhou, D.L. Yuan, X.H. Gao, B.J. Wang,; H.J.
Zhao, H.H. Liu, J. Catal., 2013, 298, 102.
[4] D.D. Guo, B.J. Shen, G.D. Qi, L. Zhao, J. Xu, F. Deng, Y.Ch. Qin, Q.X. Guo, Sh. Y. Ren, X.H. Gao, S.
Qin, B.J. Wang, H.J. Zhao, H.H. Liu, X.M. Pang. Chem. Commun. 2014, 50, 2660
[5] D.D. Guo, B.J. Shen, Y.Ch. Qin, J.X. Sun, Q.X. Guo, Sh. Y. Ren, X.H. Gao, X.M. Pang, B.J. Wang, H.J.
Zhao, H.H. Liu. Microporous Mesoporous Mater. 2015, 211, 192
IT-28
Flexible Crystals: Stretching the Boundaries of a Single Crystal
Jack K. Clegg1, John C. McMurtrie, 2 Anna Worthy, 2 Michael Pfrunder,1 Aidan Brock1 and
Arnaud Grosjean1
1
School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane St
Lucia, QLD, Australia, 4072
2
School of Chemistry, Physics and Mechanical Engineering, Queensland University of
Technology, Brisbane 4001, Australia
* [email protected]
Abstract
A crystal is normally thought of as a homogenous solid formed by a periodically repeating,
three-dimensional pattern of atoms, ions, or molecules. Indeed, the regular arrangement of
molecules, in a single crystal lead to many useful characteristics (in addition to diffraction!)
including unique optical and electrical properties, however, molecular crystals are not
typically mechanically robust, particularly compared to crystals of network solids like
diamond. Upon the application of stress or strain, these crystals generally irreversibly deform,
crack or break resulting in the loss of single crystallinity.
We have recently discovered a class of crystalline compounds that display the intriguing
property of elastic flexibility – that is they are capable of reversibly bending without
deforming, cracking or losing crystallinity. A number of these crystals are flexible enough to
be bent into a loop! (See Figure 1). We hypothesise that these intriguing properties stem from
the nature and arrangement of intermolecular forces present between molecules in the crystal
lattice, whereby weak interactions allow molecules to move sufficiently within a crystal lattice
(resulting in flexibility) while stronger interactions between molecules maintain the
crystallinity. This in turn leads to a loss of periodicity due to irregular compressions and
expansions of intermolecular distances throughout the lattice, challenging the definition of a
crystal. When the force is removed the crystals return to their perfectly ordered state. We are
currently investigating ways that we can tune the physical and mechanical properties of
materials through the combination and control of intermolecular interactions.
Figure 1: A crystal of [Cu(acacBr)2] showing elastic flexibility.
IT-29
Dual Template Synthesis of A Nanosheet ZSM-5 Zeolite:
Precise Tuning the Morphology
Yunshan Shang, Yu Song, Jiarong Li, Guodong Li, Yongqiang Xu, Yanjun Gong*
State Key Laboratory of Heavy Oil Processing, The Key Laboratory of Catalysis of CNPC,
China University of Petroleum, Beijing 102249, China.
E-mail: gongyj@cup .edu.cn, Fax: +86 108973 4979;Tel: +86 1089733066
Abstract
Nanosheet ZSM-5 is a kind of promising hierarchical zeolites with intrinsic micropores and
bypass-intracrystalline mesopores structure , However, exploring a facile and inexpensive
strategy to assemble hierarchical nanosheet ZSM-5 remains a great challenge. Dual-template
route is an effective method to fabricate nanosheet ZSM-5 and tailor the texture properties as
well as its catalytic performance [2].
Herein, C18-6-6(S1) and S2(home-made) are used as co-template, altering the ratio of
concentration of S1to S2 in the synthesis of ZSM-5. When the molar ratio of S1:S2 is 10:1
and 10:5, respectively, SEM characterization showed that the ZSM-5morphology still is
house-of-cards-like (Fig 1a-1b). Further increasing the ratio to 10:10, the cross-stacking
pattern turns to simple homophase sheet stacking, corresponding the crystallinity decreased,
but the ratio increase to 10:30, the so-obtained zeolite converted traditional shape (fig 1d). It
can be deduced that the S2 has an important role in changing the zeolite orientation growth. In
order to investigate the role of S2 and cost reduction, the amount of expensive S1 was
decreased, the plate sheet cross-stacking pattern begin to weaken with reducing ratio of S1:S2
from 10:10 to 5:10 (fig 1c 1e 1f), these results suggest that S2 restrained the sheet packing
behavior and slow down growth rate. As is well known, crystallization temperature has a
significant impact on the morphology, SEM showed that the morphology varied from platelike nanosheet structures (150-160℃), prism stacking(170℃), then turn to analogous coffinshaped when temperature up to 180℃, but all the particle size were around 1-1.5μm (Fig1g-j),
which are consistent with XRD results. The presence of S2 could induce the zeolite growth
and tailor the morphology and texture properties remarkably. This may be a valid way to
enhance the practicability of nanosheet ZSM-5 for different catalytic reaction.
a 10:1
b 10:5
c 10:10
d 10:30
e 6.7:10
f 5:10
g 150℃
h 160℃
i 170℃
j 180℃
Fig1 SEM images of ZSM-5 samples, with different ratio of S1:S2(a-f), and different temperature(g-j)
The State key development program for basic research (2012CB215002) and the national
natural science foundation of China (21176255, 21276278) financially support this work.
Reference
[1] L. Emdadi, Y. Q. Wu, G. D. X. Liu, Chemistry of Materials 2014, 26, 1345-1355.
IT-30
Calculation of Viscosity of Polymers in Nanopores
Stefano Bernardi,1 Sarah J. Brookes,2 Debra J. Searles1,2,3,*
Bioengineering and Nanotechnology, The University of Queensland, Brisbane, Qld 4072
2
Queensland Micro- and Nanotechnology Centre, Griffith University, Brisbane, Qld 4111
3
School of Chemistry and Molecular Biosciences, Australian Institute for Bioengineering and
Nanotechnology, The University of Queensland, Brisbane, Qld 4072
* [email protected]
1
Abstract
Molecular level computational studies provide a useful approach to establish
structure/property relationships for materials. One property of particular interest for the study
of polymers is their viscosity.
In this talk we will discuss nonequilibrium approaches to determination of polymer viscosities,
which offer advantages over the conventional equilibrium methods when relaxation times are
slow or we are interested in nonlinear systems. We will show results of various approaches to
evaluation of the response of a fluid confined in a nanopore and subjected to shear. The shear
is induced by the movement of the boundaries in opposite directions and is made of moving
atoms. The viscous heat generated inside the pore is removed by a thermostat applied
exclusively to the atomic walls, so as to leave the dynamics of the fluid realistic. [1]
We will also discuss how position dependent properties can be determined, [2] and how the
size of the simulation cell can affect the results obtained from simulations. [3]
References
[1]
[2]
[3]
S. Bernardi, S. J. Brookes, D. J. Searles and D. J. Evans, J. Chem. Phys. 2012, 137, 074114;
S. Bernardi and D. J. Searles, Mol. Sim. 2016, 121, 236-244.
S. Bernardi, S. J. Brookes, and D. J. Searles, Chem. Eng. Sci. 2015, 121, 236-244.
IT-31
Supramolecular Helical Polymers
Qianghua Lu, Kun Liu, Jun Wang, Xin Zhao, Afang Zhang*
Department of Polymer Materials, Shanghai University, China
* [email protected]
Abstract
Combination of chirality with dynamic characteristics from supramolecular chemistry affords
supramolecular helical polymers with tunable supramolecular structures and helical
conformation, which may provide wide applications in chiral recognition and asymmetric
catalysis.[1] Peptides integrate chirality, abandoned secondary structures, and high tendency to
self-assemble which play key rule in mediating supramolecular helical formation. Here we
report on supramolecular helical polymers mediated by peptides of different sequence and
topologies, including (a) oligopeptides from amyloid proteins into left-handed helical fibers,[2]
(b) amphiphilic codendrimers into well-defined helical fibers, (c) enhanced helical assembly
from collagen-mimetic polypeptides, (d) polylysinses pendanted dendritic oligoethylene
glycols through dynamic covalent linkages with tunable helical conformation.[3]
Figure 1: Supramolecular helical polymers formed from sequenced oligopeptides (a), amphiphilic chiral
codendrimers (b), collagen-mimetic polypeptides (c), as well as polypeptides through dynamic covalent
chemistry (d).
Reference
[1]
(a) P. H. J. Kouwer, M. Koepf, V. A. A. Le Sage, et al. Nature 2013, 493, 651–655. (b) J. Wang, A.
Zhang, Prog. Chem. 2015, 27, 1413–1424;
[2]
C. Lara, N. P. Reynolds, J. T. Berryman, A. Xu, A. Zhang, R. Mezzenga. J. Am. Chem. Soc. 2014, 136,
4732–4739;
[3]
J. Yan, K. Liu, W. Li, H. Shi, A. Zhang, Macromolecules 2016, 49, 510–517. (b) J. Yan, K. Liu, X.
Zhang, W. Li, A. Zhang, J. Polym. Sci., Part A, Polym. Chem. 2015, 53, 33–41.
IT-32
Nanoadditives for Antibacterial Food Packaging
Venkata Chevali*, Belas A Khan, Hao Wang
Centre for Future Materials, University of Southern Queensland, Toowoomba QLD 4350
* [email protected]
Abstract
A bio-based future hinging on the usage of biomass for biodegradable plastic applications
promises economic and environmental sustainability. The abundance of lignocellulosic
biomass as precursor for bioenergy and organic macromolecule has assumed key importance
in the bio-future, albeit biomass supply chains and value chains are underdeveloped and
inadequate for contemporary fuel, energy, food, and sustainability challenges. Particularly for
food packaging, the demand is ever increasing for thermally stable, minimally toxic and
antibiotic materials, which deliver food quality, freshness, and safety, in a market where
traditional petrochemical derived plastics are predominant in the current market. Nanoscale
additives play a key role in this pursuit of nano-biocomposites engineered from industrial
hemp, bamboo, and wood with a bioplastic and antibacterial nanoparticle. The case study
presented on glycidyl methacrylate-grafted polylactic acid with silver-loaded hemp hurd will
be analysed for its effectiveness as a thermally- and structurally-stable rigid food packaging,
with acceptable levels of heavy metal migration in food simulants. The question of whether
the technological innovations can translate into practical application will be tackled through
cost–benefit and sensitivity analyses on the suitability of these biocomposite for food
packaging. Our results show an attractive benefit-to-cost ratio, and exhibit predictive
sensitivities of outcomes with respect to identified risks and uncertainties. The economic cost
versus benefit, and technical propositions present a strong case for utilising biomass in
Australia and elsewhere, and demonstrate financial robustness vis-à-vis market fluctuations.
Reference
[1]
[2]
[3]
Khan BA, Warner P and Wang H. BioResources 2014; 9: 3642-59.
Khan BA, Wang J, Warner P and Wang H. J Appl Polym Sci 2015; 132: 1-6
Khan BA, Chevali VS, Na H, Zhu J, Warner P and Wang H. Composites Part B 2016; 100: 10-8.
IT-33
Doxycycline Loaded Nanoparticles of PLGA for Controlled Delivery and
Effective Therapy Against Lymphatic Flariasis.
Dr Rahul Shukla* ,Dr V.R. Sinha
UIPS,Panjab University,Chandigarh
* [email protected]
Abstract
Lymphatic Filariasis is neglected,tropical,vector borne disease prevalent in economically poor
countries. The aim of the study is to target the macro filarae(adult) in lymphatic filariasis and
sustained action of the doxycycline (DOX) for extended period of time and with enhanced
efficacy, and minimize its toxic effects.
Biodegradable, FDA approved polymers PLGA were selected to prepare polymeric
nanoparticles(np) for delivery of doxycycline as antifilarial drug. It shows the adulticidal
action,by mode suppressing the wolbachia. Filarial nematodes Wuchereria bancrofti, and
B.malayi, the causative agent of lymphatic filariasis, harbors the bacterial endosymbiont
wolbachia, essential for worm development, fecundity and survival.
Methods
Polymeric nanoparticles of PLGA for DOX were prepared using solvent displacement method
using pluronic F-68 (PF68) as surfactant. Formulations were optimized for their charge, size
and entrapment efficiency by varying the concentration of PF 68 and 0.26 %w/v of PF 68 was
found to be optimizing PLGA nanoparticles. Particle size and surface charge for optimized
nanoparticles of PLGA. The drug entrapment for optimized formulation of PLGA
nanoparticles was 49.5 % w/v.
Results
The in-vitro release study conducted for PLGA polymeric nanoparticles initial burst release
and further sustained release was observed for 24 hours. In-vivo release for antifilarial drug
loaded PLGA nanoparticles were conducted in formulations were conducted in BALB/c mice.
FT-IR spectra for compatbility studies were performed of the formulations. The nanoparticles
have shown sustained release characteristics compared to intact drug administration. Stability
study conducted at 25 ± 2°C and 4 ± 2°C by measuring the size, zeta potential and drug
loading.Morphology determined by TEM images.
Conclusion
Doxycyclines shows macrofilaricidal action sustained action will increase drug efficacy and
reduce therapeutic dose.PLGA nanoparticles have better Pharmacokinetics parameters
compared to pure drug. Nanoparticulate delivery approach of doxycycline is armament for
combating deeply penetrated adult worms in lymphatic system for intervention of neglected
disease lymphatic filariasis.
Figure showing TEM Image of the PLGA-NPs
and Pharmacokinetic profile of PLGA NPs with
respect to time respectively
Reference
[1]
[2]
[3]
Mohammad Ali , Shailaja M Bhattacharya , Parasitology Research 2014, Volume 113, 681-691;
Su, Zhigui, Lei Xing, Yinan Chen, Feifei Yang,Molecular Pharmaceutics, 2014,volume 11, 1823–1834;
R. Shukla, J. Gupta, Shailaja M Bhattacharya,P R Mishra, RSC Advances,2015, 5 (85), 69047-69056
IT-34
Stimuli-Responsive Dendronized Polymers for Nanomaterials
Wen Li,* Jie Liu, Xiacong Zhang, Xiao Chen, Jiatao Yan, Afang Zhang
Department of Polymer Materials, Shanghai University, Shanghai, China
* [email protected]
Abstract
Dendronized polymers carrying linear polymer backbone and dendritic pendent groups have
attracted intense research interest due to their multivalency, nano-sizes, three-dimensional
geometry, as well as high encapsulation ability to small molecules. Combination of unique
structure characteristics of dendritic polymers with stimuli-responsive properties will broaden
their applications. Here, we present our recent research in developing a series of oligoethylene
glycol (OEG)-based dendritic (co)polymers (Figure 1), which were constructed via
conventional covalent chemistry, dynamic covalent chemistry or supramolecular host-guest
interactions.[1] These polymers are highly biocompatible and exhibit unique thermo- or pH
responsive behaviors. Their applications as nanomaterials including colorimetric sensors,
separators and drug carriers will be presented.[2] Furthermore, hydrogels constructed from
these OEG-based dendronized polymers via supramolecular and dynamic covalent chemistry
will also be introduced, which exhibit stimuli-responsive and self-healing ability. Notably,
thickness of these dendritic polymers provides switchable screening and protective ability to
the interior units through thermally-induced phase transitions. These properties make them
superior candidates for controlled transfer, release and recognition.
Figure 1.Chemical structures of the OEG-based dendronized polymers and the photo of their thermally induced
phase transition behavior.
Reference
[1] a) W. Li, A. Zhang, A. D. Schlüter, Chem. Commun. 2008, 5523; b) M. J. N. Junk, W. Li, A. D. Schlüter, et
al., Angew. Chem. Int. Ed. 2010, 49, 5683; c) J. Yan, W. Li, A. Zhang, Chem. Commun. 2014, 50, 12221.
[2] a) L. Liu, W. Li, K. Liu, et al, Macromolecules 2011, 44, 8614; b) L. Liu, W. Li, J. Yan, A. Zhang, J. Polym.
Sci., Part A: Polym. Chem. 2014, 52, 1706; c) L. Xu, L. Liu, F. Liu, et al., J. Mater. Chem. B 2015, 3, 3062.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (Nos. 21474060 and
21574078) and Shanghai Rising-Star Program (No. 16QA1401800).
IT-35
Surfactant-Free Assembly of Mesoporous Carbon Hollow Spheres with
Tunable Structural Parameters and Morphologies
Hongwei Zhang, Meihua Yu, Owen Noonan, Hao Song, Chengzhong Yu*
Australia
* Email: [email protected] (C. Y.)
Abstract
Mesoporous carbon hollow spheres (MCHS) have wide applications, including catalysis,
absorption, and energy storage/conversion. A big challenge in materials science is surfactantfree synthesis of hollow carbon nanoparticles with tunable mesostructures. Herein we report a
new surfactant-free sequential heterogeneous nucleation pathway to prepare mesostructured
hollow carbon nanoparticles. This strategy relies on two polymerizable systems, i.e.
resorcinol-formaldehyde and tetraethyl orthosilicate (TEOS), each of which undergoes
homogeneous nucleation and particle growth. By controlling the polymerization kinetics of
two systems when mixed together, sequential heterogeneous nucleation can be programmed
leading to monodispersed and MCHS with controllable mesostructures (bi- and triple-layered)
and rich morphologies (invaginated, intact and endo-invaginated spheres).[1] By simply
changing the silica precursor to tetrapropyl orthosilicate (TPOS), a co-condensation process
between the in situ generated silica primary particles and the polymer oligomers is regulated,
leading to monodispersed MCHS with adjustable pore sizes from micropores to 13.9 nm.
These particles not only show potentials in biomedical applications, but also present excellent
performance for electrochemical double-layer capacitors with high capacitance, excellent rate
capability, and outstanding cycling stability.[2]
Reference
[1]
Zhang, H. W., Yu, M. H., Song, H., Noonan, O., Zhang, J., Yang, Y. N., Zhou, L., Yu, C. Z. Chem.
Mater. 2015, 27, 6297−6304;
[2]
Zhang, H. W., Noonan, O., Huang. X. D., Yang, Y. N., Zhou, L., Yu, C. Z. ACS Nano, 2016, 10,
4579–4586
IT-36
Spacer-controlled Supramolecular Assemblies of Cu(II) with Bis(2hydroxyphenylimine) Ligands. From Monoligand Complexes to Doublestranded Helicates and Metallomacrocycles
Karsten Gloe,* Norman Kelly, Kerstin Gloe, Thomas Doert, Jan J. Weigand
01062 Dresden, Germany
*[email protected]
Abstract
The coordination chemistry of multifunctional Schiff base ligands has been the focus of a
considerable number of investigations, because they offer application possibilities in catalysis,
optics, magnetic materials, sensing, separation, etc. [1]. One of the main areas of research
relates to the self-assembly of corresponding metal complexes; gaining an understanding of
the factors that affect such processes remains a challenge. Among the ligand types studied, the
bis(2-hydroxyphenylimine) ligands linked by different spacer units has been of considerable
interest. We have employed a series of such ligands, like the examples H2L1-H2L4, as
versatile building blocks for new supramolecular architectures. In case of Cu(II) monoligand
complexes, double-stranded helicates and metallomacrocycles have been isolated and
characterized [2,3]. The different structures will be compared and discussed in detail.
References
[1]
[2]
P. A. Vigato, S. Tamburini, L. Bertolo, Coord. Chem. Rev. 2007, 251, 1311-1492;
N. Kelly, J. Schulz, K. Gloe, T. Doert, K. Gloe, M. Wenzel, M. Acker, J. J. Weigand, Z. Anorg. Allg.
Chem. 2015, 641, 2215-2221;
[3] N. Kelly, F. Taube, K. Gloe, T. Doert, W. Seichter, A. Heine, J. J. Weigand, K. Gloe, Crystals 2016, in
press.
IT-37
Amino Acid Functionalised Calixarenes and Resorcinarenes:
Synthesis and Supramolecular Chemistry
Mauro Mocerino
Department of Chemistry, Curtin University, GPO Box U1987, Perth, 6845, Australia
E-mail: [email protected]
Abstract
Calixarenes functionalised with amino acids have been studied for potential use in a number
of applications.[1][2] Calixarenes functionalised with aspartic acid or glutamic acid moieties
have been shown to have a significant impact on the growth of sparingly soluble salts such as
calcite and barite.[3] These had comparable performance to commercial scale inhibitors. A
proline-functionalised calixarene derivative has been developed that acts as a hydrogelator
where the gelation process can be switched on by the addition of electolyte solutions.[4]
Recently, this calixarene has also been shown to exhibit enantioselective inhibition of human
papillomavirus L1 pentamer formation.[5] The synthesis and supramolecular chemistry of
amino acid functionalised calixarenes and resorcinarenes will be presented.
Reference
[1] H. Jędrzejewska, M. Wierzbicki, P. Cmoch, K. Rissanen, A. Szumna, Angew. Chem. Int. Ed. 2014, 53,
13760 –13764
[2] L. Baldini, F. Sansone, G. Faimani, C. Massera, A. Casnati, R. Ungaro, Eur. J. Org. Chem. 2008, 869–886
[3] C. Y. Goh, L. Baldini, A. Casnati, F. Jones, M. Mocerino, M. I. Ogden, F. Sansone, R. Ungaro, Supramol.
Chem., 2014, 26, 488-499
[4] C. Y. Goh, T. Becker, D. H. Brown, B. W. Skelton, F. Jones, M. Mocerino, M. I. Ogden, Chem. Commun.,
2011, 47, 6057-6059.
[5] Y. Wu, D.-Y. Fu, T. Fu, Y.-X. Liu, Y. Wang, F. Li, M. I. Ogden, M. Mocerino, unpublished results
IT-38
Metal-Directed Assembly of Discrete Coordination Systems
Feng Li*
School of Science and Health, Western Sydney University, Penrith NSW 2751, Australia
*[email protected]
Abstract
The design of suitable organic ligands and the selection of the correct metal ions for favoring
structure-specific self-assembly play important roles in the construction of discrete
coordination architectures. Herein, my talk will be focused on the synthetic approach and the
structural control of coordination architectures, especially for those with multidimensional
structures. The organic components to be employed all incorporate schiff base sites motivated in part by the availability of the extremely well documented metal coordination
behaviour of these ‘classical’ coordination entities. Furthermore, characterization and
functionality of such systems will be investigated for specific applications in optical and
magnetic properties including spin-crossover (SCO).1-3
Reference
[1]
F. Reichel, J. K. Clegg, K. Gloe, K. Gloe, J. J. Weigand, J. K. Reynolds, C.-G. Li, J. R. Aldrich-Wright,
C. J. Kepert, L. F. Lindoy, H.-C. Yao and F. Li, Inorg. Chem., 2014, 53, 688-690.
[2]
L. Li, N. Saigo, Y. Zhang, D. J. Fanna, N. D. Shepherd, J. K. Clegg, R. Zheng, S.Hayami, L. F. Lindoy,
J. R. Aldrich-Wright, C.-G. Li, J. K. Reynolds, D. G. Harman and F. Li, J. Mater. Chem. C, 2015, 3, 7878-7882.
[3]
D. J. Fanna, Y. Zhang, L. Li, I. Karatchevtseva, N. D. Shepherd, A. Azim, J. R. Price, J. Aldrich-Wright,
J. K. Reynolds and F. Li, Inorg. Chem. Front., 2015, 3, 286-295.
IT-39
A Digold(I) Metalloligand System with Mixed Penicillamine and
Bis(diphenylphosphino)alkane
Takumi Konno
Department of Chemistry, Graduate School of Science, Osaka University
*[email protected]
Abstract
In recent years, considerable progress has been made in the design and creation of polynuclear
and supramolecular coordination compounds. The most common approach to create these
compounds is the coordination-driven self-assembly of well-designed organic ligands in
combination with transition metal ions. On the other hand, our interest has been directed
toward the use of thiolato metal complexes as an S-donating metalloligand. Previously, we
showed that the aurate(I) complex with two D-penicillaminates, [Au(D-pen)2]3–, functions as a
chiral multidentate metalloligand that can bind to metal ions through coordinated thiolato and
non-coordinated amine and carboxylate groups, producing a variety of chiral polynuclear and
supramolecular species. To expand the range of this chemistry, we thought it worthwhile to
introduce a digold(I) unit with bis(diphenylphosphino)alkane linker, in place of Au I atom in
[Au(D-pen)2]3–.1 Here we report on the coordination behavior of digold(I) metalloligands of
this class,2 focused on the correlation between linker lengths and molecular structures
constructed.
