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2015 Fall

Nanomaterials,Nanostructures and Nano devices


Responsive materials operating outside of thermodynamic equilibrium

The proposed symposium will focus on materials that – akin to biological matter – operate away from thermodynamic equilibrium. Such materials are at the forefront of modern materials science research because they are capable of performing « smart », life-like functions, including responsiveness to external cues, taxis, or even self-replication. 




Traditionally, materials are sought to have immutable and thermodynamically stable structures offering desired properties, be it mechanical, magnetic, electrical, thermoelectric, or other. In sharp contrast, material systems found in nature are capable of change and are operating away from thermodynamic equilibrium. It is only under the non-equilibrium conditions that cells, tissues and organisms can transmit/signal chemical information, sense and adapt to the environment, or self-replicate. One of the grand challenges of modern materials science is to develop principles for the engineering of « smart » materials that would perform at least some of these life-like properties. This challenge calls for an interdisciplinary effort bridging materials science with the chemical synthesis or responsive molecules, the self-assembly of dynamic structures, and the physics describing the fundamental principles governing the non-equilibrium regime. The Symposium we propose will bring together some of the world’s leaders in this exciting area of research. Specifically, Prof. Steve Granick will lecture on his work, described in several recent Nature papers, on the synthesis and application of active colloids – that is, colloids engineered to respond to external stimuli, to move directionally, or to assemble into unusual supra-structures. Prof. Stefano Scana will describe his pioneering work (Science 2013) on light activated colloidal structures. Professors Frisic is one of the leaders of mechanochemistry research (numerous Angewandte, JACS papers) and will talk about materials (polymers, MOFs) that change upon mechanical stimuli. Prof. Lee Cronin will talk on materials that can controllably evolve (based on several of his Nature-family articles) while Prof. Sijbren Otto will narrate his exciting work on self-replicationg materials (e.g., from his recent Angewandte and Science papers). Additional contributions for oral presentations and posters will be sought after the Symposium is approved. Overall, the Symposium will be a unique venue defining the current status, the key challenges, and future prospects for research on non-equilibrium materials. At the horizon of this emerging area of research lie entirely new types of « smart » materials capable of performing various tasks depending on the state of external controls, of self-optimization, self-repair, or even evolution.


Hot topics to be covered by the symposium 



The symposium will cover several topics that are at the very forefront of modern materials science and often covered on the pages of leading journals including Nature or Science. Topic will include

  • Active colloids and nanoparticles
  • Non-equilibrium materials and systems
  • Mechnochemistry
  • Molecular evolution
  • Self-replication

Tentative list of invited speakers


  • Steve Granick, Urbana Champaign, “New developments in active colloids”
  • Stefano Scana, New York University, “Colloidal assemblies controleld by light”
  • Lee Cronin, Glasgow “Nonequilibrium materials discovery and design using evolutionary programming”
  • Sijbren Otto, Groeningen, “Self-Synthesizing Materials and Self-Replicators from Dynamic Molecular Networks”
  • Tomislav Frisic, Toronto, “Structural transformations of metal-organic materials under minimal mechanical stimuli‏”

Tentative list of scientific committee members 

  • Oren Scherman University of Cambridge, UK
  • James Stuart Queen's University Belfast, UK • Mircea Dincă MIT, Cambridge, USA
  • Leon Gradon Warsaw University of Technology, Faculty of Chemical Engineering, Poland
  • Marcin Fialkowski Institute of Physical Chemistry, Polish Academy of Sciences, Poland 

No abstract for this day

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Authors : Steve Granick
Affiliations : IBS Center for Soft and Living Matter and UNIST, South Korea

Resume : A fundamental challenge of modern soft matter physics is to form structure that is not frozen in place but instead reconfigures internally driven by energy throughput and adapts to its environment robustly. Predicated on fluorescence imaging at the single-particle level, this talk describes quantitative studies of how this can happen. With Janus colloidal clusters, we show the powerful role of synchronized motion in self-assembly. In living cells, we find that transportation efficiency problems bear a provocative parallel with polymer chain trajectories with their spatial extent, and with jammed matter in their time evolution. A picture emerges in which simple experiments, performed at single-particle and single-molecule resolution, can dissect macroscopic phenomena in ways that surprise.

Authors : Stefano Sacanna
Affiliations : New York University

Resume : Anisotropic colloids with complex shapes and tunable compositions, are synthesized in bulk via an emulsion-based method. Solid particles are systematically dewetted from polymerizable micro-droplets yielding a whole new class of asymmetric colloids. We demonstrate that the method is applicable to a broad spectrum of materials, from polymer particles to inorganic semiconductors and magnetic materials. This synthetic methodology represent a new and general tool for designing functional colloids, such as micro swimmers, colloidal surfactants and self-assembling building blocks.