Reference
[1] A. Toyota, T. Yamaguchi, A. I.-Kamiyama, T. Kawamoto, T. Konno, Angew. Chem. Int. Ed. 2005, 44, 10881092: M. Taguchi, A. I.-Kamiyama, T. Kajiwara, T. Konno, Angew. Chem. Int. Ed. 2007, 46, 2422-2425; Y.
Sameshima, N. Yoshinari, K. Tsuge, A. I.-Kamiyama, T. Konno, Angew. Chem. Int. Ed. 2009, 48, 8469-8472; A.
I.-Kamiyama, T. Konno, Dalton Trans. 2011, 40, 7249-7263 (Perspective); A. Igashira-Kamiyama, A.
Fukushima, T. Konno, Chem. Eur. J. 2013, 19, 16532-16536; P. Lee, A. Igashira-Kamiyama, N. Kuwamura, N.
Yoshinari, T. Konno, Chem. Eur. J. 2014, 20, 6646-6649.
[2] R. Lee, A. I.-Kamiyama, M. Okumura, T. Konno, Bull. Chem. Soc. Jpn. 2013, 86, 908-920; Y. Hashimoto, N.
Yoshinari, D. Naruse, K. Nozaki, T. Konno, Inorg. Chem. 2013, 52, 14368-14375; K. Igawa, N. Yoshinari, and
T. Konno, Chem. Commun. 2014, 50, 15573-15576; K. Oji, A. Igashira-Kamiyama, N. Yoshinari, T. Konno,
Angew. Chem., Int. Ed. 2014, 53, 1992-1996; N. Yosinari, A. Kakuya, R. Lee, T. Konno, Bull. Chem. Soc. Jpn.
2015, 88, 59-68; N. Yoshinari, C. Li, R. Lee, N. Kuwamura, T. Konno, Inorg. Chem. 2015, 54, 8881-8883.
IT-40
Thermodynamics of Novel Spin States in Organic Charge Transfer
Complexes with Multiple Quantum Mechanical Freedoms
Yasuhiro Nakazawa*, Ryo Yoshimoto, Satoshi Yamashita, and Hiroki Akutsu
Dept. of Chemistry & Research Center for Structural Thermodynamics,
Osaka University, Japan
* [email protected]
Abstract
We report low-temperature thermodynamic properties studied by micro-calorimetry technique
for tiny single crystals of organic charge transfer complexes of -(BEDT-TTF)2Cu2(CN)3,
EtMe3Sb[Pd(dmit)2]2
and
-H3(Cat-EDT-TTF)2,
where
BEDT-TTF
is
bis(ethylenedithio)tetrathiafulvalene, dmit is 1,3-dithiole-2-thione-4,5-dithiolate and CatEDT-TTF is catechol-fused ethylenedithiotetrathiafulvalene. These compounds are known as
two-dimensional dimer-Mott systems with triangle structure with geometric frustration.
Thermodynamic features characteristic of gapless liquid-electron
spins are observed as common aspects. [1,2] We discuss magnetic field effects for these low
energy excitations from the analyses of heat capacity and magnetic entropy data. Through
detail studies of X[Pd(dmit)2]2 of which cation layers are chemically controlled by making
solid-solution of different size of cations, we derived information on the systematic variation
of electronic ground states. We observed that the spin-liquid state exists as a distinct phase
and kind of quantum phase transitions to AF and CO phases by changing chemical pressures.
The relation with spin properties and coupled with proton dynamics is discussed in H3(Cat-EDT-TTF)2 and its deuterated compound to clarify the electronic structures in such
organic compounds.
The liquid state of spins is considered as interesting bases to induce novel quantum
mechanical features. A kind of nano-layer polarization produced by the ordered arrangement
of non-symmetric counter cations part X in dimer-Mott system in X[Ni(dmit)2]2 was found to
induce curious magnetic properties of organic layers characteristic of dimer-Mott system. The
magnetic and thermodynamic measurements of these compounds show an unusual
ferromagnetic states produced by a kind of doping in the X[Ni(dmit)2]2 compounds. [3] The
doping in the frustration layer in -type spin liquids produces curious superconductive state
with strong Hc2 in its transport properties.
Reference
[1]
[2]
[3]
Y. Nakazawa and S. Yamashita, Chem. Lett. 42, 1446-1454 (2013) .
M. Soari, Y. Nakazawa, M. Nakano, and Y. Miyazaki, Chem. Rev. 113, PR41-PR121 (2013)
R. Yoshimoto, Y. Nakazawa et al., in preparation.
IT-41
Thiamacrocycle-based Coordination Polymers and Nanomaterials
Shim Sung Lee
Gyeongsang National University, Jinju 52828, South Korea
[email protected]
Abstract
Macrocyclic coordination chemistry has been a center of supramolecular science for last four
decades. Among the macrocycles, the versatility of sulfur-containing macrocycles makes
them useful because the sulfur donor favors the binding toward soft metals in either endo- or
exocyclic mode (see below).1-3 In this presentation, our results on the assemblies of the
metallosupramolecules of the thiamacrocycles are introduced.4-7 The regioisomers of the bisthiamacrocycle induce the formations of the different copper(I) iodide clusters and the
physical properties.4 Such adaptive cluster formations indicate that the interdonor distances
play decisive roles. Several [2:2] cyclization-based extra-large thiamacrocycles have been
synthesized and their metallosupramolecules such as binuclear and double-decker type
complexes are isolated.5 An NO2S2-macrocycle and its silver(I) complexes with different
coordination modes and topologies depending on the anions have been isolated.6 A
mechanistic process for the anion-induced crystal-to-crystal transformations is proposed. An
O2S2-macrocycle reacts with a mixture of CuI and HgI2 to yield the heteronuclear 2D CP1, in
which L-Cu-L-Cu chains are cross-linked by Hg2I4 linker.7 When the single crystals of CP1
was immersed in methanol, the patent crystals were transformed to the homonuclear 2D CP2
through the removal of the Hg2I4 linker. A pathway for the conversion process is also
proposed.
Reference
[1]
J. Y. Lee, S. Y. Lee, W. Sim, K.-M. Park, J. Kim, S. S. Lee, J. Am. Chem. Soc. 2008, 130, 6902.
[2]
S. Park, S. Y. Lee, K.-M. Park, S. S. Lee, Acc. Chem. Res. 2012, 45, 391.
[3]
E. Lee, S. Y. Lee, L. F. Lindoy, S. S. Lee, Coord. Chem. Rev. 2013, 257, 3125.
[4]
S. Kim, A. D. Siewe, E. Lee, H. Ju, I.-H. Park, K.-M. Park, M. Ikeda, Y. Habata, S. S. Lee, Inorg.
Chem. 2016, 55, 2018.
[5]
Y. Kang, I.-H. Park, M. Ikeda, Y. Habata, S. S. Lee, Dalton Trans. 2016, 45, 4528.
[6]
E. Lee, K.-M. Park, M. Ikeda, S. Kuwahara, Y. Habata, S. S. Lee, Inorg. Chem. 2015, 54, 5372.
[7]
S. Kim, I.-H. Park, E. Lee, H. Ju, Y. Habata, S. S. Lee, Unpublished data.
IT-42
Scalable and Cost-effective Synthesis of Highly Efficient Catalysts for
Chemical Reactions
Xiangdong Yao*
School of Natural Sciences, and Micro- and Nanotechnology Centre, Griffith University,
Nathan Campus, Qld 4111, Australia
* [email protected]
Abstract
The concept of hydrogen economy, aiming to solve the critical issues that we are facing
currently, such as the depletion of fuels and the problems caused by heavy usage of fossil
fuels, comprises mainly three challenging areas, e.g. hydrogen production from renewable
resources, high density hydrogen storage and fuel cells. Chemical reactions, such as hydrogen
and oxygen evolution (HER and OER), oxygen reduction reactions (ORR), play important
roles for hydrogen production from water splitting by electrolyers (HER and OER) and fuel
cells (ORR is the rate determining process). Unfortunately, the current commercialized
catalysts to enable the reactions are noble metals, e.g. platinum (Pt) for HER and ORR, and
Iridium or Ruthenium (Ru) oxides for OER, which hinders the large scale use of electrolysis
and fuel cells due to the scarcity and high cost of the noble metals.
Extensive research has been performed to develop non-noble metal catalysts for the
aforementioned reactions. However, the scalable fabrication and the cost of the catalysts are
still the issues. Recently, we explored simple methods to produce highly efficient
electrocatalysts in massive amount from various cheap resources including black coal, waste
seaweeds and macadamia shell. The characteristics of high activity, low cost and scalable
production for the electrocatalysts show promising potential for the applications in hydrogen
production and fuel cells.
Reference
[1] N. Ma, Y. Jia, X. Yan, X. She, L. Zhang, Z. Peng, X. Yao, D. Yang, J Mater. Chem. A 2016, 4, 6376.
[2] L. Liu, X. Yang, N. Ma, H. Liu, Y. Xia, C. Chen, D. Yang and X. Yao, Small 2016, 12, 1295.
[3] W. Zhao, P. Yuan, X. She, Y. Xia, S. Komarneni, K. Xi, Y. Che, X. Yao, D. Yang, J Mater Chem A 2015, 3,
14188.
IT-43
Synthesis of Mesoporous Carbon From Bovin Bone Gelatin And
Co/Mesoporous Carbon As Hydrocracking Catalysts of Waste
Lubricant
Trisunaryanti, W.*., Swasdika, F., Kartini, I., Sutarno, Falah, I.I, and Triyono
Department of Chemistry, Faculty of Mathematic and Natural Science, University of
Gadjah Mada, Yogyakarta, Indonesia
*email : [email protected]
Abstract
Synthesis of mesoporous carbon (MC) from bovine bone gelatin as carbon precursor and
Co/mesoporous carbon (Co/MC) as hydrocracking catalysts of waste lubricant had been
carried out. Gelatin was extracted from bovine bone pretreated with 4.0% CH3COOH
followed by 0.1 M NaOH, and 1.0 M HCl. The MC material was synthesized using bovine
bone gelatin as carbon precursor and SBA-15 as a template. The Co/MC catalyst was
synthesized by loading a small amount of cobalt into the MC using wet impregnation method.
The gelatin was analyzed by Fourier Transform Infra Red spectroscopy (FTIR) and Sodium
Dodecyl Sulfate-Poly Acrylamide Gel Electrophoresis (SDS-PAGE). The characterization of
catalyst was analyzed by FTIR, N2 adsorption-desorption, and Transmission Electron
Microscope (TEM). The activities of Co/MC catalysts was carried out in hydrocracking of
waste lubricant. The hydrocracking products including total conversion, liquid and gas
product, and selectivity for gasoline and diesel fraction were evaluated. The result showed
that the MC material has hexagonal pore structure with surface area, total pore volume, pore
diameter, and acidity of 743.22 m2/g, 1.17 cm3/g, 3.85 nm, and 4.56 mmol/g, respectively.
The Co/MC which contained Co metal of 0.14 wt.% has surface area, total pore volume, pore
diameter, and acidity each of 702.68 m2/g, 1.05 cm3/g, 3.82 nm,and 4.78 mmol/g, respectively.
The Co/MC catalyst showed catalytic activity in producing the liquid product of 36.45 wt.%
consisted of gasoline and diesel fraction of 43.71 and 56.29 wt.%.
Keywords : Gelatin, Mesoporous Carbon, Cobalt, Hydrocracking, Catalyst
IT-44
The Development of Inorganic-Organic Hybrid Nanocrystals as Precursors
for Supported Hydrodesulfurization Catalysts with Enhanced Activity and
Selectivity
Pei Yuan
China University of Petroleum, Beijing. China
*[email protected]
Abstract
We innovatively developed a novel organic-inorganic hybrid nanocrystals (HNCs) with a
core-shell structure, uniform size and good dispersion in water. Such HNCs can
spontaneously self-assemble into lamellar mesoscale nanocomposites with an alternative
arrangement of inorganic and organic layers when simply removing water and can be
disassembled into well-dispersed HNCs when the assembled nanocomposites are re-dispersed
into a large amount of water [1]. HNCs are comprised of Mo8O264- or W6O192- as the inorganic
core and long-chain quaternary ammonium cations such as cetyltrimethylammonium bromide
(CTAB) [2] or tetraethylammonium bromide cations (TEAB) as the organic shell [3].
Interestingly, using HNCs as a superior precursor, we successfully fabricated highly dispersed
NiMo/Al2O3 catalyst which exhibits the remarkably enhanced HDS performance compared
with the conventional impregnation method (as shown in Scheme 1). Such organic shell can
effectively reduce the strong metal-support interaction and facilitate Mo species depositing
onto/into the pores of γ-Al2O3 and thereby result in tuning the size and morphology of active
phases with short length and suitable stacking layer numbers. Similarly, NiW/Al2O3 HDS
catalyst with well-dispersed metal sulfide nanoparticles can be also prepared which achieves
highly selective HDS performance in hydro-upgrading fluid catalytic cracking (FCC) naphtha.
Our work points out a route to achieve the nano-scale manipulation of particle size and
morphology of supported metal sulfides, shedding a light on the rational design and
controllable fabrication of supported metal sulfide catalysts.
Reference
[1] W. Han, P. Yuan, Y. Fan, H. Liu and X. Bao, J. Mater. Chem 2012, 22, 12121-12127;
[2] W. Han, P. Yuan*, Y. Fan, G. Shi, H. Liu, D. Bai and X. Bao, J. Mater. Chem 2012, 22, 25340-25353;
[3] S. Shan, P. Yuan*, W. Han, G. Shi and X. Bao, J. Catal. 2015, 330, 288-301.
Scheme 1. Schematic diagram of the HNCs-based preparation process
IT-45
SYNTHESIS OF Cr-Al2O3/BENTONITE NANOCOMPOSITE
AS HYDROCRACKING CATALYST OF CASTOR OIL
Karna Wijaya*, Ani Devi Ariyanti*, Iqmal Tahir*
*Physical Chemistry Laboratory, Chemistry Department,
Faculty of Mathematics and Natural Science, Universitas Gadjah Mada,
Sekip Utara, Yogyakarta 55281, Indonesia
Telp./Fax.: +62-274-545188
*Corresponding author: [email protected], [email protected]
Abstract
Synthesis and characterization of Cr-Al2O3/bentonite nanocomposite as a hydrocracking
catalyst of castor oil have been conducted. The catalyst was prepared according to the
following method. At the first step, bentonite was activated using H2SO4 to obtain Hbentonite, after that the activated clay was pillarized by Al2O3, Next, a salt solution of
Cr(NO3)3•9H2O was impregnated in the pillared bentonite sample, followed by calcination
and reduction to obtain the final catalyst, i.e. Cr-Al2O3/bentonite. The catalysts including
unpillared bentonite were characterized using infrared spectrometer (FT-IR), X-Ray
diffractometer (XRD), X-ray Fluorescence spectrometer (XRF), Transmission Electron
Microscope (TEM) and gas sorption analyzer. GC-MS analysis was conducted to characterize
the hydrocracking product. The research results showed that pillarization of bentonite caused
an increasing of the basal spacing of bentonite in an amount of 1.01 nm. Although Chrom
was unevenly dispersed on the bentonite and it probably blocked the bentonite framework
resulted in the decrease of catalyst specific surface area, Cr-Al2O3/bentonite catalyst gave the
best conversion of 64.03%. The GC-MS analysis data showed that the hydrocracking products
contained various kinds of organic compounds such as acetone, acetic acid, methyl benzene,
octane, heptanal, 2-octene, 1-undecanoic acid, 9-octadecenal and 10-undecenoic acid.
Keywords : Cr-Al2O3/bentonite,nanocomposite, hydrocracking, castor oil
Reference
[1]. Jujarama, Wijaya, K., Fahrurrozi, M., and Suheryanto, 2014, Asian J.of Chem., 26, 15, 16299.
[2].Wijaya, K., Syoufian, A., and Ariantika, S. D., 2013, , Asian J of Chem., 25, 18.
IT-46
Design Efficient Catalysts for The Catalytic Conversion of Syngas to
Dimethyl Ether
Konarova Ma., J. N. Beltramini*a , W. Aslam, K.V.R. Charyb and A. Venugopalb
a
The University of Queensland , Nanomaterials Centre , St Lucia, QLD, 4072, Australia
b
Catalysis Division, Indian Institute of Chemical Technology, Hyderabad, India
* [email protected]
Abstract
Syngas-mixture of carbon monoxide and hydrogen can be derived from non-edible biomass
gasification[1]. Syngas conversion to methanol and hydrocarbons are well-developed
chemical processes where syngas is sourced from fossil fuels (natural gas or coal)[2]. Nonrenewable nature of fossil-fuel sources shifted most research activities towards development
of alternative energy sources[3]. Latest extraction technologies are not only rapidly depleting
fossil sources but also raising CO2 concentrations resulting to carbon imbalance and disturbed
ecosystem. Although, theoretical predictions to obtain CO2 neutral, renewable fuels are vastly
available, their practical applications are hampered by low priced crude oil and insufficient
experimental data. To accelerate the transition from fossil fuels to bio-based economy, we are
designing catalysts that selectively convert biomass-derived syngas into fuels (ethanol,
dimethyl ether, diethyl ether). In this talk I will present data obtained during our study for
syngas conversion to dimethyl ether; specifically, catalyst synthesis, characterization and
catalytic properties.
Methods & Characterizations
All catalysts are prepared by traditional impregnation method, where porous support alumina
are impregnated with aqueous solution of Zn, Cu, Ni and basic oxides at various ratios. The
prepared sets of sample are used for comparison purpose. To enhance active metal dispersion
and to obtain narrow particle size distribution, reverse microemulsion method is used. In the
typical experiment, non-ionic surfactant (Triton, Brij-30) is dissolved in cyclohexane (oil
phase), to this mixture aqueous solution of zinc nitrate and copper (II) nitrate are added at
ratio of 25:1 (oil:water). The formed thermodynamically stable microemulsion is then mixed
with dispersed alumina-water suspension, to destabilize the microemulsion and subsequently
transfer zinc and copper ions to the support structure (alumina). The collected filtrate is then
calcined and reduced under hydrogen flow before the catalytic test. The catalytic tests were
performed at 300°C, 30 bar, GHSV=1044 h-1 in a high-pressure fixed bed reactor setup. The
stainless-steel fixed bed reactor (i.d. 10 mm; length 100 mm) with a thermocouple positioned
inside was inserted in a furnace. The catalyst was reduced under hydrogen atmosphere at
450°C for 4 hours before the reaction. In all catalytic tests, premixed syngas with H2/CO ratio
of 2/1 and 4% of N2 (internal standard) was used as feed. The mass flow controller (MFC,
Bronkhorst High-Tech B.V) regulated the inlet gas flow rate. Gaseous products leaving the
reactor passed through the condenser to obtain the liquid fraction of products. The outlet gas
stream composition was analysed by gas chromatography equipped with a thermal
conductivity detector (Shimadzu GC-2014). Liquid samples were discharged from the
condenser every 12 hours and analysed by GC equipped with a flame ionization detector
(Shimadzu GC-8A).
Reference
[1]
R. Rauch, J. Hrbek Wiley Interdisciplinary Reviews: Energy and Environment 3 (2014) 343-362.
[2]
C. Higman, S. Tam, Chemical Reviews 114 (2014) 1673-1708.
[3]
G. Anitescu, T.J. Bruno, Energy & Fuels 26 (2012) 324-348.
IT-47
Nanoparticle Mediated Organic Synthesis (NAMO synthesis):
CuI-NP catalyzed for the Synthesis of Pharmaceutical Entities using Vit-E
analogues as Amphiphile in Water
Dr Ajay Kumar*, Manoj Kumar, Lalita, Ramandeep Kaur, Dr Manoj Kumar
UIPS, Panjab University Chandigarh, India*
[email protected]
Abstract
The use of nano transition-metal catalysts to perform organic reaction is becoming
increasingly popular. Metal nanoparticles have been enticed the synthetic chemistry due to the
edge over the heterogeneous and homogeneous catalyst. Recyclability and recovery offered
by nanoparticles catalysis keep the main advantage of heterogeneous system. CuInanoparticle catalyzed inter and intramolecular N-arylation of amines and amides using
vitamin E analogues (TPGS) as amphipile have been developed in water. Application of this
transition metal-amphiphile C-N bond formation methodology is further extended for the
synthesis substituted indole, bioactive natural product tryptanthrin and intermediates of
pharmaceutical entities such as Imatinib, Nilotinib, selective D3 agonist/antagonist ligand,
and Oxacarbazpine. The Nano CuI mediated organic synthesis (NAMO-Synthesis) in aqueous
media via micellar catalysis has immense future in application in the area of medicinal
chemistry and material science.
Reference
[1]
[2]
Atul Kumar, and Ajay Kumar Bishnoi; RSC adv., 2015, 5, 20516-20520.
Atul Kumar, and Ajay Kumar Bishnoi; RSC Adv., 2014, 4, 41631–41635.
IT-48
Near-Infrared Light Mediated Photodynamic Therapy by Upconversion
Nano-particles with Graphitic Carbon Nitride Quantum Dots
Ru-Shi Liu*
Department of Chemistry, National Taiwan University, Taipei 106 (Taiwan)
* [email protected]
Abstract
Photodynamic therapy (PDT) is a promising anti-tumor treatment that is based on
photosensitizers. This therapy kills cancer cells by generating reactive oxygen species (ROS)
after irradiation with specific laser wavelengths. Being a potential photosensitizer, graphitic
carbon nitride quantum dots (g-C3N4 QDs) is non-cytotoxic. Although the use of g-C3N4 QDs
is challenged by the limited tissue penetration of UV light, g-C3N4 QDs display excellent
ultraviolet (UV) light-triggered cyto-toxicity. The g-C3N4 QDs were synthesized using solid
phase hydrothermal method. The well-distributed hydrophilic g-C3N4 can be combined with
NaYF4:Yb3+/Tm3+ upconversion nanoparticles via the positive ligand poly-L-lysine to
produce the final nanocomposite, NaYF4:Yb/Tm-PLL@g-C3N4. Upconversion nanoparticles
can transfer infrared light into UV light and promote g-C3N4 to release blue to green visible
light to generate different images. Moreover, g-C3N4 is a promising photosensitizer in PDT
because g-C3N4 can transfer oxygen into toxic ROS. The singlet oxygen formed by g-C3N4
displays great potential for use in the treatment of cancer.
Figure. Near-infrared light mediated photodynamic therapy by upconversion nano-particles
with graphitic carbon nitride quantum dots.
IT-49
Imidazole Appended Anthracene Fluorescent Probes for Molecular
Recognition
Hong-Seok Kim
Department of Applied Chemistry, Kyungpook National University, Daegu, 41566, S. Korea
*[email protected]
Abstract
A series of imidazole appended-anthracene probes were designed and synthesized for
selective recognition of phenol derivatives such as 3,5-dinitrosalicylic acid and
pentafluorophenol [1,2].
Herein, we developed novel imidazole-appended diaminomethylanthracene “turn on” probe P,
and anthracenedicarboxamide “turn off” probe PA. Probe P selectively detected Zn2+ ions
through the “turn on” mode with 1:1 binding stoichiometry in 80% aqueous DMSO. Selective
off-on mode of recognition occurred in the P after the complexation, mainly due to the
inhibition of photo induced electron transfer (PET) as well as chelation induced enhanced
fluorescence (CHEF) effects. The in-situ generated P●Zn2+ (1:1) ensemble sequentially
detected the phosphate ions by “turn off” mode by extruding Zn2+ ions from ensemble. The
nano level molecular logic gate operations based on probe P fluorescence emission intensity
modulations Zn2+/phosphate ions response and pH profile will be presented. Probe PA
selectively detected 2,4,6-trinitrophenol (TNP) relative to other nitrophenol derivatives
through the ratiometric fluorescence response in 1:1 EtOH-H2O with 1:2 binding mode. The
mechanism and application will be discussed.
H
N
N
N
H
N
P
N
N
O
H
N
N
O
N
H
N
PA
N
N
References
[1]
[2]
A. Pandith, A. Kumar, J.-Y. Lee, H.-S. Kim, Tet. Lett., 2015, 56, 7094-7099.
A. Pandith, A. Kumar, H.-S. Kim, RSC Adv., 2015, 5, 81808-81816.
IT-50
Particle Assisted Laser Desorption/Ionization Mass Spectrometry as an
Advanced Diagnostic Tool
Kun Qian*
School of Biomedical Engineering, Med-X Research Institute, Shanghai Jiao Tong University,
Shanghai 200030, P. R. China.
*[email protected]
Abstract
Profiling and quantitation of small metabolites are essential for monitoring the physiological
and pathological process in bio-systems and can lead to the set-up of new biomarkers
benchmark.1-3 Despite that mass spectrometry (MS) enjoys huge application benefits over
traditional methods, present MS approaches, particularly laser desorption/ionization (LDI)
MS techniques, urgently need novel particles as efficient matrices and their LDI mechanism is
still to be explored, in order to overcome the major limitations in terms of selectivity,
throughput, accuracy, and practicability for metabolic diagnostics in clinical laboratory. In
this talk, we showed our recent progress on the design of inorganic particles as new matrices
for LDI MS analysis and their practical application in detection of small metabolites in biofluids for advanced molecular diagnostics.
Reference
[1]
Nicholson, J. K.; Connelly, J.; Lindon, J. C.; Holmes, E. Nat. Rev. Drug Discov. 2002, 1, (2), 153-161.
[2]
Georganopoulou, D. G.; Chang, L.; Nam, J. M.; Thaxton, C. S.; Mufson, E. J.; Klein, W. L.; Mirkin, C.
A. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, (7), 2273-2276.
[3]
Elliott, P.; Posma, J. M.; Chan, Q.; Garcia-Perez, I.; Wijeyesekera, A.; Bictash, M.; Ebbels, T. M.;
Ueshima, H.; Zhao, L.; van Horn, L. Sci. Transl. Med. 2015, 7, (285), 285ra62-285ra62.
IT-51
Photo-induced Binding of [60]Fullerene with Aza-Crown Macrocyclic
Ligand Tweezer Tethered through an Azobenzene Linker
a
Bahram Ghanbaria*, Mahsa Mahdaviana, Niloofar Mahloojia
Department of Chemistry, Sharif University of Technology, Tehran, Iran, PO Box 111553516
*[email protected]
Abstract
Since the first purposely report on the designed hosts for fullerenes by Ringsdorf group [1]
which was consisted of aza-crown ethers bearing appropriate alkyl chains on the nitrogens,
the trapping of fullerenes by aimed hosts have attracted extensive attention of researchers. In
our previous works [2], the effect of macrocycle ring size in benzo-azacrown macrocyclic
ligands of types O2Nx (x=2,3) as donor or host molecules in complexation with [60]Fullerene
were investigated. Herein, we report the synthesis of a new tweezer-like molecule containing
azobenzene group in a multistep route.
Fig. 1. The general structure of L (right), and its photo-isomerization recorded by UV-vis spectroscopy in chloroform (left).
The spectra in Fig. 1 revealed that L existed in both cis-trans isomers in the solution. More
complementary experiments illustrated that the superior complex formation of the cis isomer
with [60]Fullerene could facilitate during the trans-to-cis isomerization of L. Besides, 1H
NMR studies suggested a significant association constant (Ka = 2500 M-1) for [60]Fullerene/L
which was 8 times larger than Ka value reported for its parent macrocyclic ligand [2a]. Taking
into account structural and electronic optimization of [60]Fullerene/L employing DFT
calculations using the B3LYP functional and 3-21G basis set, confirmed on large tendency of
[60]Fullerene for stabilization of cis-L isomer.
Reference
[1] F. Diederich, J. Effing, U. Jonas, L. Jullien, T. Plesnivy, H. Ringsdorf, C. Thilgen, D. Weinstein,
Angewandte Chemie International Edition 1992, 31, 1599-1602.
[2] (a) B. Ghanbari, M. Alishah Aratboni, Fullerenes, Nanotubes Carbon Nanostructures 2013, 21, 394-402; (b)
B. Ghanbari, N. Mahlooji, Fullerenes, Nanotubes and Carbon Nanostructures 2014, 22, 322-331; (c) B.
Ghanbari, P. Gholamnezhad, M. Hatami, Journal of Thermal Analysis and Calorimetry 2014, 118, 1631-1637.
IT-52
Will Nanopowders be the “Sixth” Ingredient of Concrete in the Future?
Zuhua Zhang 1*, Jin Zou 2, Hao Wang 1*
1. Centre for Future Materials, University of Southern Queensland,
2. School of Mechanical and Mining Engineering and Centre for Microscopy and
Microanalysis, The University of Queensland
* [email protected]; [email protected]
Abstract
Concrete is the largest material commodity used by the society. It forms the base of our
modern life. The annually global production of concretes is estimated as 25 billion tonnes (10
billion m3), with massive impact on the environment, in terms of natural resources usage,
energy consumption, and CO2 emissions (contributes ~10% global emission). Any technology
breakthrough may bring sustainability effect to the cement and concrete industry and entire
society as well, given the large production volume. The recent scientific research has led to
the development of nanopowder blended Portland cement concrete that has shown the
potential of using nanopowders in reducing water demand, pore sizes and porosity, and
increasing strength and durability, which all mean the possibility of using less
cement/concrete to meet the structure strength requirements. Will nanopowders become the
‘sixth’ ingredient of developing high performance concrete in the future, bringing another
revolution in concrete industry like the use of ‘fifth’ ingredient - chemical agents, such as
superplasticizer, in reducing water/cement ratio and increasing concrete strength? The other
four basic components are cement, coarse aggregates, fine aggregates and water. This
presentation reviews the impact of nanopowders in the hydration process of Portland cement,
the microstructure features of calcium silicate hydrates (C-S-H), the rheology and hardening
behaviour of freshly mixed binder and concrete. The perspectives of using nanopowders in
large manufacturing are also discussed based on the most recent developed theory of C-S-H
nanostructure and nanomechanics, and the life cycle analysis for sustainability consideration.
Fig. 1. Particle size vs. specific surface area in concrete materials and the role of nano technology [1]
Reference
[1] K. Sobolev, M. Ferrara, Am. Ceram. Bull. 2005, 84, 14–17.
IT-53
Functional Nanoporous Graphene for Electrochemical Energy Storage
Xiaodan Huang, Chengzhong Yu,*
Brisbane, QLD, 4072 (Australia)
* [email protected]; [email protected]
Abstract
Constructing nanoporous architectures with graphene building units has attracted vast
interests owning to the combined functionalities of porous structure and graphene materials.
The extraordinary properties of nanoporous graphene materials, such as high surface area,
large pore volume, controllable pore size, and excellent electronic conductivity, enable them
to serve as key components in high-performance electrochemical energy storage and
conversion devices such as rechargeable lithium batteries, supercapacitors and Al-ion
batteries. This talk will introduce the controllable synthesis of nanoporous graphene materials
by both hard and soft template methods. The synthetic mechanisms and the applications of the
products will also be presented.
IT-54
Titanium Tetraiodide Mediated Organic Transformations
Makoto Shimizu
Department of Chemistry for Materials, Graduate School of Engineering
Mie University, Tsu, Mie 514-8507, Japan
* [email protected]
Abstract
Titanium(IV) iodide [1] is a rare molecular binary metal iodide, consisting of isolated
molecules of tetrahedral Ti(IV) centers. TiI4 can be distilled without decomposition at one
atmosphere (bp 377 oC). It is also conveniently purified by sublimation (180 °C / 0.8 mmHg).
The compound is a close relative to TiCl4. The difference in melting point between TiCl4 (m.p.
-24 °C) and TiI4 (m.p. 150 °C) is comparable to the difference between the melting points of
CCl4 (m.p. -23 °C) and CI4 (m.p. 168 °C), reflecting the stronger intermolecular van der
Waals bonding in the iodides. Regarding the use of titanium halides in organic synthesis,
although titanium tetrachloride is frequently used in Mukaiyama type aldol reaction and
pinacol coupling reaction via low valent species, titanium iodide is rarely used for such
reactions. Recent studies show that titanium tetraiodide is an excellent reagent for the
-halo carbonyl or imino compounds, and the
subsequent reactions with carbonyl compounds give aldol products in good yields. Regarding
-imino carbonyl
compounds were chemoselectively reduced with TiI4
-hydroxy- or amino ketones,
respectively. Subsequent reactions with aldehydes or imines realize the selective formation of
1,2-diol or diamine derivatives. Pinacol coupling of aromatic and unsaturated aldehydes was
effciently promoted by titanium tetraiodide in propionitrile to give the l,2-diol derivatives
with high selectivities in high yields. Chemoselecdve deoxygenation of sulfoxides was also
carried out successfully to give sulfides in good to excellent yields. In this presentation the
following three types of reactions are discussed.[2]
(1) Use as Lewis acid
(2) Iodination reaction
(3) Reduction
Reference
[1] (a) W. B. Blumenthal, H. Smith, Ind. & Eng. Chem., 1950, 42, 249-251. (b) R. N.Lowry , R. C. Fay, B. L.
Chamberland, Inorg. Synth., Vol. X, 1967, pp 1-6. (c) E. G. M. Tornqvist, W. F. Libby, Inorg. Chem., 1979, 18,
1792-1796. (d) L. Jongen, T. Gloger, J. Beekhuizen, G. Meyer, Z. Anorg. Allg. Chem., 2005, 631, 582-586
[2] (a) I. Hachiya, M. Shimizu，Tetrahedron Lett., 2014, 55, 2781-2788. (b) T. Haneishi, I. Hachiya,
M. Shimizu, 2014, Arab. J. Sci. Eng., 39, 6599-6616. (c) M. Shimizu, I. Hachiya, J. Inanaga, "Metal
Iodides–Mediated Reaction" in Iodine Chemistry and Applications, ed by T. Kaiho, Wiley-Blackwell,
Hoboken, NJ, USA, 2014, pp 329-352.
IT-55
Silver Complexes with novel Inorganic 8-Membered Macrocycles
Sivathmeehan Yogendra, Felix Hennersdorf, Roland Fischer, Kerstin Gloe, Karsten Gloe, Jan
J. Weigand*
01062 Dresden, Germany.
* [email protected]
Abstract
A high-yielding and facile synthesis for diphosphane monochalcogenides and their
constitutional isomers, diphosphanylchalcoganes was developed, featuring a condensation
reaction between chlorophosphanes (R2PCl), and sodium chalcogenides (Na2Ch, Ch = S, Se,
(Te)). The optimized protocol selectively yields either R2(Ch)PPR2Ch(PR2)2 depending upon
the steric demand of the substituents R. Reaction pathways consistent with the distinct
reaction outcomes are proposed. The application of these new complexes as an interesting
class of ligands is exemplarily demonstrated by the preparation of selected transition metal
complexes.[1,2] This condensation protocol can also be used to access novel inorganic 8memberd macrocycles which are suitable for the coordination of silver cations to give di- and
tetra-nuclear silver complexes.
Reference
[1]
P. S. Sues, A. J. Lough, R. H. Morris, Chem. Commun. 2014, 50, 4707–4710.
[2] S. Yogendra, S. S. Chitnis, F. Hennersdorf, M. Bodensteiner, R. Fischer, N. Burford, J. J. Weigand; Inorg.
Chem., 2016, 55, 1854-1860.
IT-56
Coordination networks based on N,N,N,́N´-tetrakis(pyridine-4yl)methanediamine
Kil Sik Min,*1 Ah Rim Jeong,2
1
Department of Chemistry Education, Kyungpook National University, Daegu 41566,
Republic of Korea
2
Department of Chemistry, Kyungpook National University, Daegu 41566, Republic of Korea
* E-mail: [email protected]
Abstract
Infinite coordination networks, for example, metal-organic framework (MOF), have attracted
much attention in chemistry, material science and the chemical industry because of their
potential and/or practical applications for molecular recognition, catalysis, magnetism, and
separation. As a building unit for the construction of MOFs, a novel ligand, N,N,N´,N´tetrakis(pyridine-4-yl)methanediamine (tpmd) including 4,4'-bipyridine moieties, has been
prepared and characterized. From the self-assembly of transition metal ions (Zn, Cd, Ag) and
the tpmd ligand, we have prepared and characterized a variety of multidimensional metalorganic frameworks. Two zinc(II) and cadmium(II) MOFs based on the tpmd are shown
interesting structures, catalytic activities, and photoluminescence properties by hydration and
dehydration. Three silver(I) coordination polymers have been obtained by the self-assembly
of AgX (X = NO3, CF3SO3, CF3CO2) and tpmd in MeOH/MeCN. The coordination
geometries of silver(I) ions are distorted tetrahedral structures and a distorted trigonal
bipyramid, respectively. All feature three-dimensional coordination polymers formed by
coordination of the silver(I) ions to the tpmd ligands and display strong emissions at 331, 342,
and 326 nm, respectively. By changing
anion, a new porous coordination polymer
with Cd(II) ion, NaNCBH3, and tpmd
ligand has been synthesized by the selfassembly in a dry box. Each Cd(II) ion has
a distorted octahedral geometry with the
four nitrogen atoms of tpmd ligands and
two nitrogen atoms of NCBH3 anions and
extended into three-dimensional porous
MOF through the linkage of four tetraconnected tpmd ligands and four tetraconnected Cd(II) ions. In this presentation,
we will describe the detailed preparation,
structure, photoluminescence, and sorption
properties.
Reference
[1]
J. W. Shin, K. S. Min, Acta Cryst. E 2012, 68, o1600.
[2]
J. W. Shin, J. M. Bae, C. Kim, K.S. Min, Inorg. Chem. 2013, 52, 2265-2267.
[3] J. W. Shin, K. S. Min, Bull. Korean Chem. Soc. 2016, 37, 19-26.
IT-57
Amplification of Chirality by
Ag Complexes with Chiral-Argentivorous Molecules
+
Mari Ikeda,1 Yasuhiro Hosoi,2 Chizuko Okazaki,2 Shunsuke Kuwahara2,3 and
Yoichi Habata,*2,3
1
Department of Chemistry, Education Centre, Faculty of Engineering, Chiba Institute of
Technology, Narashino, Chiba 275-0023, Japan
2
Department of Chemistry, Faculty of Science & 3Research Centre for Materials with
Integrated Properties, Toho University, Funabashi, Chiba 274-8510, Japan
*[email protected]
Abstract
It is well known that “cyclen” is a 12-membered
cyclic tetraamine that forms stable complexes
with typical and transition metal ions. It is also
known that Ag+ ions interact with aromatic rings
by the Ag+–
orbital) of Ag+ and HOMOs of aromatic rings.1
Recently, we have reported2 that tetra-armed,
triple-armed, and double-armed cyclens with
aromatic side-arms behave like an insectivorous
plant (Venus flytrap) when they form complexes
with Ag+. The aromatic side-arms in the armedcyclens cover the Ag+ incorporated into the
cyclen cavities by Ag+–
–
We named the armed cyclens argentivorous
(silver-eating) molecules. “Argentivorous” is a
coined word that was made by a combination of
argentum (silver) and vorous (eating) in the Latin.
It is important to note that argentivorous is
different from argentophilic. Argentophilic is
used in the sense of Ag+–Ag+ interactions.3
Here we report amplification of chirality by Ag+ complexes with chiral argentivorous
molecules (1 and 2).
Reference
[1] R. S. Mulliken, J. Am. Chem. Soc. 1952, 74, 811.
[2] Y. Habata, M. Ikeda, S. Yamada, H. Takahashi, S. Ueno, T. Suzuki and S. Kuwahara, Org. Lett. 2012, 14,
4576 ; Y. Habata, A. Taniguchi, M. Ikeda, T. Hiraoka, N. Matsuyama, S. Otsuka and S. Kuwahara, Inorg.
Chem. 2013, 52, 2542; Y. Habata, Y. Oyama, M. Ikeda and S. Kuwahara, Dalton Trans. 2013, 42, 8212
(Front cover paper); Y. Habata, Y. Okeda, M. Ikeda and S. Kuwahara, Org. & Biomol. Chem. 2013, 11,
4265; Y. Habata, J. Kizaki, Y. Hosoi, M. Ikeda and S. Kuwahara, Dalton Trans. 2015, 44, 1170.
[3] H. Schmidbaur and H. Schier, Angew. Chem. Int. Ed. 2015, 54, 746.
IT-58
Structural Dynamics of Guest-Modified 2D Cyano-Bridged Frameworks
Ryo Ohtani,* Yuu Kitamura, Riho Yamamoto, Shinya Hayami
Department of Chemistry, Graduate School of Science and Technology, Kumamoto Univ.
*[email protected]
Abstract
Structural dynamics in coordination polymers have attracted much attention for development
of responsive materials against external stimuli. We have focused on guest molecules to tune
the dynamics of frameworks that exhibit spin transition and thermal expansion behavior. We
constructed host-guest composites and investigated their properties. Here, we focused on two
dimensional (2D) cyano network CPs consist of a [Mn(salen)]+ unit and a [Mn(N)(CN)4]2metalloligand. The [Mn(N)(CN)4]2- has a distorted square pyramidal coordination geometry
producing zigzag layers with a guest interactive site. We investigated guest dependent
anisotropic thermal expansion behavior of the 2D CPs.
[Mn(salen)]2[Mn(N)(CN)4]·guest (guest = MeOH (1MeOH) and MeCN (1MeCN)) were
synthesized by mixing [Mn(salen)]Cl and [PPh4]2[Mn(N)(CN)4] at a ratio of 2 : 1 in MeOH
and MeCN, respectively. Guest molecules, MeOH and MeCN, coordinated to the open metal
site of [Mn(N)(CN)4]2- and removed at 450 K. Their thermal expansion behavior was
investigated in a temperature range from 150 K to 450 K by variable temperature single
crystal and powder X-ray diffraction measurements. 1MeOH showed an anisotropic thermal
expansion behavior including in-plane shrinkage and interlayer expansion while 1MeCN
showed a different anisotropic behavior with the opposite directions. The different behavior
are caused by different lengths of guest molecules showing steric hinderance in their hostguest composites.
Reference
[1] R. Ohtani, S. Egawa, M. Nakaya, H. Ohmagari, M. Nakamura, L. F. Lindoy, S. Hayami, Inorg. Chem. 2016,
55, 3332
[2] R. Ohtani, M. Nakaya, H. Ohmagari, M. Nakamura, K. Ohta, L. F. Lindoy, S. Hayami, Sci. Rep. 2015, 5,
16606
[3] R. Ohtani, K. Shimayama, A. Mishima, M. Ohba, R. Ishikawa, S. Kawata, M. Nakamura, L. F. Lindoy, S.
Hayami, J. Mater. Chem. C 2015, 3, 7865
[4] R. Ohtani, M. Inukai, Y. Hijikata, T. Ogawa, M. Takenaka, M. Ohba, S. Kitagawa, Angew. Chem. Int. Ed.,
2015, 54, 1139.
IT-59
Supramolecular Chemistry of Cucurbit[n]uril with Tetravalent Actinide
ions
Yingjie Zhang,a,* Mohan Bhadbhade,b Max Avdeev,a Inna Karatchevtseva,a Jason R. Price,c
Kim Lu,a Gerry Triani,a Qing Li,d Feng Lie Zhu Tao,d and Gang Weif
a
Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC,
NSW 2232, Australia
b
Mark Wainwright Analytical Centre, University of New South Wales, Kensington NSW 2052,
Australia
c
Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168, Australia
d
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province,
Guizhou University, Guiyang, Guizhou 550025, P. R. China
e
School of Science and Health, Western Sydney University, Locked Bag 1797, Penrith, NSW
2751, Australia.
f
CSIRO Manufacturing Flagship, PO Box 218, Lindfield, NSW 2070, Australia.
* [email protected]
Abstract
The cucurbit[n]urils {Q[n]s} each contain a rigid hydrophobic macrocyclic cavity with two
identical opposite portals rimmed with carbonyl groups. Their complexes with alkali and
alkaline earth metal ions have been well-documented. In addition, their complexes with
selected transition metal ions are also available. In the last ten years, the coordination
chemistry of {Q[n]} with lanthanide(III) ions has been extensively studied, greatly motivated
by the fact that Q[n] can form slightly different structures with lanthanide ions, suggesting the
potential of using Q[n] for lanthanide separations. As for actinide ions, advances on the
structure chemistry of uranyl ions (UO2)2+ with Q[5-8] have been made. However, tetravalent
actinide ions have been less studied with only two discrete structures reported so far, both for
Q[6] with thorium(IV) (Th4+) ion: one with two Th4+ ions on each side of the portals of Q[6]
making it a dinuclear Th4+ complex and the other with only second shell interactions between
hydrate Th4+ ion and Q[6]. We present the first systematic study on the structures of fourteen
Q[5-8] complexes with Th4+/U4+ ions via direct complexation and supramolecular assembly in
neutral to acidic solutions.
IT-60
ECR/Students Oral Presentation
Abstracts
13-16 July 2016
Synthesis of Novel Silica Vesicles and Their Pharmaceutical and Cosmetic
Applications
Jun Zhang, Chengzhong Yu*
Australia
* [email protected]
Abstract
Silica hollow spheres show advantages in high pore volume and specific surface area, tunable
structural parameters and chemical/thermal stability compared to organic counterparts, thus
they have been considered to be advantageous nano-carriers for various cargos. This
presentation introduces the development of novel silica vesicles (SV, silica hollow spheres
synthesized with cooperative vesicle templating method) with finely controlled structures for
therapeutical and cosmetic applications. Firstly, a systemic study has been carried out to
investigate the structure-release behavior relationship of a series of silica nanoparticles using
volatile (-)-menthol as a model drug. It is revealed that pore size, structure, wall thickness and
surface functionality of nanoporous silica materials are four important parameters that
influence the isothermal release properties. SV with thick wall and hydrophobic functional
groups were shown to possess the slowest release performance. Precise control on the the
entrance sizes of SV for therapeutical protein carriers has then been achieved via a two-step
synthesis approach. The optimized SV show high loading, sustained release and cellular
delivery of model therapeutical proteins. The skin safety of the SV has also been evaluated in
an ex vivo pig skin model for the potential application in cosmetics. It is demonstrated that SV
with a lower density are skin friendly and penetrate only in the upper part of stratum corneum
compared to dense nanoparticles with the same size. A hydrophobic organic UV absorber has
been loaded in SV exists in an amorphous state, which exhibits superior UV-attenuating
efficiency and an extremely high sun protection factor in sunscreen formulations.
Figure 1. Schematic representation of silica vesicle with finely controlled structure as
advantageous nano-carriers in drug/protein delivery and in sunscreen applications.
ECR-01
Efficiency of MoS2/C nanocatalysts anchored with promoters (Ni, Co) for
hydrodeoxygenation of guaiacol
Swathi Mukundan, Luqman Atanda, Muxina Konarova and Jorge Beltramini*[a]
Nanomaterials center- AIBN, The University of Queensland
* [email protected]
Abstract
Synthesis of highly active MoS2 nanocatalysts anchored with Ni or Co nanocrystallites by
microemulsion technique (ME) and their efficacy in hydrodeoxygenation of lignin model
compound- guaiacol were demonstrated. Depending on the promoter, final products of
guaiacol differ forming phenol (MoS2/C), cyclohexane (NiMoS2/C) and benzene (CoMoS2/C),
respectively. These results indicate if desired products from intact lignin are aromatics, cobalt
promoted molybdenum sulphide is best suited for complete deoxygenation. The synthesised
nanocatalysts were characterized using analytical techniques such as XRD, nitrogen
physisorption, Raman spectroscopy, FE-SEM, HR-TEM, ICP, XPS, and TPR. TEM of assynthesised catalysts revealed uniformly dispersed short sulphide layers (length∼ 4nm) on the
activated carbon. Catalyst activity was retained even after three cycles, retaining catalytic
active edges consisted of short layers and high stacking (up to 7 layers) with a minimal
sulphur leaching, maintaining S: Mo= ∼2. Thus, ME technique resulted in highly active and
robust MoS2 catalysts favoring deoxygenated products.
Fig. 1. HR-TEM images of (a) MoS2/C (b) NiMoS2/C and (c) CoMoS2/C catalysts.
Fig. 2. Catalyst reusability study showing the yield of products, mol % for the guaiacol conversion by
(a) MoS2/C (b) NiMoS2/C (c) CoMoS2/C catalysts at 5 h of reaction.
ECR-02
The Textural Properties of Zirconia Pillared Bentonite
Ahmad Suseno1,2*, Karna Wijaya1 , Wega Trisunaryanti1, Roto1 and Priyono3
1 Department of Chemistry , Faculty of Mathematics and Natural Sciences, Gadjah Mada
University, Bulaksumur, Jogjakarta, Indonesia
2 Department of Chemistry, Faculty of Sciences and Mathematics, Diponegoro University,
Tembalang, Semarang, Indonesia
3 Department of Physic, Faculty of Sciences and Mathematics, Diponegoro University,
Tembalang, Semarang, Indonesia
*[email protected]
Abstract
Zirconia pillared bentonite is interest for use in catalysis as a support or catalyst. In this study,
natural bentonite from Indonesia was used in the preparation of pillared bentonite intercalated
by zirconia. The mixture is obtained by mixing suspensions of bentonite and zirconium
chloride octahydrate solution followed by drying (at 343 K) and calcination (at 673 K). The
changes in the specific surface area; the pore volumes are studied by varying the zirconia
concentration in the composite. The XRD, T E M a n d Nitrogen adsorption results of the
composite indicated that zirconia was successfully distributed as pillar. The analysis showed
that the surface area and pore volume of ZrO2 pillared bentonite increased from 52.830 m2/g
and 0.152 cc/g into 269.165 m2/g and 0.204 cc/g. The XRD and TEM analysis also showed that
the presence of metal oxide ZrO2 was able to increase the basal spacing of 1.38 to 1.89 nm and
did not damage the structure of bentonite.
Key word : pillared bentonite; zirconia; surface area;spacing
ECR-03
Planar-Vacancy Engineered Sn1-xBixTe Nanoribbons
Yichao Zou,1 Zhi-Gang Chen*,1 Fantai Kong,3 Jing Lin,1 John Drennan,4 Kyeongjae Cho,3
Zhongchang Wang,2 Jin Zou*,1,4
1
Materials Engineering, University of Queensland, Brisbane, QLD 4072, Australia
2
WPI, Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aobaku, Sendai 980-8577, Japan
3
Department of Materials Science & Engineering, The University of Texas at Dallas,
Richardson, TX 75080, USA.
4
Centre for Microscopy and Microanalysis, University of Queensland, Brisbane, QLD 4072,
Australia.
* [email protected] *[email protected].
Abstract
Vacancy engineering is a crucial approach to manipulate physical properties of
semiconductors.[1-3] However, few experiments have been investigated to explore the
vacancy engineering in tin chalcogenides, especially in their nanosystem. Here, we
demonstrate a new form of planar vacancies that can be effectively engineered in Sn 1-xBixTe
nanoribbons by using Bi dopants via a facile chemical vapour deposition. Through
combination of sub-ångström-resolution imaging and calculation within density functional
theory, these planar vacancies are found to be associated with Bi segregations, which
significantly lower the formation energies of the vacancies. The planar vacancies exhibit
polymorphic structures with local variations in lattice relaxation level, determined by their
proximity to nanoribbon surface. Such polymorphic planar vacancies, in conjunction with Bi
dopants, trigger distinct localized electronic states, offering new device platforms for ternary
chalcogenide materials.
Reference
[1]
Voneshen, D. J.; Refson, K.; Borissenko, E.; Krisch, M.; Bosak, A.; Piovano, A.; Cemal, E.; Enderle,
M.; Gutmann, M. J.; Hoesch, M.; Roger, M.; Gannon, L.; Boothroyd, A. T.; Uthayakumar, S.; Porter, D. G.;
Goff, J. P. Nat. Mater. 2013, 12, 1028-1032.
[2]
Kim, C. E.; Kurosaki, K.; Ishimaru, M.; Jung, D. Y.; Muta. H.; Yamanaka, S. Phys. Status Solidi RRL
2009, 3, 221-223.
[3] Wang, Z.; Xu, K.; Li, Y.; Zhan, X.; Safdar, M.; Wang, Q.; Wang, F.; He, J. ACS Nano 2014, 8, 4859-4865.
ECR-04
SYNTHESIS OF C-2-ETHOXYPHENYLCALIX[4]RESORCINARENA
AND APLICATION ITS AS ANTIOXIDANT
Santi Nur Handayani1,2*, Jumina1*, Mustofa3 dan Respati Tri Swasono1
1
Department of Chemistry, Faculty of Mathematics and Natural Sciences University of
Gadjah Mada
Sekip utara Yogyakarta 55281, indonesia
2
Department of Chemistry, of Mathematics and Natural Sciences, University of Jenderal
Soedirman
Jl. Dr. Suparno Karangwangkal Purwokerto, 53123 Indonesia
3
Pharmacology and Therapy Unit, Faculty of Medicine, University of Gadjah Mada
Yogyakarta
Corresponding Author Telp: + 62-8156550910
* [email protected] dan [email protected]
[email protected]
Abstract
C-2-ethoxyphenylcalix[4]resorcinarene can be synthesized in 2 steps; i.e. ethylation of 2hydroxybenzaldehyde with diethyl sulphate (DES) and condensation of 2ethoxybenzaldehyde and resorcinol with acid catalyst. Structural elucidation of products was
performed using FT-IR spectrophotometer, GC-MS, 1H NMR and 13C NMR. The product of
condensation was subjected to antioxidant assays using DPPH(1-1-diphenyl-2-picrylhydrazyl)
method.
Reaction of 2-hidroxybenzaldehyde, DES, and NaOH was performed by refluxing the
mixture for 2.5 hours and gave 2-ethoxycalix[4]resorcinarene in viscous dark yellow 84.68 %
yield. The aromatic electrophilic substitution-cyclization of ethylation product and resorcinol
in presence of HCl gave C-2-ethoxyphenylcalix[4]resorcinarena as yellow solid in 99.26 %
yield with m.p > 380 oC. The product 2-ethoxybenzaldehyde was analyzed with infra red (FTIR) spectrophotometer and GC-MS. The product 2-ethoxy-phenylcalix[4]resorcinarene was
analyzed with FT-IR, 1H NMR and 13C NMR. It has strong antioxidant activity in DPPH
methods with ES50 83.62 ppm.
Keywords : synthesis, antioxidant assay, 2-ethoxyphenylcalix[4]resorcinarene
ECR-05
Development of High-Performance Bismuth Telluride-Based
Thermoelectric Nanomaterials through Structure manipulating and Band
Engineering
Min Hong1, Zhi-Gang Chen1* and Jin Zou1, 2*
1
Materials Engineering, University of Queensland, Brisbane, QLD 4072, Australia
2
Centre for Microscopy and Microanalysis, University of Queensland, Brisbane, QLD 4072,
Australia
*[email protected], [email protected]
Abstract
Thermoelectrics enabling the direct conversion between heat and electricity are a potential
solution for the environmental pollutions and the up-coming energy crisis.[1] Thermoelectric
efficiency is evaluated by the figure of merit ZT (ZT=S2σT/κ, where S is Seebeck coefficient, σ
is electrical conductivity κ is thermal conductivity, and T is the working temperature).[2]
Currently, the low ZT especially for n-type materials restrains the application of
thermoelectric devices, which require the synergetic developments of n- and p-type systems.[3]
Here, we employed a fast microwave-assisted solvothermal approach to successfully fabricate
large-scale and Bi2Te-based nanostructures including n-type Bi2Se3 nanosheets,[2] Te/Bi2Te3
hierarchical nanostructures,[3] Bi2Te3-xSex nanoplates and p-type BixSb2-xTe3.[1] The obtained
Bi2Te-based nanostructures exhibit enhanced ZT due to the remarkably low κ and preserved
high S2σ. From the advanced electronic microscopy characterisations and theoretical
simulations, the high dense grain boundaries and dislocations induce to super low κ.
Moreover, ternary phases or structure design can effectively tune band structures to reserve
the high S2σ, which is synergetic with lower κ to finally result in higher ZT compared with the
similar material systems (refer to Figure 1 for the ternary phases as an example). These
studies indicate that high-performance Bi2Te-based thermoelectric nanomaterials can be
achieved through structure manipulating and band Engineering.
Figure 1 Our ZT of a) Bi2Te3-xSex, and b) BixSb2-xTe3 compared with the reported values.
Reference
[1]
M. Hong, Z. G. Chen, L. Yang, J. Zou, Nano Energy 2016, 20, 144.
[2]
M. Hong, Z.-G. Chen, L. Yang, G. Han, J. Zou, Adv. Electron. Mater. 2015, 1, 1500025.
[3]
M. Hong, Z. G. Chen, L. Yang, J. Zou, Nanoscale 2016, DOI: 10.1039/C6NR00719H.
ECR-06
Synthesis and Structural Determination of Metal Complexes with a
Julolidine-quinoline Based Ligand
Daniel J. Fanna,a* Dr Yingjie Zhang,b Dr Jason K. Reynolds,a Feng Lia
a
School of Science and Health, Western Sydney University, Locked Bag 1797 Penrith, NSW 2751, Australia
b
Australian Nuclear Science and Technology Organisation, Locked Bag 2001Kirrawee DC, NSW 2232,
Australia
*[email protected]
Abstract
The synthesis and structural determination of metal-coordinated julolidine-quinoline based
optical sensor systems were undertaken. The optical sensor, a Schiff base ligand HL, is
assembled through the condensation between 8-hydroxyjulolidine-9-carboxaldehyde and 8aminoquinoline molecular units.[1] Complexation was conducted with transition metal ions
(Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II)), and lanthanide metal ions (Eu(III) and
Gd(III)). Single crystal X-ray structures measured at synchrotron facilities show different
structural arrangements between metal ions. Complexes of Fe(III), Co(II) and Ni(II) exhibit
dimer structures. Coordination with Cu(II) resulted in a monomer arrangement. While
complexes of Mn(II), Zn(II), Eu(III) and Gd(III) result in bridged dinuclear structures.
Investigation of the optical properties in solution demonstrates that this ligand is not only
sensing for Co(II),[1] but also can act as a photoluminescent sensor for Zn(II).[2] Sensing for
Zn(II) is observed when the resulting complex solution is excited with 470nm light.[2] Further
work of the optical properties with lanthanide metal ions (Eu(III) and Gd(III)) also show
photoluminescent properties when excited with 360nm light in both solution and solid states.[3]
HL
Reference
[1]
G. J. Park, Y. J. Na, H. Y. Jo, S. A. Lee, C. Kim, Dalton Trans. 2014, 43, 6618-6622.
[2]
D. J. Fanna, Y. Zhang, L. Li, I. Karatchevtseva, N. D. Shepherd, A. Abdul, J. R. Price, J. AldrichWright, J. K. Reynolds, F. Li, Inorg. Chem. Front. 2016, 3, 286-295.
[3]
D. J. Fanna, Y. Zhang, J. K. Reynolds, F. Li, J. Coord. Chem. 2016, accepted 5th April 2016.
ECR-07
Physiological Glucose-responsive Insulin Release via An Enzyme-polymer
Layer-by-layer Coating Strategy
Chun Xu, Chengzhong Yu,*
* [email protected]
Abstract
Diabetes is a challenging problem for public health all over the world. For diabetics,
especially for those with type I diabetes characterized by deficient insulin production, daily
multiple insulin administration is essential which causes poor patient compliance. Moreover,
it is hard to administrate the correct dose each time by this direct injection manner, which
may cause hypoglycemia and serious problems such as unconsciousness or even death. To
overcome these problems and improve patient satisfaction, a physiological glucose responsive
system which can release insulin in a way mimicking the physiological secretion and last for
long time is of great importance.
In this study, a novel physiological glucose responsive insulin release system has been
developed with tunable release threshold and multiple “ON-OFF” release behaviour (Fig. 1A).
Silica vesicles (SV)1 with large pore volume and amino surface functionalization was chosen
as the insulin reservoir to provide high insulin loading capacity. Glucose responsive layers
(enzyme layers) were coated onto the SV by Schiff base bond and function as “gates”–
preventing insulin release in the absence of glucose. The enzymes (GOD and CAT) convert
glucose into gluconic acid with oxygen; the production of gluconic acid decreases the local
pH value and protonates the Schiff base bond resulting in the permeability increase and
insulin release. Comparing to reported design,2 pH buffering polymer-polyethylenimine (PEI)
was introduced into the enzyme layers to increase the insulin release threshold by utilizing the
strong proton affinity of PEI to control the pH variation (Fig. 1B). By adjusting the PEI
amount, the insulin release threshold can be tuned either according to the normal/diabetes
critical threshold (7 mM) in human, or a higher critical threshold (above 10 mM) in mice. A
multiple “ON-OFF” release behaviour according to normal/diabetic glucose levels can be also
achieved. To our knowledge, this is the first report of a glucose responsive insulin release
nano-system designed according to the physiological needs in both human and animals.
Fig. 1 Illustration showing our design of physiological glucose responsive insulin release
system (A) with adjustable insulin release threshold (B).
Reference
[1]
[2]
9461.
J. Zhang, S. Karmakar, M. H. Yu, N. Mitter, J. Zou, C. Z. Yu, Small 2014, 10, 5068-5076;
W. R. Zhao, H. T. Zhang, Q. J. He, Y. S. Li, J. L. Gu, L. Li, J. L. Shi, Chem Commun 2011, 47, 9459-
ECR-08
Carbonization temperature influence of mesoporous carbon hollow
nanoparticles on therapeutic protein delivery
Trisha Ghosh, Meihua Yu, Anand Kumar Meka, Zhengying Gu, and Chengzhong Yu*
* [email protected]
Abstract
Innovative nanomaterials that can deliver large molecules (e.g. functional proteins), provide
new opportunities in improving human health. As a class of biocompatible nano-carriers,
carbon based nanomaterials, including carbon nanotubes, nano-sized graphene/graphene
oxide, fullerenes and nano-diamonds, have found various biomedical applications (1).
However, these 1D, 2D and 3D solid structures aren’t quite suitable as therapeutic agents,
such as nanocarrier systems due to their low loading capacity, which limits their bioapplication to a large extend. Recent progress in the research on mesoporous carbon
nanoparticles has demonstrated their great potential as intracellular delivery systems owing to
the improved loading capacity and controlled release behavior (2, 3). However, their
application for intracellular delivery of large therapeutic agents is rarely reported because
pure carbon is generally inert, thus, treatments under harsh conditions are needed to label
carbon nanoparticles and monitor their intracellular trafficking. Herein, we have developed
Mesoporous carbon Hollow spheres (MCHSs) as a new generation of therapeutic nanocarriers
with tailored structures for the delivery of large therapeutic agents. The interaction between
MCHSs and biological systems at molecular, organelle and cellular levels has been
investigated. The specific aim is to investigate the influence of carbonization temperature on
the structural integrity, its hydrophobicity and therapeutic protein delivery efficiency of
MCHSs along with its cellular uptake pathway, endosome escape mechanism.
Fig: Images representing MCHS-t carbonized at different temperatures (A) at 500 °C (B) at
700 °C (C) at 900°C along with (D) cytotoxicity assay to demonstrate delivery efficiency in
SCC25 cell line.
Reference:
1. Vashist SK, Zheng D, Pastorin G, Al-Rubeaan K, Luong JHT, Sheu FS. Delivery of drugs and biomolecules
using carbon nanotubes. Carbon. 2011;49(13):4077-97.
2. Gu J, Su S, Li Y, He Q, Shi J. Hydrophilic mesoporous carbon nanoparticles as carriers for sustained release of
hydrophobic anti-cancer drugs. Chem Commun. 2011;47(7):2101-3.
3. Kim T-W, Chung P-W, Slowing II, Tsunoda M, Yeung ES, Lin VSY. Structurally Ordered Mesoporous Carbon
Nanoparticles as Transmembrane Delivery Vehicle in Human Cancer Cells. Nano Lett. 2008;8(11):3724-7.
ECR-09
Multifunctional Nitrogen-doped Loofah Sponge carbon Blocking Layer for
High Performance Rechargeable Lithium Batteries
Xingxing Gu†, Yanglong Hou‡,* Shanqing Zhang†,*
†Centre for Clean Environment and Energy, Griffith School of Environment, Gold Coast
Campus, Griffith University, QLD 4222, Australia
‡Department of Materials Science and Engineering, College of Engineering, Peking
University Beijing 100871, China)
* [email protected]; [email protected];
Abstract
Low cost, long life and high performance lithium batteries not only provide economically
viable power to electric vehicle and smart electricity grids, but also address the issues of the
energy shortage and environmental sustainability[1-3]. Herein, low cost, hierarchical porous
and nitrogen doped loofah sponge carbon (N-LSC) derived from the loofah sponge has been
synthesized via a simple calcining process and then applied as a multifunctional blocking
layer for Li–S, Li–Se and Li–I2 batteries, respectively. Due to the ultra-high specific area
(2551.06 m2 g−1), highly porous (1.75 cm3 g−1), highly conductive (1170 S m−1), and
heteroatoms doping of N-LSC, the resultant Li–S, Li–Se and Li–I2 batteries with the N-LSC900 membrane, deliver outstanding electrochemical performance stability in all cases, i.e.,
high reversible capacities of 623.6 mA h g−1 at 1675 mA g−1 after 500 cycles, 350 mA h g−1 at
1356 mA g−1 after 1000 cycles and 150 mA h g−1 at 10550 mA g−1 after 5000 cycles,
respectively. The successful application to Li–S, Li–Se and Li–I2 batteries suggests that loofa
sponge carbon could play a vital role in modern rechargeable battery industries as a universal,
cost-effective, environmentally friendly and high performance blocking layer.
Reference
[1]
Gu, X., Wang, Y., Lai, C., Qiu, J., Li, S., Hou, Y., Martens, W., Mahmood, N., Zhang, S., Nano Res.
2015, 8, 129-139.
[2]
Gu, X., Lai, C., Liu, F., Yang, W., Hou, Y., Zhang, S., J. Mater. Chem. A 2015, 3, 9502-9509.
[3]
Gu, X., Hou, Y., Zhang, S., Chin. J. Chem. 2016, 34, 13-31
ECR-10
Designed SiO2@Au Particles for Laser Desorption/Ionization Mass
Spectrometry Analysis of Small Molecules
Xuming Sun, Xiang Wei, Kun Qian*
* [email protected]
Abstract
Small molecules profiling and quantitation based on laser desorption/ionization mass
spectrometry (LDI MS) are essential and to be developed in clinical diagnosis.1-3
Nanoparticles have been widely applied as matrices for the analyses of biomolecules in LDI
MS due to their desirable properties, such as high laser absorption and large surface area et al.
Herein, we demonstrated a novel platform using optimized SiO2@Au core-shell particles as
matrices for highly efficient LDI MS analysis of small biomolecules (MW < 700 Da).4 By
surface modification with aptamers, Apt-SiO2@Au allowed simultaneously targeted
enrichment and detection of analytes (e.g. kanamycin) with a detection limit at 200 pM.
Furthermore, we explored the fundamental plasmon enhancement mechanism in LDI MS and
demonstrated the antibonding modes of SiO2@Au provided unique opportunity for the
generation of hot carriers in the ultra-violet (UV) optical range for enhanced LDI MS. And we
achieved LDI MS profiling and detection of small metabolites from serum samples by
SiO2@Au,5, 6 superior to normal Au nanorods and nanospheres. Our work not only shed light
on the enhanced LDI MS detection using designed plasmonic particles, but also contributed to
the real case application of LDI MS in clinical study.
Reference
[1]
Zenobi, R. Science 2013, 342, (6163), 1201.
[2]
Chiang, C. K.; Chen, W. T.; Chang, H. T. Chem. Soc. Rev. 2011, 40, (3), 1269-1281.
[3]
Van Kampen, J. J.; Burgers, P. C.; de Groot, R.; Gruters, R. A.; Luider, T. M. Mass Spectrom. Rev. 2011,
30, (1), 101-120.
[4]
Gan, J.; Wei, X.; Li, Y.; Wu, J.; Qian, K.; Liu, B. Nanomedicine: NBM 2015, 11, (7), 1715-1723.
[5]
Wei, X.; Liu, Z.; Jin, X.; Huang, L.; Sun, X.; Liu, B.; Ye, J.; Qian, K. 2016, submitted.
[6]
Sun, X.; Wei, X.; Huang, L.; Liu, B.; Qian, K. 2016, in preparation.
ECR-11
Dual Activation of OH Radical on Green Rust with Ni Doping and SO42Intercalation for The Synergetic Phenol Degradation
Yuan Gao a, Weikang Shu, Zhenbang Cao, Guangren Qian, Jizhi Zhou,*
Center of Green Urban Mining & Industry Ecology，Shanghai University
* [email protected]
Abstract
Green rust (GR), one of anionic clays composed of Fe(II) and Fe(III), is a promising material
for organic contaminate removal. With H2O2 addition, the degradation of organic contaminate
was responsible for the Fenton-like reaction where ·OH radical was provided by Fe(II) on
GR[1-4]. However, the low amount of ·OH radical was usually observed in such process due
to the self-decay of Fe(II) on GR. In current work, a novel GR with Ni doping and SO42intercalation (GR(SO42-)/Ni) was developed for the improvement of OH radical activation.
The kinetics of phenol removal on GR(SO42-)/Ni illustrated that 45.9 mg/g of TOC was
removed when Ni doping is 20% of Fe(II). This removal efficiency was higher than that in the
case of common GR (31.2 mg/g), indicating that the adding amount of Ni and TOC removal
rate were positively correlated. Moreover, the Fe2+ content in GR(SO42-)/Ni is approximately
less than that in GR(SO42-). This was attributed to more ·OH generated on GR(SO42-)/Ni,
which was supported by the TBA probe test. X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS) and Inductively Coupled Plasma (ICP) were used to characterize the
crystallization, chemical component and content of residue after phenol removal, respectively.
The residue after phenol removal illustrated a layered structure, consistent with the pristine
structure of GR(SO42-)/Ni. This indicated that the structure of GR(SO42-)/Ni was much stable,
which provided more exposed Fe(II) in GR structure for ·OH generation. Our results
proposed a dual activation of OH radical on green rust with Ni doping and SO42- intercalation
for organic contaminate removal.
Reference
[1]
Xiaofei Xue, Khalil Hanna, Nansheng Deng, Journal of Hazardous Materials 2009, 166, 407-414;
[2]
T. Kone, K. Hanna, M. Usman, Colloids and Surfaces A: Physicochemical and Engineering Aspects
2011, 385, 152-158;
[3]
Khalil Hanna, Tiangoua Kone, Christian Ruby, Environmental Science and Pollution Research 2010,
17, 124-134;
[4]
Ph. Refait, O. Benali, M. Abdelmoula, J.-M.R. Genin, Corrosion Science 2003, 45, 2435-2449.
ECR-12
Acidity, Porosity, Thermal Stability, and Catalytic Activity Of SilicaZirconia/Montmorillonite-K10 Nanocomposite
Serly Jolanda Sekewael1,3,*, Karna Wijaya1, Triyono1 and Arief Budiman2
1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Gadjah Mada
University, Yogyakarta, Indonesia.
2
Department of Chemical Engineering, Faculty of Engineering, Gadjah Mada University,
Yogyakarta, Indonesia.
3
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Pattimura
University, Ambon, Indonesia.
* [email protected]
Abstract
Chemical and physical modification of the montmorillonite K10 (Mt-K10) catalyst with a
mixture of silica-zirconium dioxide has been conducted. The product was then attributed as
SZMK-700. Modification resulted in the increase of the total surface acidity, porosity,
thermal stability and catalytic activity. Through ammonia adsorption tests on catalysts were
verified by FTIR and TGA/DTA seen that the acidity of silica-zirconia/montmorillonite-K10
nanocomposite (SZMK-700) was higher as much as 16.23% compared to the montmorillonite
K10 (Mt-K10). Catalytic performance was evaluated by the esterification reaction of lauric
acid. Reflux for 20 hours lauric acid with methanol (molar ratio of 1:20) in the presence of a
20% (w/w) catalyst showed that SZMK-700 had high catalytic activity, i.e. produced methyl
laurate as much as 97.57% (w/w).
Key Words: acidity, catalytic activity, montmorillonite K10, silica-zirconia,
ECR-13
Ultrasensitive ELISA+ Enhanced by Dendritic Mesoporous Silica
Nanoparticles
Chang Lei, Chun Xu, Amanda Nouwen and Chengzhong Yu*
* c,[email protected]
Abstract
Enzyme-linked immunosorbent assay (ELISA) is one of the most widely used analytical
methods in both laboratorial and clinical analysis of biomolecules. It uses antibodies and
colour change to identify analytes and measure the concentration. For the diagnosis of
diseases in early stage and the detection of biomarkers with trace amount, the colour changes
could be below the limit of detection (LOD). Therefore, improving the sensitivity of ELISA
by signal amplification for the detection of analytes with ultralow concentrations below the
LOD of conventional ELISA is of great importance in many applications.
In this study, an ultrasensitive enzyme linked immunosorbent assay (ELISA+) is successfully
developed by using dendritic mesoporous silica nanoparticles (DMSN) with a high
horseradish peroxidase (HRP) loading capacity and easily accessible dendritic pore channels
for the colour signal amplification. The large surface area (484 m2 g-1) and high pore volume
(1.39 cm3 g-1) of designed DMSN enables a high loading of HRP (390 mg g-1), while the open
dendritic channels with large pore sizes (16 nm) allow easily accessible space for substrate
molecules to react with enzymes and promote colour reaction. A 2000 times enhancement of
detection sensitivity compared to commercial ELISA kit for insulin detection in serum is
achieved in this study.
ECR-14
High-efficiency Bulk Heterojunction Memory Devices Fabricated Using
Organometallic Halide Perovskite: Poly(N-vinylcarbazole) Blend Active
Layers
Luxin Wang, Bin Zhang and Yu Chen*
* [email protected]
Abstract
The bulk heterojunction (BHJ) concept has been widely used for mainstream polymer solar
cells, in which an interpenetrated charge channel connecting the two electrodes was formed
by blending of the polymer as an electron donor with electron acceptor material.1,2 The
driving force for the charge transport was ascribed either to the concentration-gradientinduced diffusion or the electric-field-induced drift of charge carriers.3 In this contribution, a
solution-processed organometallic halide perovskite-based BHJ memory device with a
configuration of indium-doped tin oxide (ITO)/CH3NH3PbI3:PVK/Al has been successfully
fabricated. Under a threshold voltage of −1.57 V, this device shows a nonvolatile write-once
read-many-times (WORM) memory effect, with a maximum ON/OFF current ratio exceeding
103. In contrast, the ITO/CH3NH3PbI3/Al device showed only conductor characteristics, while
the PVK-based device exhibited insulator behavior. Upon being subjected to voltages, an
interesting filamentary nature of the CH3NH3PbI3:PVK film was also observed in situ at the
microscopic nanometer level using a C-AFM technique with a device configuration of
Si/Pt/CH3NH3PbI3:PVK/Pt. The mechanism associated with the memory effect is discussed.
The electric field-induced intermolecular charge transfer effect between CH3NH3PbI3 and
PVK, and the possible conformational ordering of the PVK side-chains/backbone under an
applied bias voltage, may cause the electrical conductivity switching and WORM effect in the
reported BHJ device.
Figure 1. (Left) Device structure of the as-fabricated Al/ CH3NH3PbI3:PVK/ITO BHJ
memory and (Right) I–V characteristics of the device.
References
(2) C. J. Brabec, N. S. Sariciftci and J. C. Hummelen. Adv. Funct. Mater. 2001, 11, 15.
(3) A.J. Heeger. Adv. Mater. 2014, 26, 10.
(4) V. Dyakonov. Phys. E (Amsterdam) 2002, 14, 53.
ECR-15
Silica Nanopollens Enhance Adhesion for Long-Term Bacterial Inhibition
Hao Song†, Yusilawati Ahmad Nor†, Meihua Yu†, Yannan Yang†, Jun Zhang†, Hongwei
Zhang†, Chun Xu†, Neena Mitter‡, Chengzhong Yu†*
† Australian Institute for Bioengineering and Nanotechnology, The University of Queensland,
Brisbane 4072, Australia
Queensland Alliance for Agriculture and Food Innovation, The University of Queensland,
Brisbane 4072, Australia
* [email protected]
Abstract
Nature’s creations with spiky topological features typically exhibit intriguing surface adhesive
properties.[1] From micrometer-sized pollen grains that can easily stick to hairy insects for
pollination[2] to nanoscale virus particles that are highly infectious toward host cells[3],
multivalent interactions are formed taking advantage of rough surfaces. Herein, this natureinspired concept is employed to develop novel drug delivery nanocarriers for antimicrobial
applications.[4] A facile new approach is developed to fabricate silica nanopollens
(mesoporous silica nanospheres with rough surfaces), which show enhanced adhesion toward
bacteria surfaces compared to their counterparts with smooth surfaces. Lysozyme, a natural
antimicrobial enzyme, is loaded into silica nanopollens and show sustained release behavior,
potent antimicrobial activity, and long-term total bacterial inhibition up to 3 days toward
Escherichia coli. The potent antibacterial activity of lysozyme-loaded silica nanopollens is
further demonstrated ex vivo by using a small-intestine infection model. Our strategy provides
a novel pathway in the rational design of nanocarriers for efficient drug delivery.
Reference
[1]
Wegst, U. G. K.; Bai, H.; Saiz, E.; Tomsia, A. P.; Ritchie, R. O. Nat. Mater. 2015, 14, 23.
[2]
Edlund, A. F.; Swanson, R.; Preuss, D. The Plant Cell 2004, 16, S84.
[3]
Sougrat, R.; Bartesaghi, A.; Lifson, J. D.; Bennett, A. E.; Bess, J. W.; Zabransky, D. J.; Subramaniam,
S. PLoS Pathog. 2007, 3, e63.
[4]
Song, H.; Ahmad Nor, Y.; Yu, M. H.; Yang, Y. N.; Zhang, J.; Zhang, H. W.; Xu, C.; Mitter, N.; Yu, C.
Z. J. Amer. Chem. Soc. 2016, DOI: 10.1021/jacs.6b00243.
ECR-16
Nano-reactor for Ferrate(VI)
---- a Non-radical Oxidant for Groundwater Purification
Shu weikang, Gao yuan, Qian guangren, Huang xin, Zhou jizhi*
Center of Green Urban Mining & Industry Ecology, Shanghai University
* [email protected]
Abstract
Ferrate has been extensively applied in water purification[1,2]. On the basis of its extraordinary
oxidative capability, it can target on a wide variety of organic contaminants and without
generation of undesirable by-product. However, due to the extremely high reactivity, its
stability has been severely vitiated in ambient environment[3]. In this work, a Ca-based nanoreactor for ferrate was prepared. As characterized by X-Ray diffraction (XRD), it’s been
calculated that the d003 value was approximately 0.943 nm, which is analogous to the typical
CaAl-CrO42--LDH structure[4], and in good accordance with identical ferrate species. The XRay Photoelectron Spectroscopy (XPS) also verified the existence of hexavalent-Fe.
Interestingly, the alkalinity provided by the Ca2+ has significantly expanded persistency of
ferrate. And an external vehicle form by the interlayer matrix has strengthened the interaction
between ferrate and pollutant. Consequently, the LDH-ferrate has achieved a total organic
carbon (TOC) removal of 50%, which forms a sharp contrast with the traditional ferrate with
only approximately 5% TOC removal. The oxidation induced by ferrate was regarded as a
non-radical reaction. And a plausible pathway can be described as follow. As pollutant
entered the nano-scale reactor, it could be oxidized rapidly by the ferrate. Meanwhile, since
the LDH matrix was still well maintained (substantiated by XRD), thus the intermediate was
retained within the reactor and further decomposed by an adsorption/oxidation process. Such
deduction was also validated by HPLC analysis.
Reference
[1] Karlesa A, De Vera G A, Environmental Science & Technology, 2014, 48(17):10380-9;
[2] Qi H, Dong W, Separation & Purification Technology, 2013, 108(16):74-82;
[3] Lee Y, Kissner R, Gunten U V. Environmental Science & Technology, 2014, 48(9):5154-5162;
[4] Qian G, Feng L, Chemical Engineering Journal, 2012, s 181–182(1):251-258;
ECR-17
Adjuvant property of invaginated mesostructured hollow carbon spheres
Manasi Jambhrunkar, Meihua Yu, N. Mitter and Chengzhong Yu*
* [email protected]
Abstract
Adjuvants have attracted much attention since the inception of subunit vaccines. Currently
available adjuvants face issues like safety, stability and bioavailability. These issues have
encouraged the researchers to find new and safe adjuvants. Nanoparticles have shown promise
in this regard. In this study, invaginated mesostructured hollow carbon spheres (MHCS) were
synthesized [1] and studied for their adjuvant effect. MHCS have a high loading capacity
(1045 µg/mg) of ovalbumin (OVA). In vivo studies have shown that MHCS induced antibody
response 3 times higher compared to QuilA. From the IgG1/IgG2a ratio, it is evident that
MHCS induced a T cell mediated antibody response
ECR-18
In-situ Synthesis and Bistable Electrical Switching Behavior of
Poly(aryleneethynylene)-grafted Reduced Graphene Oxide
Sai Sun, Bin Zhang and Yu Chen*
* [email protected]
Abstract
As the first truly 2D material, graphene is being considered as an ideal material for
modern electronic devices because of its fantastic physical properties.1 Most recently,
fruitful results provide us opportunities to tailoring the electronic structures of graphene
controllably. A soluble PAE-g-RGO, in which the amount of RGO in the structure was
calculated as approximately 15.42 wt%, was synthesized by in-situ polymerization from a
graphene surface via the Sonogashira–Hagihara coupling reaction. Molecular orbital
calculations revealed that the HOMO was located predominantly on the RGO sheets,
while the LUMO centered at the PAE chain. The distinct distribution of the LUMO and
HOMO of PAE-g-RGO suggested the existence of a charge-transfer state (PAE•–-RGO•+).
The distinct distribution of the LUMO and HOMO of PAE-g-RGO suggested the
existence of a charge- transfer state (PAE•–-RGO•+). The negative ΔGCS value (–2.57 eV)
indicated that the occurrence of the charge separation via 1RGO* in o-DCB was
exothermic and favorable. Upon irradiation with 365 nm light, a typical radical signal
centered on g=2.0037 in the electron paramagnetic resonance spectrum of PAE-g-RGO
almost completely disappeared due to a decrease in the spin-state density as a result of
photoinduced intramolecular electron transfer events in this material system. As
expected, the nonvolatile rewritable memory effect was observed in the prepared PAE-gRGO-based device. The electric field-induced structural and morphological changes give
rise to an increase in both the height and roughness of the sample surface in the on state.
Reference
(5) Chen, B. Zhang, G. Liu, X.D. Zhuang, E.T. Kang, Chem. Soc. Rev. 2012, 41, 4688-4707
ECR-19
Lipid-coated Calcium Carbonate/Phosphate Hybrid Nanoparticles as a
Novel Vector for Gene Delivery to Cancer Cells
Yilun Wu, Wenyi Gu, Jie Tang, Zhi Ping Xu,*
Australian Institute for Bioengineering and Nanotechnology, the University of Queensland, St
Lucia, QLD 4072, Australia
* [email protected]
Abstract
Oligonucleotides are vulnerable under physiological conditions so that proper vectors are
required in the application of gene therapy. Among all the reported gene vectors, calcium
phosphate and carbonate based nanoparticles are sparking because of the high payload
capability, colloidal stability, and good biodegradability.[1,2] In this study, we report a kind
of lipid-coated calcium carbonate/phosphate hybrid nanoparticles (LCCP NPs) as an efficient
vector for gene delivery. The hydrodynamic diameter of LCCP NPs with a P/C ratio of 3/1
was 41.4±2.4 nm, and the zeta potential -18.6±0.8 mV. The TEM image (Fig. 1a) shows the
nanoparticles were uniform in size. Compared to lipid-coated calcium phosphate
nanoparticles (LCP NPs), LCCP NPs do not compromise the high payload capability to
oligonucleotides, with the dsDNA loading efficiency of LCP vs LCCP NPs being 52% vs
51%. The dsDNA from LCCP was released in a pH-sensitive manner (Fig. 1b). About 80% of
dsDNA was released from LCCP NPs at pH 5.5 within 4 h, while only 50% at pH 6.0 and 20%
at pH 7.4 in the same conditions. In comparison, the accumulative release of dsDNA from
LCCP NPs (80% and 50%) was higher than that from LCP NPs (55% and 20%) at pH 5.5 and
6.0 within 4 h. Moreover, both LCP and LCCP NPs with dsDNA-cy5 were efficiently taken
up by B16F0 cells, a melanoma cell line for Mus musculus (Fig. 1c) in a dose dependent way.
The uptake efficacy of these two nanoparticles was not much different at low concentrations,
but significantly more LCCP NPs were taken up by cells at 50 nM than LCP NPs (analyzed
via student t-test). In summary, the hybrid LCCP NPs are a more potential vector for gene
delivery to treat cancer cells in vitro and in vivo.
Figure 1. (a) TEM image of LCCP NPs, scale bar: 200 nm; (b) sustained dsDNA release
from LCP and LCCP NPs under different pH conditions at 37 oC. Lane 1:16 ng dsDNA in
comparison; and (c) the mean fluorescent intensity of all gated B16F0 cells after 4 h
incubation with LCP-dsDNA-cy5 or LCCP-dsDNA-cy5 NPs. **, p<0.01.
Reference
[1]
[2]
J. Tang, L. Li, et al, J Mater. Chem. B 2015, 3, 6805-6812;
S. K. Kim, M. B. Foote, et al, Cancer Lett. 2013, 334, 311-318.
ECR-20
Engineering Mesoporous Silica Nanoparticles for Immobilization of Lipase
Mohammad Kalantari, Meihua Yu, Yannan Yang, Jun Zhang, Hao Song and Chengzhong
Yu*
Australian Institute of Bioengineering and Nanotechnology, The University of Queensland,
QLD 4072, Australia
* [email protected]
Abstract
In recent years, the utilization of lipase (triacylglycerol ester hydrolases, EC 3.1.1.3) has
gained important industrial applications, e.g., in pharmaceutical synthesis, food processing
and biofuel production.[1] To overcome the limitations of native lipase including its proclivity
to denaturation and the difficulty in recycling, immobilization of lipase including physical
adsorption and chemical attachment approaches have been developed.[2] Even with promising
achievements in the field of lipase immobilization, it remains an ongoing challenge to develop
a simple approach with high loading, activity and stability. Herein, hydrophobically modified
mesoporous silica nanoparticles with a high octadecylalkyl content of 19 wt% and adjustable
pore sizes (1.6-13 nm) have been synthesized via a facile co-condensation approach (Figure
1a and b). It is demonstrated that both the increased hydrophobic content and a tailored pore
size (~ 5 nm) slightly larger than the size of enzyme are responsible for hyper-activation of
immobilized lipase. The optimized C18-MSN exhibits a loading capacity of 711 mg g-1 with a
specific activity 5.23 times than that of free enzyme with > 93% of initial activity retained
after 5 times’ reuse (Figure 1c and d), which is better than the best performance reported to
date.[3] Our findings have paved the way towards robust immobilization of lipase for
biocatalytic applications.
Figure 1 (a) SEM and (b) TEM images, (c) adsorption isotherm and (d) reusability over five
cycles of octadecylalkyl modified mesoporous silica nanoparticles.
Reference
[1]
P. Adlercreutz, Chemical Society Reviews 2013, 42, 6406-6436.
[2]
Y. Zhang, J. Ge, Z. Liu, ACS Catalysis 2015, 5, 4503-4513.
[3]
Z. Zhou, R. N. K. Taylor, S. Kullmann, H. Bao, M. Hartmann, Advanced Materials 2011, 23, 26272632; Q. Jin, G. Jia, Y. Zhang, Q. Yang, Can Li, Langmuir 2012, 28, 9788-9796; S.H. Jun, J. Lee, B. C. Kim, J.
E. Lee, J. Joo, H. Park, J. H. Lee, S.-M. Lee, D. Lee, S. Kim, Y.-M. Koo, C. H. Shin, S. W. Kim, T. Hyeon, J.
Kim, Chemistry of Materials 2012, 24, 924-929; J. Lee, Y. Lee, J. K. Youn, H. B. Na, T. Yu, H. Kim, S. M. Lee,
Y. M. Koo, J. H. Kwak, H. G. Park, H. N. Chang, M. Hwang, J. G. Park, J. Kim, T. Hyeon, Small 2008, 4, 143152.
ECR-21
Development of Manganese-doped Layered Double Hydroxide
Nanoparticles for Therapeutic Delivery and Magnetic Resonance Imaging
Bei LI1, Zi GU2, Nyoman KURNIAWAN3, Zhi Ping XU1,*
1
Australian Institute of Bioengineering and Nanotechnology, the University of Queensland,
Brisbane, QLD 4072, Australia; 2School of Chemical Engineering, University of New South
Wales, Sydney, UNSW 2052, Australia; 3Centre for Advanced Imaging, the University of
Queensland, Brisbane, QLD 4072, Australia.
* [email protected];
Abstract
Nanobiomaterials have been introduced into medicine by engineering functional components
and nanomaterials to incorporate novel contrast agents for disease diagnosis and simultaneous
therapy. This talk will present our recent work on developing a manganese-containing layered
double hydroxide (Mn-LDH) nanosystem for magnetic resonance imaging (MRI) and the
well-known cellular delivery. In the first part, we will present the newly synthesized Mn-LDH
nanoparticles with size of 30-120 nm (Figure 1A) by adopting a two-step method, i.e. coprecipitation and the subsequent isomorphic substitution1. This Mn-LDH NP showed a pHresponsive longitudinal relaxivity (r1), being 0.29, 8.24 and 9.48 mM-1 s-1 at pH of 7.4, 6.0
and 5.0, respectively (Figure 1B). The relaxivities at pH 6.0 and 5.0 are much higher than that
of Gd-DTPA2 (~3.4 mM-1 s-1), and also higher than that of MnO2 nanoparticles reported
recently3. In the second part, we will report the incorporation of anti-cancer drug fluorouracil
(5-FU) into Mn-LDH nanoparticles, and efficient delivery to colon cancer HT-29 cells. The
efficacy was indicated by reduction of IC50 from 3.29 to 1.55 µg/ml (Figure 1C). In summary,
this engineered Mn-doped LDH nanosystem shows a great promise as a theranostic agent for
both diagnostic MR imaging and anti-cancer therapy.
Figure 1. The TEM image and elemental mapping of Mn-doped LDH (A); the T1-MR images
under different pH values after incubation at 37 ˚C for 4h and corresponding relaxivities (B);
HT-29 cell viabilities after incubation with free 5-FU and 5-FU/Mn-LDH for 48 h (C).
Reference
[1]
[2]
[3]
M. C. Richardson, P. S. Braterman, J. Mater. Chem., 2009, 19, 7965;
K. M. Donahue, D. Burstein, W. J. Manning, M. L. Gray, Magn. Reson. Med., 1994, 32, 66;
Y. Chen, D. L. M. Y. Wu, H. R. Chen, L. L. Zhang, J. L. Shi, L. Z. Wang, Adv. Mater., 2014, 26, 7019;
ECR-22
Photocatalytic Activity and NO Selective Catalytic Reduction (SCR)
Performance of Organic matter Modified Ni-Fe/Cr Layered Double
Hydroxides and Layered Double Oxides
Yuhan Chen, Jianwei Zuo, Xiuxiu Ruan*
Center of green urban mining & industry ecology, Shanghai University
[email protected]*
Abstract
Nickel containing Layered Double Hydroxides (LDH) modified by sodium dodecyl benzene
sulfonate (Ni-Fe/Cr-DBS LDH), laurate (Ni-Fe/Cr-Laurate LDH) were synthesized by coprecipitation method. The synthetic products showed enhanced photocatalytic performance in
the degradation of dye wastewater (Congo red and Methyl Orange) than that of inorganic one.
The batch of photo-catalysis experiments for phenol by organic LDHs (Ni-Cr-Laurate LDH)
indicated that the photocatalytic degradation is attributable to the unique structure of Ni-CrLaurate LDH, thus continuously generating reactive oxygen species. Furthermore，the heattreated products of Ni-Fe-DBS LDH and Ni-Fe-Laurate LDH have outstanding NO SCR
activity at 300℃, which consists of NiO, Fe2O3 , NiFe2O4 and carbon. The catalytic reduction
progress could maintain 510 min and the maximum removal amount of NO reaches 2.8
mmol/g. The above results shows the as-modified Ni-Fe/Cr LDHs and the heat-treated
products could be regarded as a promising material for the removal of contaminant.
ECR-23
Hypoxia-mimicing Bioactive Ions Doped Mesoporous Silica Nanospheres
with Multi-directional Effects on Inflammation, Osteogenesis, and
Angiogenesis
Zetao Chen1, Mengchao Shi2, Chengtie Wu2*, Yin Xiao1*
1. Institute of Health and Biomedical Innovation, Queensland University of Technology,
Brisbane, 60 Musk Ave, Kelvin Grove, Brisbane, Queensland 4059, Australia.
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure,
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, People’s
Republic of China.
* [email protected] (C.W); [email protected] (Yin Xiao)
Abstract
The application of mesoporous silica nanospheres (MSNs) loaded with drugs/growth factors
to induce osteogenic differentiation of stem cells has been trialed by a number of researchers
recently. However, limitations such as high cost, complex fabrication and unintended side
effects from supraphysiological concentrations of the drugs/growth factors represent major
obstacles to any potential clinical application in the near term. In this study we reported an in
situ one-pot synthesis strategy of MSNs doped with hypoxia-inducing copper ions and
systematically evaluated the nanospheres by in vitro biological assessments. The Cucontaining mesoporous silica nanospheres (Cu-MSNs) had uniform spherical morphology
(~100nm), ordered mesoporous channels (~2nm) and homogeneous Cu distribution. CuMSNs demonstrated sustained release of both silicon (Si) and Cu ions and controlled
degradability. The Cu-MSNs were phagocytized by immune cells and appeared to modulate a
favorable immune environment by initiating proper pro-inflammatory cytokines, inducing
osteogenic/angiogenic factors and suppressing osteoclastogenic factors by the immune cells.
The immune microenvironment induced by the Cu-MSNs led to robust osteogenic
differentiation of bone mesenchymal stem cells (BMSCs) via the activation of Oncostation M
(OSM) pathway. These results suggest that the novel Cu-MSNs could be used as an
immunomodulatory agent with osteostimulatory capacity for bone regeneration/therapy
application.
ECR-24
Advancements in DNA-based Computers and Nanomachines
Bradley I Harding, Joanne Macdonald,
University of the Sunshine Coast
*[email protected]
Abstract
DNA-based computers and nanomachines have undergone many advancements in their
capabilities, with regards to both their physical interaction and logic computation, since their
inception two decades ago [1]. These advancements range from input-dependent cleavage of a
substrate [2] and self-assembly of DNA crystal structures [3] to interactive game-playing
computers [4, 5] and programmable molecular robots [6, 7]. Whilst DNA-based computers
continue to expand their applicability in more varied situations, with the development of
specialized biosensors [8, 9] and user viable outputs [10], their potential is rapidly being
reached unless new advancements are made. We propose that two major advancements that
would greatly increase the logic computing capabilities of DNA-based computers are a
reset/reverse mechanism and time-keeping, or “clocking”, system. A reset/reverse mechanism
would expand the logical abilities of DNA-based computers by enabling the logic gates to be
used multiple times. A time-keeping system would expand enable synchronizing of logic gate
operations. The benefits of these two key advancements would critically include greater
precision, reduced noise and cross-talk, deeper levels of logic, reusability and iterations,
further miniaturization of the systems, and improved integration for practical implementation.
Reference
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M. N. Stojanovic, D. Stefanovic, Nature Biotechnol. 2003, 21, 1069-74;
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Z. Wang, J. Elbaz, I. Willner, Nano Lett. 2011, 11, 304-9;
R. A. Muscat, J. Bath, A. J. Tuberfield, Nano Lett. 2011, 11, 982-7;
J. Chen, Z. Fang, P. Lie, L. Zeng, Anal. Chem. 2012, 84, 6321-5;
M. Rudchenko et. al., Nature Nanatechnol. 2013, 8, 580-6;
J. E. Poje et. al., Ange. Chemie. Int. Ed. 2014, 53, 9222-5;
ECR-25
Poster Presentation Abstracts
13-16 July 2016
Dendritic Mesoporous Silica Nanoparticles: Combined
Therapeutic Protein and Fluorescence-image Guided Photosensitizer for
Cancer Treatment
Prasanna Lakshmi Abbaraju, Yannan Yang, Manasi Jambhrunkar, Anand Kumar Meka,
Jianye Fu, Meihua Yu, Chengzhong Yu*
Brisbane, QLD-4072, Australia
* [email protected]
Abstract
Chemo and photodynamic therapy is considered to be effective treatment for many cancers like lung,
head, prostate and neck cancer. It includes the combination of therapeutic agent, ultra violet light and a
photosensitizer. One interesting class of inorganic nanomaterial for carrying drug and photosensitizer
is mesoporous silica nanoparticles (MSN). Conventional MSN usually have small pores, thus their
application are limited for the delivery of small biomolecules. Besides, dendritic mesoporous silica
nanoparticles (DMSN) are more suitable for carrying large biomolecules than conventional MSN.
However, the synthesized multifunctional DMSN were used for real time fluorescence imaging,
magnetic resonance imaging (MRI), 1 adsorption, 2 and drug delivery.3 The aim of this study is to make
dendritic silica on fullerene encapsulated silica spheres, for combined therapeutic, photodynamic
therapy and imaging.
DMSN with fullerene core were synthesized using the method reported by chun et al 4 with slight
modification. The synthesized material was functionalized with n-ODMS and was characterized by N2
adsorption and desorption, transmittance electron microscope and scanning electron microscopy. The
therapeutic anti-pAkt antibody was loaded into dendritic silica and the loading amount was calculated
using nanodrop. The fullerene amount was calculated using thermo gravimetric analysis. The DMSN
containing anti-pAkt antibody and fullerene were tested for combined therapy for treating human
breast cancer (MCF-7) cells.
DMSN with fullerene core were successfully synthesized using emulsion system. The combined
chemo/photo dynamic therapy was studied for unmodified and C-18 modified nanoparticles. The C-18
modified nanoparticles demonstrated high cellular uptake and intracellular delivery of therapeutic
protein in cancer cells, causing significant cell inhibition.
Reference
[1]
T. S. Atabaev 1, J. H.Lee 2, Nanotechnology 2013, 24, 34;
[2]
K. Yu 1, X. Zhang 2, Materials Letters 2013, 106, 151-154;
[3]
S. Gai 1, P. Yang 2, J. Mater.Chem 2011, 21, 16420;
[4] C. Xu 1, M. Yu 2, Small 2015;
P-01
Synthesis of Metal Complexes Using Julolidine-based Ligand
Tamara Badavi,* Daniel J. Fanna, Feng Li
School of Science and Health, Western Sydney University, Locked Bag 1797 Penrith, NSW
2751, Australia
*[email protected]
Abstract
A highly successful selective and sensitive chemosensor HL containing quinoline and
julolidine units has been studied in our group and others. [1-3] In this sequence of experiments
that was undertaken, HL was characterised, assessed and evaluated as a potential
chemosensor. Herein, a 0.02 mmol/l HL was titrated with standard metal nitrate salts
including Al(III), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II) and Zn(II). The investigation
of sensing properties towards various metal ions with HL was undertaken via UV-vis
titrations. In addition, the photoluminescence properties of metal complexes with such ligand
HL have been investigated.
Reference
[1]
G. J. Park, Y. J. Na, H. Y. Jo, S. A. Lee, C. Kim, Dalton Trans. 2014, 43, 6618-6622.
[2]
D. J. Fanna, Y. Zhang, L. Li, I. Karatchevtseva, N. D. Shephard, A. Abdul, J. R. Price, J. AldrichWright, J. K. Reynolds, F. Li, Inorg. Chem. Front. 2016, 3, 286-298.
[3]
D. J. Fanna, Y. Zhang, J. K. Reynolds, F. Li, J. Coord. Chem. 2016, accepted 5th April 2016.
P-02
Design, Synthesis and Characterization of Lanthanide Metal Complexes
Alexander R. Craze* and Feng Li.
School of Science and Health Western Sydney University, locked bag 1797 Penrith NSW 2751
Australia
* [email protected]
Abstract
Lanthanides are commonly used in the design and synthesis of magnetic materials such as
single molecule and single ion magnets, spintronics and quantum computing, optical devices
such as LED’s, bioimaging sensors, and luminescent immunoassays as well as in MRI
contrast agents.[1,2] The choice of ligand can dictate and enhance the properties of lanthanide
metal ions in a complex, and through the careful design of functional ligands, multifunctional
materials can be synthesized.[3] A tripodal, hexa/hepta dentate ligand (H3L) was synthesized
by the Schiff base condensation of N,N-diethylsalicylaldehyde and trisethylaminoamine in a
3:1 ratio. The designed ligand has extensive conjugation and the ability to form a stabilized
amine radical, both of which have been shown to enhance optical properties.[4–6] The
complexes (Eu(III), Gd(III) and Dy(III)) were characterized by FT-IR, Raman spectroscopy,
NMR, SEM-EDS, PXRD, single crystal X-ray diffraction, CHN analysis, and high resolution
ESI-MS. The optical and magnetic properties are currently being studied using UV-vis,
fluorescence spectroscopy and PPMS. The feasibility of possible practical applications of
complexes will be evaluated.
H3L
References
[1]
F. Pointillart, T. Guizouarn, B. Lefeuvre, S. Golhen, O. Cador, L. Ouahab, Chem. – Eur. J. 2015, 21
(47), 16929–16934.
[2]
K. Kuriki, Y. Koike, Y. Okamoto, Chem. Rev. 2002, 102 (6), 2347–2356.
[3]
G. Cucinotta, M. Perfetti, J. Luzon, M. Etienne, P. E. Car, A. Caneschi, G. Calvez, K. Bernot, R.
Sessoli, Angew. Chem. Int. Ed. 2012, 51 (7), 1606–1610.
[4]
H. Zheng, X. Q. Zhan, Q. N. Bian, X.J. Zhang, Chem. Commun. 2012, 49 (5), 429–447.
[5]
J. Hu, J. Wang, T. H. Nguyen, N. Zheng, Beilstein J. Org. Chem. 2013, 9, 1977–2001.
[6]
C. Train, L. Norel, M. Baumgarten, Coord. Chem. Rev. 2009, 253 (19–20), 2342–2351.
P-03
Enhancement of the Performance of Rechargeable Batteries by Proposing
New Materials
Amir Farokh Niaei1 *, Tanveer Hussain1, Marlies Hankel1, Debra J. Searles1,2
Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072,
Australia
2
School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane,
QLD 4072, Australia
* [email protected]
1
Abstract
The selection of a suitable material for the anode and cathode of a rechargeable battery has a
direct effect on the battery performance. Two important aspects of this issue are the charge
storage capacity and the battery discharge time. We have considered an anode composed of a
carbon allotrope, graphdiyne (GDY), in conjunction with sodium (Na) as a charge transfer
agent. A comprehensive theoretical study has been carried out by applying density functional
theory calculations (DFT) to study the binding of Na atoms on the GDY layers and to
determine the maximum capacity, as well as energy barriers for Na diffusion throughout the
layers. According to the results, Na intercalates to the GDY bulk layers with a maximum
capacity of NaC5.14 (equivalent to an electrical capacity of 316 mAh/g). The energy barrier for
in-plane movement of Na from one pore to another pore in GDY bulk layers is found to be
0.819 eV. Furthermore, the barrier of energy for continuous zigzag movement of Na through
centroids of the pores is found to be only 0.029 eV. Therefore, the combination of GDY with
Na atoms is proposed as an alternative anode material for rechargeable batteries.
Figures:
Figure 1: The top and side views of 7 Na atoms on the GDY bulk layers, proposed as the maximum loading, with binding
energy of -1.95 eV
References:
[1] C. Sun, D. J. Searles, Journal of Physical Chemistry C, 2012, 116, 26222-26226;
[2] H. Zhang, Y. Xia, H. Bu, X. Wang, M. Zhang, Y. Luo, M. Zhao, Journal of Applied Physics, 2013, 113,
044309;
[3] G. Luo, Q. Zheng, W. N. Mei, J. Lu, S. Nagase, The Journal of Physical Chemistry C, 2013, 117, 1307213079;
[4] C. Huang, S. Zhang, H. Liu, Y. Li, G. Cui, Y. Li, Nano Energy, 2015, 11, 481-489.
P-04
Bacterial-morphologically Mesoporous Silica Adjuvant with
Multifunctional Rough Surface Enhance Macrophage Phagocytosis and
Ovalbumin-specific Immune Responses
Zhengying Gu, Meihua Yu and Chengzhong Yu*
Australian Institute of Bioengineering and Nanotechnology, the University of Queensland,
Brisbane, Queensland, 4067, Australia
* [email protected]
Abstract
Nanocarriers have attracted increasing attention to the complexation with subunit vaccines for
improving immune responses. However, several limitations are still associated with
nanoparticle-based adjuvants, such as low antigen loading capacity [1-3] and unsatisfactory
engulfment of antigen proteins by antigen presenting cells [4, 5]. Understanding the structurefunction relationships in natural system, such as rod-like bacteria (bacillus), provides a useful
guide for the design of new nanocarriers.
Here we report a novel mesoporous silica adjuvant that combines bacterial morphology with a
rough surface comprised of labelled shell particles. The bacterial topographic properties and
increases in roughness promote macrophage phagocytosis, further inducing strong ovalbumin
(OVA)-specific immune responses and significantly improving overall antibody titers.
Furthermore, the shell particles not only act as a component to form the rough morphology,
but also be an ideal marker for adjuvant itself, providing solid evidence that silica adjuvant
deliver and release antigen intracellularly by exhibiting different colour from antigen and cells.
Key words: mesoporous silica adjuvant, bacterial-inspired morphology, vaccine adjuvant
Fig 1. Scheme of mesoporous silica adjuvant (MSA) with rough surface
Reference
1.
2.
3.
4.
5.
Zhang, W.F., et al., Immune responses to vaccines involving a combined antigen-nanoparticle mixture and
nanoparticle-encapsulated antigen formulation. Biomaterials, 2014. 35(23): p. 6086-6097.
Tobio, M., et al., A novel system based on a poloxamer PLGA blend as a tetanus toxoid delivery vehicle.
Pharmaceutical Research, 1999. 16(5): p. 682-688.
Thomasin, C., et al., Tetanus toxoid and synthetic malaria antigen containing poly(lactide)/poly(lactide-coglycolide) microspheres: Importance of polymer degradation and antigen release for immune response. Journal
of Controlled Release, 1996. 41(1-2): p. 131-145.
Xu, L.G., et al., Morphologically Virus-Like Fullerenol Nanoparticles Act as the Dual-Functional Nanoadjuvant
for HIV-1 Vaccine. Advanced Materials, 2013. 25(41): p. 5928-5936.
Niikura, K., et al., Gold Nanoparticles as a Vaccine Platform: Influence of Size and Shape on Immunological
Responses in Vitro and in Vivo. Acs Nano, 2013. 7(5): p. 3926-3938.
P-05
Self-Assembly of Homometallic Ni(II)/Ni(II) and Heterometallic
Ni(II)/Cu(II) Coordination Cages
Kyle. J. Howard-Smith*, Nicholas. Shepherd and Feng. Li
School of Science and Health, Western Sydney University, Locked Bag 1797, Penrith, NSW,
2751, Australia.
*[email protected]
Abstract
Both homo- and heterometallic coordination cages have continued to receive considerable
attention over recent years, motivated by a range of potential applications as new materials for
gas adsorption, drug delivery, catalysis, magnetic materials and host-guest phenomena that
include their use as ‘molecular flasks’.[1,2] In previous studies, our group has reported the
structure of a heteronuclear Cu(II)/Fe(II) metallocage[3] where, Cu(II) and Fe(II) typically
displaying square pyramidal and octahedral coordination geometries, respectively. Through
the use of a metalloligand assembly, a homo- Ni(II) and a heterometallic Ni(II)/Cu(II) cubic
coordination cages were synthesised. The vertices are eight octahedral coordinated Ni(II)
metal centres, while an additional six Ni(II) (homo) and Cu(II) (hetero) metal centres,
respectively, occupy the faces of the cubic arrangement. The synthesis of two new
coordination cages Ni(II)/Ni(II) and Ni(II)/Cu(II) was successful, both coordination cage
structures were investigated by X-ray crystallography, HR-ESI mass spectrometry and Raman
spectroscopy.
Reference
[1] M. D. Ward, Chem. Commun., 2009, 4487-4499.
[2] L. Li, D. J. Fanna, N. D. Shepherd, L. F. Lindoy and F. Li, J. Incl. Phenom. Macro., 2015, 82, 3-12
[3] F. Reichel, K. J. Clegg, K. Gloe, J. J. Weigand, J. K. Reynolds, C-G. Li, J. R. Aldrich-Wright, L. F. Lindoy,
H-C. Yao and F. Li. Inorg. Chem., 2014, 53, 688-690.
P-06
Metallic Ni nanocatalyst in situ formed from a metal–organic-framework
by mechanochemical reaction for hydrogen storage in magnesium
Yi Jia and Xiangdong Yao*
Queensland Micro- and Nanotechnology Centre (QMNC), Griffith University, Nathan, QLD
4111, Australia.
* [email protected]
Abstract
The facile and scalable fabrication of ultrafine (<5 nm) nanoparticles (NPs) as effective
catalysts is the key for enhancing the kinetics of most hydrogen storage materials (HSMs).1-3
The direct fabrication of ultrafine NPs in HSMs is obviously a challenge because of the
inevitable NPs agglomeration during the thermo-reduction. Herein, we report a
mechanochemical-force-driven procedure for the one-step preparation of Ni NPs (2–3 nm) in
a MgH2 matrix, which capitalizes on the in situ bottom-up reduction of Ni-MOF-74 in the
presence of MgH2 as a reducing and sacrificing agent at room temperature. Both theoretical
calculations and experimental investigations show that ultrafine Ni NPs are much more
effective on catalytic hydrogenation/dehydrogenation in Mg due to the size effect. These
findings may facilitate the fabrication of other catalyzed HSMs using different MOFs as
catalyst precursors.4
Reference
[1]
Y. Jia, L. Cheng, N. Pan, J. Zou, G. Q. (Max) Lu, X. D. Yao, Advanced Energy Materials 2011, 1, 387393.
[2]
Y. Jia, C. H. Sun, L. Cheng, M. A. Wahab, J. Cui, J. Zou, M. Zhu, X. D. Yao, Physical Chemistry
Chemical Physics 2013, 15, 5814-5820.
[3]
Y. Jia, C. H. Sun, S. H. Shen, J. Zou, S. S. Mao, X. D. Yao, Renewable & Sustainable Energy Reviews
2015, 44, 289-303.
[4]
Y. Jia, C. H. Sun, Y. Peng, W. Q. Fang, X. C. Yan, D. J. Yang, J. Zou, S. S. Mao, X. D. Yao, Journal of
Materials Chemistry A 2015, 3, 8294-8299.
P-07
Ag(I) Extraction Rate and Interfacial Activity with Ketonic Derivatives of
Calix[4]arene in Nitrate Media
1
Jee Young Kim1, Keisuke Ohto1*, Yang Kim2
Department of Chemistry and Applied Chemistry, Faculty of Science and Engineering,
Saga University, 1-Honjo, Saga 840-8502, Japan.
2
Department of Chemistry & Advanced Materials, Kosin University, 194, Wachi-Ro,
Yeongdo-gu, Busan, 49104, South Korea.
*[email protected]
Abstract
Ketonic derivatives of calix[4]arene (Fig. 1) as
extraction reagents have been prepared and
investigated Ag(I) extraction in nitrate media by
batch-wise method, which showed effective
extraction. (Fig. 2) However, the extraction rates
of Ag(I) in 0.1 M HNO3 were significantly
dependent on the types of extractant. (Fig. 3) The
extraction equilibrium of Ag(I) were reached
Fig. 1. Chemical structures and
within 3 hours for EATOC, while it took more
abbreviations of ketonic calix[4]arene
than 72 hours for MKTOC and 96 hours for
derivatives as extractants
PKTOC, respectively. The interfacial tension was
measured by the drop volume method to elucidate the cause of the different extraction rates
Ag(I). (Fig. 4) The interfacial tension in 0.1 M HNO3 for EATOC was significantly smaller
compared to those for MKTOC and PKTOC. Thus, it was suggested that the extraction rate
of Ag(I) is proportional to interfacial activity and EATOC is the most active, which attributes
high polar nature of EATOC and adsorbs easily on the interface. The different extraction rate
of Ag(I) and interfacial activity would be due to different chemical structures of the
extractants.
Fig. 2. Ag(I) Extractability Fig. 3. Ag(I) Extraction Rate Fig. 4. Interfacial Tension
P-08
Pd(II)-Macrocycle Catalyst for Hiyama Reaction of Aryl Halides
Jee Young Kim,1 Young Hoon Lee,2 Keisuke Ohto,1 Yang Kim3*
Dept. Chem. & Appl. Chem. Saga University, 1-Honjo, Saga 840-8502, Japan
2
Dept. Chem. & EHSRC, University of Ulsan, 44610, S. Korea
3
Dept. Chem. & Adv. Mat., Kosin University, 194, Wachiro, Yeongdo-gu, Busan, S. Korea
*[email protected]
1
Abstract
Polyazamacrocycles have been attracted for several decades to the coordination chemistry as
powerful ligands on the transition metal ions not only due to the important role as bio-mimic
ligand in biology but also due to thermodynamic and kinetic stabilities to their metal
complexes. Macrocyclic Pd(II) complexes were encapsulated into ionic liquid layers coated
on the surface of Fe3O4 and applied to catalyst. They exhibited both high catalytic activity and
stability for Hiyama coupling between aryl chlorides and arylsilanes in water. The catalyst
was simply recovered by an external permanent magnet and recycled without a significant
loss in the catalytic activity.
P-09
Synthesis, Structure, and Magnetic Properties of
Multinuclear Nickel(II) Clusters
Fumiya Kobayashi,1 Ryo Ohtani,1 Shinya Hayami,1 Masaaki Nakamura,1
1
Department of Chemistry, Graduate School of Science and Technology,
Kumamoto University, Japan.
*[email protected]
Abstract
The design and synthesis of polynuclear metal complexes have attracted tremendous attention
because of their interesting physical or catalytic properties. Up to now, a great number of
polynuclear metal complexes have been synthesized and investigated.[1, 2] In our group, we
found out that the 3-methoxysalicylic acid derivatives form polynuclear metal complexes.
Here, we report crystal structure and magnetic property of a heptanuclear Ni(II) cluster
[Ni7(HL)6(CH3O)6]Cl 2 (1) and a tetranuclear Ni(II) cluster [Ni4L4(CH3O)4(CH3OH)4] (2).
1 crystallizes in the cubic space group Pa-3. Seven nickel(II) ions are linked by six
monoanionic ligands and six methoxy groups, resulted in a disk-like structure. This [Ni7] core
of 1 incorporates a central Ni ion that is surrounded by a [Ni6] hexagon.
Temperature-dependent magnetic susceptibility for 1 was measured in the form of the χmT
versus T curve, where χm is the molar magnetic susceptibility and T is the temperature (Figure
2). At room temperature, χmT value of 8.91 cm3 K mol-1 is higher than the expected value for
seven uncoupled Ni(II) ions with g = 2 (7 cm3 K mol−1). Upon cooling, χmT continuously
increases and reaches a maximum of 14.92 cm3 K mol-1 at 10 K. This behavior indicates
dominant inter-cluster ferromagnetic interactions in 1. Abrupt decrease of χmT value is
observed at very low temperature, being considered as a contribution of the zero field splitting
(ZFS) of the resulting S = 7 ground spin state and inter-cluster antiferromagnetic interactions,
but will be discussed in detail.
-1
10
mT / cm K mol
12
3
14
8
6
0
50
100
150
200
250
300
Temperature / K
Fig 2. Thermal dependence of
the χmT product of 1.
Fig 1. Crystal structure of 1.
Reference
[1]
S. Petit, P. Neugebauer, G. Pilet, G. Ghastanet, A. L. Barra, A. B. Antunes, W. Wernsdorfer, D. Luneau,
Inorg. Chem, 2012, 51, 6645-6654.
[2]
J. D. Leng, S. K. Xing, R. Herchel, J. L. Liu, M. L. Tong, Inorg. Chem, 2014, 53, 5458-5466.
P-10
PLATINUM/GOLD BIMETALLIC NANOPARTICLES FOR NONVIRAL GENE DELIVERY
G. Lazarus*, M. Singh
Non-viral gene delivery and mammalian tissue culture laboratory, Discipline of Biochemistry,
University of KwaZulu-Natal, Durban,
South Africa
* [email protected]
Abstract
Metallic nanoparticles such as gold and platinum have been used for cancer detection,
imaging and treatment over the past decade 1,2. Platinum has emerged as an advancement of
nanomedicine because it is an exclusive noble element and constitutes exceptional optical and
high surface-area-to-volume ratios. The study reports the synthesis of PVP-protected Pt/Au
BNPs functionalized with chitosan. TEM images revealed small, monodispersed Pt/Au BNPs
with an average size of 76.8 nm. The addition of chitosan to the BNPs produced a size
increase of 134.1 nm. Chit/BNPs and pDNA complexation was efficiently demonstrated in
the band shift assay and ethidium bromide intercalation assay respectively. MTT cell viability
showed high tolerance to the BNP and Chit/BNPs in the MCF7 and Caco-2 cell lines as
observed. Chit/BNPs nanoparticles exhibited a high 168.2% in Caco-2 cells and 148.9% in
MCF7. The results suggest that the Chit/BNPs low cytotoxicity coupled with the ability to
parametrically control particle size and surface properties make these unique nanoparticles
suitable for non-viral gene delivery vectors.
Transfection studies are currently being investigated and future work could include pegylation
and other combination of cationic polymers to enable efficient gene delivery.
Reference
[1] H. Zhang and N. Toshima, Journal of colloid and interface science 2013, 394, 16-176.
[2] R. Jawaid, M.U. Rehman, M.A. Hassan, Q.L. Zhao, P. Li, Y. Miyamoto, M. Misawa, R. Ogawa, T. Shimizu,
T. Kondo, Ultrasonics sonochemistry 2016, 31. 206-215.
P-11
Halide effects on formation and chemical properties of
mercury(II) complexes containing Y-type tridentate N-donor
Nam Kwon, Young-A Lee*
Department of Chemistry, Chonbuk National University, Jeonju 54896, Republic of Korea
* [email protected]
Abstract
Self-assembly of HgX2 (X- = Cl-, Br-, and I-) with Y-type 2,6-bis[(2-isonicotinoyloxy-5methylphenyl)methyl]-1-isonicotinoyloxy-4-methylbenzene (L) yields 2D consisting of
alternate prismatic P- and M-helical-linked-layers, 1D consisting of P- and M-helices, and
simple 2D sheet in a unique Y-type mode, respectively. The L/Hg(II) ratio of each product
(3/3 for Cl-; 2/3 for Br-; 1/3 for I-) is dependent on the nature of the halide anions. The
coordinating environments around of Hg(II) ion approximate to a square pyramid for Cl-, a
square planar and a distorted tetrahedral geometry for Br-, and distorted tetrahedral
arrangement for I-, respectively. Photoluminescence wavelengths are strongly depending on
the halide anions, and coordination ability to L is in the order of X- = Cl- > Br- > I-. Such
physicochemical properties were explained by electronic and steric natures of halide anions.
Reference
[1] J.L. Atwood, Nat. Mater. 2002, 1, 91-92.
[2] S.A. Bourne, J. Lu, A. Mondal, B. Moulton, M.J. Zaworotko, Angew. Chem. Int. Ed., 2001, 40, 2111-2113;
[3] E. Kim, H. Lee, T.H. Noh, O.-S. Jung, Cryst. Growth Des., 2014, 14, 1888-1894;
[4] Y. Ke, L.L. Ong, W.M. Shih, P. Yin, Science 2012, 338, 1177-1183.
[5] J.G. Kim, T.H. Noh, Y. Cho, J.K. Park, O.-S. Jung, Chem. Commun., 2016, 52 , 2545-2548;
[6] K. Tahara, S. Okuhata, J. Adisoejoso, S. Lei, T. Fujita, S.D. Feyter, Y. Tobe, J. Am. Chem. Soc., 2009, 131,
17583-17590.
P-12
Self-Assembly of a Unique 3d/4f Heterometallic Square Prismatic Box-Like
Coordination Cage
Li Li,a* Yingjie Zhang,b Maxim Avdeev,b Leonard F. Lindoy,c David G. Harman,d Rongkun
Zheng,e Zhenxiang Cheng,f Feng Lia and Janice R. Aldrich-Wrighta
a
School of Science and Health, Western Sydney University, Locked Bag 1797 Penrith, NSW
2751, Australia
b
Australian Nuclear Science and Technology Organisation, Locked Bag 2001 Kirrawee DC,
NSW 2232, Australia
c
School of Chemistry, The University of Sydney, NSW 2006, Australia
d
Molecular Medicine Research Group, School of Medicine, Building 30, University of
Western Sydney, Goldsmith Avenue, Campbelltown, NSW 2560, Australia
e
School of Physics, The University of Sydney, NSW 2006, Australia.
f
Institute for Superconducting & Electronic Materials (ISEM), University of Wollongong,
North Wollongong, NSW 2500, Australia
*[email protected]
Abstract
The use of symmetrical metalloligands in metal directed self-assembly processes has been
widely employed for generating a variety of metallo-cage structures. However, the use of noncentrosymmetric metalloligands in such a role appears not to have been reported previously.
Such ligands might be anticipated to provide a route to cage structures displaying reduced
symmetry. Here, we present the synthesis and characterization of a unique, slightly distorted
square
prismatic,
box-like
coordination
cage
of
type
[Cu6Dy8L8(MeOH)8(H2O)6](NO3)12•χsolvent obtained via the supramolecular assembly
between a non-centrosymmetric Dy(III) metalloligand and Cu(II) nitrate.[1] The eight corners
of the box are defined by eight 8-coordinate Dy(III) ions while 5-coordinate Cu(II) ions
occupy the center of its six faces (see below). Cage formation was idenfitied by X-ray
crystallography, ESI high resolution mass spectrometry, CHN analysis, SEM-EDS, FT-IR and
UV-Vis-NIR spectroscopy. Magnetic susceptibility measurements indicate that the complex
behaves as a single-molecule magnet with frequency dependent out-of-phase (χ”) component
maxima below 2.5 K.
Reference
[1]
L. Li, Y. Zhang, M. Avdeev, L. F. Lindoy, D. G. Harman, R. Zheng, Z. Cheng, J. R. Aldrich-Wright
and F. Li, Dalton Transactions. 2016, Submitted.
P-13
Amphiphilic Peptide-based Codendrimers and their Supramolecular
Assembly
Qinhua Lu, Kun Liu, Afang Zhang*
Department of Polymer Materials, Shanghai University, Shanghai 200444, China
Abstract
Amphiphilic dendrimers have been a promising candidate to form various ordered
nanostructures through supramolecular assembly for advanced material applications, mainly
due to their highly branched but uniform structures as well as multivalent peripheral groups.[12]
We here report on a new class of amphiphilic peptide-based codendrimers and their
supramolecular assembly. As shown in Figure 1, these codendrimers are composed of
hydrophobic L-lysine-based second or third generation dendrons (LysG2 and LysG3) with
hydrophilic three-fold oligoethylene glycol (OEG)-based first or second generation dendrons
(MeG1 and MeG2). Their supramolecular assembly is dominated by size matching and
hydrophilicity difference of the two dendritic components. When MeG2 dendron combined
with LysG3, the target codendrimer can form long range ordered helical fibers with uniform
diameter. The presence of multiple chiral centers in Lys-based dendrons is supposed to be the
driving force for the helical conformation. However, this ordered supramolecular assembly is
dismissed when the size matching is broken as shown in the case of codendrimers MeG1LysG2 and MeG1-LysG3.
Figure 1. Molecular structures of amphiphilic codendrimers a), as well as their AFM images on mica
from MeG1-LysG2 b), MeG1-LysG3 c) and MeG2-LysG3 d) in THF/H2O, respectively.
Keywords: Codendrimer; Amphiphilic molecules; Supramolecular assembly
Reference
[1]
B. N. S. Thota, L. H. Urner, R. Haag, Chem. Rev. 2016, 116, 2079-2102;
[2] B. M. Rosen, C. J. Wilson, D. A. Wilson, M. Peterca, M. R. Imam, V. Percec, Chem. Rev. 2009, 109, 62756540.
Acknowledgement
This work is financially supported by National Natural Science Foundation of China (No. 21574078).
P-14
Superior Flame Retardancy of Epoxy Resin by the Combined Addition of
Graphene Nanosheets and DOPO
Shan Liu, Hao Wang*
Centre for Future Materials, University of Southern Queensland, Toowoomba, Queensland
4350, Australia
* Email address: [email protected]
Abstract
Halogen based flame retardants are effective as flame retardants. However, there are many
concerns on their use due to the potential release of corrosive and toxic chemicals during
combustion. Novel halogen-free flame retardants are replacing toxic halogen based flame
retardants in polymer and polymer matrix composites. Graphene nanosheet (GNS) is proved
to be a promising flame retardant to increase char residues and inhibit the flammable drips of
epoxy resin (ER) [1, 2]. In this study, GNS is investigated in combination with traditional
phosphorus-based flame retardant (DOPO) to enhance the flame retardancy of ER. Addition
of GNS and DOPO changed the decomposition pathway of ER. During combustion, DOPO
played a key flame retardant role in the gas phase and the char enhancement in the condensed
phase, while GNS played an effect in the condensed phase. Addition of 5 wt% GNS and
DOPO separated, the peak heat release rate of ER was reduced from 1194 kW m -2 to 513.9
kW m-2 and 937.1 kW m-2, respectively. With the combined addition of GNS and DOPO, a
synergistic flame retardancy effect is achieved. The PHRR was reduced to 396 kW m-2 at the
addition of 2.5% GNS and 2.5% DOPO. The same tendency was obtained for the total heat
release, showing a synergistic effect between GNS and DOPO in improving the flame
retardancy of ER composites. The combined addition of GNS and DOPO extended the
diffusion path for heat and combustible gas while DOPO captured the free radicals which
further retarded ER degradation.
Figure 1 Schematic illustration of the flame retardancy effect of GNS and DOPO in ER combustion.
Reference
[1]
[2]
Liu, S., et al., Composites Science and Technology, 2014, 90: 40-47.
Liu, S., et al., RSC Advances, 2014. 4: 18652-18659.
P-15
Kinetically Controlled Assembly of Nitrogen-doped Invaginated Carbon
Nanospheres with Tunable Mesopores
Yang Liu, Xiaodan Huang and Chengzhong Yu*
Australian Institute for Bioengineering and Nanotechnology. The University of
Queensland.Brisbane QLD 4072, Australia
[email protected]
Abstract
Mesoporous hollow carbon nanospheres (MHCS) have been extensively studied owning to
their unique structural features and diverse potential applications.[1-3] Surfactant-free selfassembly approach between resorcinol/formaldehyde and silicon alkoxide has emerged as an
important strategy to prepare MHCS.[4] Extending such a strategy to other substituted phenols
to produce heterogeneous atoms doped MHCS remains a challenge due to the very different
polymerization kinetics of various resins. Herein, we report an ethylenediamine-assisted
strategy to control the cooperative self-assembly between 3-aminophenol/formaldehyde resin
and silica templates. Nitrogen-doped mesoporous invaginated carbon nanospheres (N-MICS)
with a N content of 6.18 at%, high specific surface area (up to 1118 m2 g-1), large pore
volume (2.47 cm3 g-1), and tunable mesopores (3.7 to 11.1 nm) have been prepared. When
used for electrical double layer supercapacitors, N-MICS show a high capacitance up to ∼261
F g-1, outstanding cycling stability (∼94 % capacitance retention after 10000 cycles), and
good rate performance (Please copy and paste the abstract here)
Scheme 1 The schematic illustration of the typical synthesis of N-MICS.
Reference
[1]
[2]
[3]
[4]
S. Mezzavilla, C. Baldizzone, K. J. Mayrhofer and F. Schüth, ACS Appl. Mat. Interfaces, 2015, 7, 12914-12922.
Y. Xia and R. Mokaya, Adv. Mater., 2004, 16, 886-891.
L. Guo, L. Zhang, J. Zhang, J. Zhou, Q. He, S. Zeng, X. Cui and J. Shi, Chem. Commun., 2009, 6071-6073.
H. W. Zhang, O. Noonan, X. D. Huang, Y. N. Yang, C. Xu, L. Zhou and C. Z. Yu, ACS Nano, 2016, 10, 4579–
4586.
P-16
A vesicle Supra-assembly Approach to Synthesize Amine-functionalized
Hollow Dendritic Mesoporous Silica Nanosphere for Protein Delivery.
Anand Kumar Meka, Prasanna Lakshmi Abbaraju, Hao Song, Chun Xu, Jun Zhang, Hongwei
Zhang, Meihua Yu*, Chengzhong Yu*
Brisbane, QLD 4072, Australia.
* [email protected], [email protected]
Abstract
Mesoporous silica nanoparticles (MSNs) with tunable structures and morphologies have
gained wide range of promising applications, particularly in drug delivery. (1) Hollow MSNs
are a special type of drug delivery systems with unique interior cavities as reservoirs. (2, 3) In
this work, we report a vesicle supra-assembly approach to synthesize novel aminefunctionalized hollow dendritic mesoporous silica nanospheres (A-HDMSN). An amine silica
source is introduced into a water-oil reaction solution prior to the addition of conventional
silica source tetraethylorthosilicate. This strategy favors the formation of composite vesicles
as the building blocks which further assemble into the final product. The obtained A-HDMSN
have a cavity core of 170 nm, large dendritic mesopores of 20.7 nm in the shell and high
pore volume of 2.67 cm3g-1. Compared to the calcined counterpart without amine groups (CHDMSN), A-HDMSN possess enhanced loading capacity to large negative proteins (IgG and
β-galactosidase) and improved cellular uptake performance, contributed by the cationic
groups. A-HDMSN enhances the intracellular uptake of β-galactosidase by up to 5-fold and
40-fold compared to C-HDMSN and free β-galactosidase, respectively. The active form of βgalactosidase delivered by A-HDMSN retains its intracellular catalytic functions.
Scheme 1. Proposed formation mechanism of A-HDMSN
Reference
[1]
M.Vallet-Regí; F.Balas; D.Arcos, Angew. Chem. Int. Ed. 2007, 46, 40, 7548-7558.
[2]
Y.S.Li; J.L.Shi, Adv. Mater. 2014, 26, 20, 3176-3205.
[3] Y.Zhang; B.Y.W.Hsu; C.L.Ren; X.Li; J.Wang, Chem. Soc. Rev. 2015, 44, 1, 315-335.
P-17
In Situ Stöber Templating: Facile Synthesis of Hollow Mesoporous Carbon
Spheres from Silica–polymer Composites for Ultra-high level in-cavity
Adsorption
Owen Noonan, Hongwei Zhang, Hao Song, Chun Xu, Xiaodan Huanga and Chengzhong Yu*
* [email protected]
Abstract
Hollow structuring of carbon materials with mesoporous walls has been shown to enhance
performance in a range of adsorption-based applications. However, utilization of the in-cavity
volume towards the maximum capacity offered by hollow nano-reservoirs is yet to be
demonstrated. To achieve this goal, further development in the control of nanostructure in
porous hollow carbons is paramount. Herein, we demonstrate a facile in situ Stober
templating approach for the synthesis of hollow mesoporous carbon spheres from
silica/polydopamine composites. We present a conclusive mechanism for the assembly of
such surfactant-free silica/polymer systems, based on the dynamic and controllable selfassembly between the silica core, silica primary particle and polymer precursors in a mixed
Stober system. We employ this new understanding for the generation of novel hollow
mesoporous carbon spheres with tunable pore sizes, high pore volumes and controllable shell
thicknesses tailored for high-level in-cavity adsorption. When used as an adsorbent for a
wastewater pollutant di-(2-ethylhexyl)phthalate, our hollow mesoporous carbon spheres
achieve an ultra-high adsorption capacity of 5084 mg g-1, more than 10 times higher than
previous reports. For the first time, we demonstrate that the cavity space offered by hollow
structures can facilitate near-100% volumetric uptake in adsorption applications. These
developments shed new light on the mechanism of silica-polymer composite assembly and the
designed synthesis of functional nanoporous materials with versatile applications.
Reference
[1]
Owen Noonan, Hongwei Zhang, Hao Song, Chun Xu, Xiaodan Huanga and Chengzhong Yu*, J. Mater.
Chem. A, 2016,4, 9063-9071.
P-18
Engineering Iron Oxide Hollow Nanospheres to Enhance Antimicrobial
Property: Understanding the Cytotoxic Origin in Organic Rich
Environment
Yusilawati Ahmad Nor, † Liang Zhou, † Anand Kumar Meka, † Chun Xu, † Yuting Niu, †
Hongwei Zhang, † Neena Mitter, ‡ Donna Mahony, ‡ Chengzhong Yu*†
†Australian Institute for Bioengineering and Nanotechnology, The University of Queensland,
‡Queensland Alliance for Agriculture and Food Innovation, The University of Queensland,
* [email protected]
Abstract
Engineered magnetic iron oxide nanoparticles with surprisingly high antimicrobial activity
and excellent safety profiles to mammalian cell lines have been developed. Hematite hollow
nanospheres (HNSs) were prepared by a facile hard templating method; reduction of hematite
HNSs by H2 leads to magnetite HNSs. The antimicrobial activity of magnetite HNSs towards
Gram positive (E. coli) and Gram negative bacteria (S. epidermidis) was evaluated against
hematite HNSs and conventional magnetite (C-magnetite; diameter < 50 nm). Superior
antibacterial performance was observed for magnetite HNSs towards both E. coli and S.
epidermidis over hematite HNSs and C-magnetite. The origin of the antimicrobial activity of
magnetite HNSs was the high leaching of iron ions in the presence of microorganisms, which
led to high generation of reactive oxygen species (ROS). Magnetite HNSs allow multiple-fold
increase in the generation of soluble iron ions over hematite HNSs and C-magnetite, showing
that control over both the composition and nanostructure is crucial to tune the antimicrobial
activity of iron oxides. Based on the current findings, magnetic HNSs show promising
potential antimicrobial applications.
Reference
[1]
E. Leung, D. E. Weil, M. Raviglione, H. Nakatani, Ant, W. H. O. W. H. D. The WHO policy package
to combat antimicrobial resistance. B World Health Organ 2011, 89 (5), 390-392.
[2]
N. Tripathy, R. Ahmad, S.H. Bang, J.H. Min, Y.B. Hahn, Tailored lysozyme-ZnO nanoparticle
conjugates as nanoantibiotics. Chem Commun 2014, 50 (66), 9298-9301
[3]
J. A. Lemire, J.J. Harrison, R.J. Turner, Antimicrobial activity of metals: mechanisms, molecular targets
and applications. Nat Rev Microbiol 2013, 11 (6), 371-384.
P-19
Visible Light-induced Photocatalytic Activity of High Surface Area NDoped Two-dimensional (2-D) TiO2 Sheets
Nikhil.A, G. S. Anjusree, Shantikumar V. Nair, A. Sreekumaran Nair *
Queensland Micro and Nanotechnology Centre & School of Engineering, Griffith University,
Nathan, 4111, Australia.
* [email protected]
Abstract
TiO2 being a wide band-gap material offers photocatalytic activity only in the UV region. The
effects of simultaneously improving the surface area and nitrogen doping on the visible lightassisted photocatalytic activity of titanate-derived two-dimensional (2-D) sheets of TiO2 have
been investigated. Highly anisotropic nitrogen-doped 2-D TiO2 sheets were successfully
synthesized from electrospun TiO2–SiO2 composite nanofibers. UV-VIS DRS measurements
showed the presence of small amount of nitrogen in the catalyst giving rise to a higher visible
absorption. Results indicate a remarkable efficiency in the photocatalytic degradation of
methyl orange in an aqueous environment when compared to undoped 2-D TiO2 sheets.
Fig. A: SEM image of Nitrogen doped 2-D TiO2 and Fig: B Photodegradation of methyl orange by Nitrogen
doped 2-D TiO2 sheets
P-20
Engineering Magnesium based/rGO hybrid Material for Arsenic
Sequestration
Swasmi Purwajantia, b, Xiaodan Huanga, Chengzhong Yua*
Brisbane, QLD 4072, Australia.
b
The Agency for Assessment and Application of Technology (BPPT), Indonesian Ministry of
Research, Technology and Higher Education, Jl. M.H. Thamrin No.8, Jakarta 10340,
Indonesia.
* [email protected]
a
Abstract
Magnesium based and reduced-graphene oxide (Mg(OH)2/MgO/rGO) hybrid material has
been prepared through simple and efficient method via precipitation followed by
hydrothermal process. Mg(OH)2 and MgO content in the composite was varied by adjusting
the feeding ratio of GO to magnesium and via calcination under N2 protection. The nature of
this hybrid material was confirmed by X-ray diffraction (XRD), Fourier transformed infrared
(FTIR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), transmission
electron microscopy (TEM), N2 adsorption-desorption, and X-ray photoelectron spectroscopy
(XPS). The Mg(OH)2/MgO/rGO hybrid material performance was evaluated for the removal
of arsenite (As(III)) and arsenate (As(V) from aqueous solution.
P-21
The MinION Device: Portable Single Molecule Sequencing Using
Nanopores
Emily Rames and Joanne Macdonald*
School of Science and Engineering, University of the Sunshine Coast, 90 Sippy Downs Dr,
Sippy Downs, Queensland, Australia
* [email protected]
Abstract
The MinION is a new format for next generation sequencing, where DNA strand sequencing
is performed using an inexpensive, pocket size USB device which is run using a laptop.
Further advantages of the portable format, include long read lengths and real-time data
analysis. The technology uses protein nanopores to sequence DNA strands. The characteristic
disruption of the electrical current that occurs when different bases of the DNA strand pass
through the nanopore is measured, to determine DNA sequence. We demonstrated use of the
MinION device for whole genome sequencing of enterovirus (~7kb genome), relevant to
clinical applications and environmental monitoring. Enteroviruses cause millions of serious
infections each year (eg. meningitis, paralysis, myocarditis, respiratory illnesses). Ongoing
improvements to the technology will facilitate the use of the MinION device for nanopore
sequencing in many biological and environmental applications.
References
[1]
356
[2]
Jain, M., Fiddes, I.T., Miga, K.H., Olsen, H.E., Paten, B. & Akeson, M. Nature Methods 2015, 12, 351Bayley, H. 2015 Clinical Chemistry, 2015, 61, 25-31.
P-22
Preparation of Functional Magnetic Particles with Controlled Surface
Chemistry for Bio-Diagnostic Applications
Chandrababu Rejeeth, Jiao Wu, Kun Qian*
* [email protected]
Abstract
The rising engagement of magnetic particles in diagnostics is strongly correlated to their key
properties including physical structures, surface chemistry, and magnetic material parameter.1,
2
For magnetic separation, through tuning the surface chemical property of magnetic particles,
various biological targets ranging from nano- to micro- scale can be selectively captured for
bio-diagnostic studies.3, 4 For the current effort of our group, we firstly demonstrated
multifunctional immuno-magnetic particles for rare cell isolation combined with the
downstream laser desorption/ionization mass spectrometry (LDI-MS). The novel approach
was applied to measure the metabolism of enriched circulating tumor cells (CTCs).5 Secondly,
we developed magnetic particles with different sizes for surface coating of designed polymers
under optimized the synthetic conditions. The as-prepared functional magnetic particles have
been tested in detection of serum biomarkers for clinical diagnostics.6 Therefore, a new
platform technology has been proposed to advance the translational research.
Reference
[1]
Lim, E. K.; Chung, B. H. Nature Protocols 2016, 11, (2), 236-251.
[2]
Shin, T.-H.; Choi, Y.; Kim, S.; Cheon, J. Chemical Society Reviews 2015, 44, (14), 4501-4516.
[3]
Jie, H.; Miao, G.; Hengte, K.; Cheng, Z.; Bin, R.; Gang, L.; He, S.; Yufei, M.; Xiaoyong, W.; Hailu, Z.;
Zongwu, D.; Huabing, C.; Zhijun, Z. Advanced Materials 2015, 27, (34), 5049-5056.
[4]
Li, Y.; Zhang, X.; Deng, C. Chemical Society Reviews 2013, 42, (21), 8517-8539.
[5]
Wu, J.; Wei, X.; Gan, J.; Huang, L.; Shen, T.; Lou, J.; Liu, B.; Zhang, J. X. J.; Qian, K. Advanced
Functional Materials 2016, 10.1002/adfm.201504184.
[6]
Rejeeth, C.; Pang, X.; Zhang, R.; Xu, W.; Sun, X.; Liu, B.; Lou, J.; Gu, H.; Yan, W.; Qian, K.
2016, in preparation.
P-23
The Space-changeable Confinement Effect by the Reduction of
Graphene Oxide (GO) and Monitored with Spin-crossover Phenomenon
Yusuke Sekimoto, Kosuke Wakata, Ryo Ohtani, Masaaki Nakamura, *Shinya Hayami
Graduate School of Science and Technology, Kumamoto University
2-39-1 Kurokami, Chuo-ku, Kumamoto, 860-8555, Japan.
* [email protected]
Abstract
The nano-scale materials and spaces are attractive due to their unique properties different
from the bulk-scale. Especially, the confinement in nano-scale spaces causes particular
phenomena. We call it
confinement effect. The nanoscale carbon materials are
frequently
used
as
the
confinement container. Herein,
we report the confinement
effect using graphene oxide
(GO) (Fig. 1).
GO is two-dimensional
carbon nanosheet, and has
various functionality. It is one
Fig. 1 Schematic images of the confinement effect.
of them that GO has many
oxygen functional groups such
as epoxide group, carboxyl group, and so on. They can be removed easily by the reduction of
GO. When GO is reduced, the interlayer distance of GO decreases. Using this property, the
confinement space can be changed even after confining the materials.
Spin-crossover (SCO) phenomenon also has attracted attention in recent years. SCO
phenomenon is the transition between high-spin (HS) and low-spin (LS) states induced by
temperature, light irradiation, pressure, etc. In this study, the confinement effect is monitored
with the SCO phenomenon of [Fe(Htrz)2(trz)](BF4) (1).
GO was synthesized by Hummers method. Each
dispersion of GO and 1 was mixed and stirred. The
black precipitation was collected as GO hybrid (2).
Reduced graphene oxide hybrid (3) was obtained by
thermal reduction of 2.
All compounds 1-3 exhibited the thermal hystereses
of more than 20 K. However, each spin transition
temperature (T1/2↑) was different. Especially, 3 which is
reduction product of 2 showed a 18 K higher T1/2↑ than
2 (Fig. 2). The interlayer distance of GO decreases after
the reduction of GO. And then, it impresses to 1 as the
chemical pressure. The chemical pressure affected the
coordination environment of 1 and T1/2↑ increases.
Reference
[1]
Shinya Hayami et al., J. Am. Chem. Soc. 2013, 135, 80978100
[2]
Shinya Hayami et al., Inorg. Chem. Front. 2015, 2, 886-892;
[3] Katsumi Kaneko et al., J. Am. Chem. Soc. 2011, 133, 2022-2024;
P-24
Fig. 2 Temperature dependence
of χmT of 2 and 3.
N-doped Mesoporous Carbon Microphere by Spray Drying-Vapour
Deposition for Supercapacitor
Xiaoran Sun, Xiaodan Huang, Hongwei Zhang, Chengzhong Yu,*
* [email protected]
Abstract
Supercapacitors, also known as electrical double-layer capacitors (EDLCs), are well-known
energy storage devices in consumer electronics, hybrid electric vehicles, uninterruptible
power supplies, and load-leveling[1]. Porous carbon materials have been extensively studied as
electrode materials for supercapacitors[2]. Therefore, the textural properties of porous carbon
play a significant role in the supercapacitor performance[3]. In the present work, carbon
microspheres were designed using spray drying-vapour deposition method. The resultant
carbon spheres have abundant mesopores, high surface area, and ultra-high nitrogen doping.
Comparing with other materials fabricated by different drying method, our carbon
microspheres show better capacitance and good cycling stability. Moreover, the close-packed
volume of porous carbon could be greatly reduced. Our work sheds light on how to enhance
the electrochemical performance per unit volume of the porous carbon materials by designing
delicate nanostructures.
Reference
[1]
Y Zhai, Y Dou, D Zhao, P. F. Fulvio, R. T. Mayes, S Dai, Adv. Mater. 2011, 23, 4828;
[2] Xiaojing Wang, Ji Feng, Yaocai Bai, Qiao Zhang, Yadong Yin, Chem. Rev. 2016,
DOI: 10.1021/acs.chemrev.5b00731;
[3] Wei Li, Jun Liu, Dongyuan Zhao, Nature Reviews Materials 2016, DOI:10.1038/natrevmats.2016.23;
P-25
Microenvironment Driving Reversible Color Switching in Aqueous
Solutions
Peinan Zhang, Xinyan Su, * Kun Liu, Wen Li, Afang Zhang
Department of Polymer Materials, College of Materials Science and Engineering, Shanghai
University, Nanchen Street 333, Shanghai 200444, China
* [email protected]
Abstract
Photochromic materials, especially switchable by visible light, attract substantial attention
because of their potential applications.1 Photoswitches based on donor-acceptor Stenhouse
adducts (DASAs) have been reported, which can switch from a conjugated, colored, and
hydrophobic form to a ring-closed, colorless, and zwitterionic structure on irradiation with
visible light, and show good reversibility in aromatic solvents.2 However, photoswitching of
DASAs in a reversible manner in aqueous phases remains a fascinating challenge. Herein, we
report on dendronized copolymers carrying DASA moieties (Figure 1), which were
constituted with oligoethylene glycol (OEG)-based dendrons to afford the
thermoresponsiveness. The photochromism of the copolymer in aqueous solutions was
investigated. It was found that thermally-induced collapse of OEG dendrons provides a
hydrophobic microenvironment in aqueous solutions to mediate the transformation of DASA
from hydrophilic zwitterionic into hydrophobic conjugated state, resulting in color switching
from colorless into purple which can be reversibly changed by irradiation with visible light.
Structural effect on reversibility of the color change was investigated in details. This work
opens a new platform to enrich the field of photochromic materials.
Figure 1. a) Chemical structure of dendronized copolymer; b) Schematic of reversible color
switching of the copolymer in aqueous solution.
Reference
[1]
[2]
W. Szymański, J. M. Beierle, H. A. V. Kistemaker et al., Chem. Rev. 2013, 113, 6114-6178.
S. Helmy, F. A. Leibfarth, S. Oh et al., J. Am. Chem. Soc. 2014, 136, 8169-8172.
Acknowledgements
This work is financially supported by National Natural Science Foundation of China (No. 21574078) and
Shanghai Natural Science Foundation (16ZR1411300).
P-26
Small-sized and Large-pore Dendritic Mesoporous Silica Nanoparticles
Enhance Antimicrobial Enzyme Delivery [1]
Yue Wang, Yusilawati Ahmad Nor, Hao Song, Yannan Yang, Chun Xu, Meihua Yu and
Chengzhong Yu*
Australian Institute for Bioengineering and Nanotechnology, The University of
Queensland, Brisbane, QLD 4072, Australia
*[email protected]
Abstract
The abuse of antibiotics has led to the emergence of antibiotic resistant bacteria and high
threats to human health. The search for safe and effective alternatives to traditional antibiotics
is growing worldwide. In this article, we report the synthesis of large pore dendritic
mesoporous silica nanoparticles (DMSNs) with controllable particle sizes and investigate the
relationship between particle size of DMSNs and their antibacterial enzyme delivery
performance. The choice of dual-functional perfluorocarbon anions with both low surface
tension and interaction with cationic surfactants enables the synthesis of DMSNs with tunable
particle sizes and pore size. After loading with lysozyme, a nature-occurring antimicrobial
enzyme, DMSNs with a large pore size of 22.4 nm and a small particle size of 79 nm show
significantly better antibacterial activity compared to either DMSNs with a larger particle size
(160 nm) or MSNs with a smaller pore size (2.4 nm) while the other parameter is similar. The
optimized DMSNs loaded with lysozyme exhibit total inhibition towards Escherichia coli
(E.coli) throughout five days. Our study provides new insights on controllable synthesis of
nano-carriers for antimicrobial protein delivery applications.
Reference
[1]
Wang, Y.; Nor, Y. A.; Song, H.; Yang, Y.; Xu, C.; Yu, M.; Yu, C., J. Mater. Chem. B, 2016, 4, 2646-
2653;
P-27
The Role of Immune Cells Response to Different Sized Nanomaterials
Fei Wei, Zetao Chen, Yin Xiao*
Institute of Health and Biomedical Innovation, Queensland University of Technology,
Brisbane, 60 Musk Ave, Kelvin Grove, Brisbane, Queensland 4059, Australia.
* [email protected] (Yin Xiao)
Abstract
Macrophages appear to be critical for nanomaterial-based bone healing. The plasticity of
macrophages implies the potential strategies to modulate macrophage response in bone
regenerative medicine. In general, macrophages responded to the material differently,
depending on the hydrophility, roughness or the surface topology of the nanomaterials.
Macrophages cultured on surfaces with different hydrophility demonstrate different protein
expression profiles and cytokine responses, implying the potential immunomodulation
properties of nanobiomaterials. Therefore, the importance of macrophage both in
physiological and nanobiomaterial-based bone healing process offers fundamental theoretical
basic for modulating osteoimmune environment through macrophage-based strategy or
developing smart materials to modulate the immune reaction and optimize osteogenesis.
P-28
Defective Activated Carbon as an Efficient Electrocatalyst for Oxygen
Reduction and Hydrogen Evolution Reactions
Xuecheng Yan, Yi Jia, Xiangdong Yao*
Queensland Micro- and Nanotechnology Centre, Griffith University,
Nathan Campus, QLD 4111, Australia
H-AC
N-AC
D-AC
Pt/C
-2
-1
Current Density (mAcm )
-2
Current Density (mAcm )
Abstract
Fuel cell is the most possible candidate to replace the current internal combustion engines in
vehicles because of its high energy conversion efficiency and pollution-free characters.[1-3]
Briefly, a fuel cell generates electricity by oxidizing a chemical fuel (e.g., hydrogen) at the
anode and reducing oxygen at the cathode, where the oxygen reduction reaction (ORR) is the
rate-limiting reaction. Meanwhile, a fuel cell as an electrolyzer can split water into hydrogen
(hydrogen evolution reaction (HER)) and oxygen if voltage bias is applied. Currently, the
expensive platinum (Pt) is the most efficient catalyst for the ORR and HER.[4-6] In the present
configuration, Pt particles are homogenously dispersed on the surface of carbon supports (e.g.,
activated carbon (AC)), serving as the active sites for these reactions. In a common sense, the
AC itself is not active for the ORR or HER, so the Pt particles are vital. Imagine that if we
remove all of the Pt particles, can the remaining AC still play the similar role? Herein, we
used a simple method for creating unique defects on the AC, which makes it highly active for
the ORR and HER. As can be seen from Figure 1(a), the ORR activity of the defective AC
(D-AC) is comparable to the commercial Pt/C (20 wt% Pt) in alkaline medium. Meanwhile,
the D-AC also exhibits excellent HER activity in acidic solution (Figure 1(b)), which is
better than most of the reported metal-free HER catalysts, but with much lower production
cost.
a 0
b 0
-2
-3
-4
-20
H-AC
N-AC
D-AC
Pt/C
-40
-60
-80
-5
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Potential (V vs RHE)
-100
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
Potential (V vs RHE)
Figure 1 ORR (a) and HER (b) performance comparison of the prepared samples.
Reference
[1]
[2]
[3]
[4]
[5]
[6]
R. Bashyam, P. Zelenay, Nature 2006, 443, 63.
M. Lefèvre, E. Proietti, F. Jaouen, J.-P. Dodelet, Science 2009, 324, 71.
Z. Zhao, M. Li, L. Zhang, L. Dai, Z. Xia, Adv. Mater. 2015, 27, 6834.
R. F. Service, Science 2007, 315, 172.
Y. Zheng, Y. Jiao, L. H. Li, T. Xing, Y. Chen, M. Jaroniec, S. Z. Qiao, ACS Nano 2014, 8, 5290.
C. G. Morales-Guio, L.-A. Stern, X. Hu, Chem. Soc. Rev. 2014, 43, 6555.
P-29
Developing an Oxidation Assisted Approach for Facile and Controllable
Resole Dissolution
Min Zhang, Xiaodan Huang, Yannan Yang, and Chengzhong Yu*
Australian Institute for Bioengineering and Nanotechnology, University of Queensland,
Brisbane, 4072, Australia
* [email protected]
Abstract
Phenolic resins have retained industrial and commercial interest for a century since they were
first introduced in 1907. As one typical type of phenolic resin, novolac, the dissolution
property in aqueous base has been studied comprehensively due to its widely application in
photoresist which plays a key role in photolithography and semiconductor industry. However,
for another type phenolic resin, resoles, our knowledge about its dissolution property is very
limited.1,2 Recently, a new nanostructured resole type resin-resorcinol formaldehyde (RF)
with controllable particle size and highly monodispersity attracts a lot of research interests
and has been utilized as hard template to synthesize various nanostructured metal oxides, but
the impregnation mechanism of metal ions into polymeric matrix remains unclear.3 Therefore,
investigation towards the dissolution property of RF is necessary which could help us to have
a better understanding of the impregnation mechanism of metal ions and further guide the
synthesis of various metal oxides. Herein, we report for the first time a facile and controllable
resole dissolution method using metal salts/ethanol solution. The dissolution mechanism was
proposed based on the cleavage of ether bond within resin matrix and we found that the
dissolution rate of RF in Al(NO)3·9H2O solution was positively correlated with the oxidation
capacity of the nitrate ions under acid condition. We also demonstrated that the dissolution
process can promote the impregnation of metal ions into RF matrix, which can be utilized for
controllable fabrication of metal oxide nanospheres with various structure.
Figure: TEM images of the RF spheres during dissolution process a) 0h; b) 1.5h; c) 2.0h; d) 3.0h; e) 4.0h; f) 5.0h；
Scale bar: 100nm. g) Solid state 13C NMR spectra of RF before (black line) and after dissolution (red line); h)
Particle volume statistics of the RF spheres during dissolution process under various temperature.
Reference
[1]
[2]
[3]
Pralay K. Pal,et al, Polymer, 1981, 22, 1699 –1704
Pavlos C. Tsiartas, et al. Macromolecules 1997, 30, 4656-4664;
J. Liu, et al, Angew. Chem. Int. Ed. 2011, 50, 5947 –5951.
P-30
Mesoporous Silica Nanospheres with Multifunctional Properties for Bone
Regeneration
Zhou Y1, Shi M2, Shao J1, Chen Z1, Song B2, Chang J2, Xiao Y1*, Wu C2*
Institute of Health and Biomedical Innovation, Queensland University of Technology,
Brisbane, Queensland, Australia
2
State Key Laboratory of High Performance Ceramics and Superfine Microstructure,
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China
1
* [email protected]; *[email protected]
Abstract
Introduction: Multifunctional bioactive materials for the reconstruction of bone defects have
attracted intensive research interest in recent years [1]. Bone regeneration requires a series of
coordinated events involving angiogenesis and osteogenesis, it is therefore pivotal to design a
biomaterial system which can simultaneously stimulate blood vessel growth and bone
formation in order to repair large bone defects. The aim of the present study is to develop a
multifunctional biomaterial system for scaffolding and therapeutic ions/drug delivery to
promote neovascularization of tissue-engineered bone constructs.
Materials and Methods: Mesoporous silica nanospheres (MSNs) with uniform sphere size and
mesopores were successfully fabricated, which could release therapeutic silicon ions (Si).
Dimethyloxaloylglycine (DMOG) [2], a chemical hypoxia mimetic, was loaded in the
mesopores of MSNs (D-MSNs). The stimulatory effects of Si ions and DMOG on both the
osteogenic and angiogenic activity of bone marrow stromal cells (BMSCs) were
systematically investigated in gene and protein levels.
Results: The sustained release of DMOG from D-MSNs could induce a hypoxic
microenvironment, which greatly enhanced the secretion of vascular endothelial growth factor
(VEGF) from BMSCs. Furthermore, the Si ions released from the nanospheres significantly
increased the expression of osteogenic markers (OCN, RUNX2 and OPN) of BMSCs.
Discussion: D-MSN, serving as both Si ion reservoir and drug carrier, has the capacity to
promote bone regeneration and induce blood vessel formation. This suggests that D-MSN is a
promising candidate as a multifunctional biomaterial system for bone tissue engineering
application.
Conclusion: The concept of delivering both therapeutic ions and functional drugs in a
multifunctional biomaterial system may offer a new strategy to construct functional tissueengineered bone.
Reference
[1] Wu C, Chang J. J Control Release. 2014; 193:282–95.
[2] Wu C, Zhou Y, Chang J, Xiao Y. Acta Biomater. 2013; 9:9159–68.
P-31
Encapsulation of Nanoscale Zero-valent Iron in Macroporous Silica for
Efficient Cr (Ⅵ) removal
Chaoxia Zhao, Guidan Tang, Jie Yang*
Key Laboratory of Green Chemistry & Technology, College of Chemistry, Sichuan University,
Chengdu 610064, China
* [email protected]
Abstract
Hexavalent chromium [Cr(Ⅵ)] is one of the most toxic inorganic contaminants in both
groundwater and surface water, since it has been greatly applied in various industries, such as
electroplating, pharmacy, textile and so on.1 Long-term exposure to Cr (Ⅵ)-contaminated
water may cause adverse effects on human health due to its carcinogenicity.2,3 Therefore, it is
necessary to depress the concentration of Cr(Ⅵ) in natural water in order to protect the public
health.
It has been demonstrated that nanoscale zero-valent iron particles (nZVIs) have great potential
in the reduction of Cr(Ⅵ) concentration due to their high surface activity.4,5 However, the
aggregation of nZVIs could significantly depress their activity in decreasing the Cr(Ⅵ)
concentration. To solve this problem, solid matrices are normally used to enhance the
dispersity and activity of nZVIs. In this work, a novel and effective Cr(Ⅵ) adsorbent was
fabricated by the incorporation of nZVIs in macroporous ordered silica foams (MOSF) with
the pore size of 80 nm and pore volume of 1.88 cm3/g. Due to the large pore volume of
MOSF, the weight content of nZVIs can be up to 62.5 wt% without aggregation. The
maximum Cr(Ⅵ) adsorption capacity was 18 mg/g.
Figure 1. SEM images of (a) MOSF and (b) nZVIs modified MOSF; (c) XRD pattern and (d) adsorption
isotherm of nZVIs modified MOSF.
Reference
[1]
Khezami, L.; Capart, R. Journal Of Hazardous Materials 2005, 123, 223.
[2]
Nahlik, M. J.; Chester, M. V.; Ryerson, M. S.; Fraser, A. M. Environmental science & technology 2016,
50, 4149.
[3]
Sarkar, B.; Naidu, R.; Krishnamurti, G. S. R.; Megharaj, M. Environmental Science & Technology 2013,
47, 13629.
[4]
Li, X.-q.; Elliott, D. W.; Zhang, W.-x. Critical Reviews In Solid State And Materials Sciences 2006, 31,
111.
[5]Gu, C.; Jia, H.; Li, H.; Teppen, B. J.; Boyd, S. A. Environmental Science & Technology 2010, 44, 4258.
P-32
RIVER CRUISE
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Please join us for a dinner boat cruise on our spectacular Brisbane River. Seafood buffet &
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Departure
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Time: 6:30 pm boarding - 7 pm departure. (We will return to the same point at 10 pm)
Departure Point: Southbank ferry terminal. Directly in front of the Wheel of Brisbane.
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