Authors : Francesco Stellacci
Affiliations : Ecole Polytechnique Fédérale de Lausanne

Resume : Dynamic molecular assemblies can arrange in equilibrium morphologies when all kinetics barriers are overcome. Similarly out-of-equilibrium arrangements can be engineered when tailor-made barriers are built in the systems. In this talk I will show approaches in my group to engineer out-of-equilibrium ligand shell structures for mixed-ligand coated gold nanoparticles. The approach will be based on building barriers during the synthesis of the nanoparticles to lead to arrangements suitable for the binding of small molecules.

11:30 Coffee break    
Authors : Sławomir Lach, Bartosz A. Grzybowski
Affiliations : IBS Center for Soft and Living Matter, UNIST

Resume : Propulsion systems are used on land and water and in the air to move to move various types of objects to desired locations. Design of such systems must take into account the fuel used, working environment and efficiency. Typically, the energy sources underlying traditional propulsion mechanisms is of chemical origin and based on either internal combustion or electrochemical processes. In addition, traditional propulsion systems require often complex mechanical motor assemblies which generate high levels of noise during their work and are responsible for emission of exhaust gases causing environmental pollution. With all these considerations in mind, tremendous research effort has focused on the identification of new and more efficient propulsion solutions. In my talk I will describe an unprecedented propulsion system powered by chemical fronts propagating over the interface of a liquid-metal “motor” and the surrounding water environment. The symmetry breaking of these fronts gives rise to counter-rotating vortices that propel the object – importantly, this scheme does not involve any movable parts such that propulsion is virtually noise-free. The phenomena behind our silent propulsion have been applied to move small prototype boats and as pumps in microfluidic systems.

Authors : Joanna Grybos, Zbigniew Sojka
Affiliations : Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow

Resume : Shape and structural defects of nanocrystalline oxides determines their electronic structure and redox properties. Being able to provide the local information, Cs-corrected high resolution transmission electron microscopy is an important tool for retrieving comprehensive morphological and structural information needed for a complete characterization of oxide nanomaterials. Increasing interest in the subtle differences of the structure (eg. atomic vacancies, location of oxygen, bonding effect in electron correlated spinels) creates need for a tools giving not only qualitative but also quantitative comparison of experimental and simulated images. HR TEM pictures are extremely sensitive to changes of the imaging parameters (both sample properties and microscope settings). It makes images simulations indispensable for correct data interpretation. Due to the combination of many factors (such as: electron scattering mechanism, aberration effects, point spread function of detector), contrast in experimental HR images is inevitably weaker, typically by about a factor of three, than that predicted by image simulations. Starting with the DFT geometry optimization, using Birch-Murnaghan equation of state, fully relaxed structure of unit cell was obtained. Than the phonon dispersion of the Co3O4 crystal lattice was measured using open source classical molecular dynamics simulations code LAMMPS.[1] According to the method proposed by Kong,[2] dynamical matrix was constructed by observing the displacement of atoms during molecular dynamics simulations, making use of the fluctuation-dissipation theory. Being not restricted to harmonic forces, molecular dynamics allows for including directly the effect of the temperature on the phonons. Further analysis of the phonon dispersion curves[3] allows for including the thermal diffuse scattering effect into the HR images simulations. Thereby, the calculated Debey-Waller factors, which in comparison with those obtained from X-Ray diffraction, are more accurate, and can be calculated for particular atoms localized at or near to the structural defects such as: surface, vacancies or dislocations and reduce the discrepancies between the simulated and experimental HR TEM images. Finally, phonon dispersion for each surface exposed by equilibrium shape of Co3O4 nanocrystal was calculated and used for analysing the modification of this shape[4] in a given temperature, by taking into account inclusions of the entropic term. [1] Plimpton S. J. Comp. Phys. 117, (1995) 1-19 [2] Kong I.T. Comput. Phys. Commun. 182 (2011) 2201-2207 [3] Parlinski, K. Software PHONON, Krakow, (2003) [4] Sojka, Z. et al. J. Phys. Chem. C, 115 (2011) 6423–6432

Authors : Leszek. M. Malec, Katarzyna M. Stadnicka
Affiliations : Faculty of Chemistry, the Jagiellonian University in Kraków

Resume : For almost 60 years ammonium sulfate (AS) has been known to exhibit ferroelectric properties below Tc at 223K. AS shows a unique dependence of spontaneous polarization (Ps ) versus temperature. Since Ps was not considered as the order parameter of the ferroelectric phase transition, AS has been classified as an improper or pseudo-proper ferroelectric. In ferroelectric phase AS belongs to polar Pna21 space group and in paraelectric phase its structure is described by centrosymmetric Pnam. Despite the variety of used experimental and theoretical approaches performed till now, the type of the phase transition and the mechanism of structural transformation is still not properly explained . In the present work the existing theories, which are often contradictory, were critically discussed and an attempt was made to investigate the structural changes by modern diffraction and spectroscopic methods. At first the series of single-crystal X-ray diffraction measurements were performed in the temperature range between 298 and 148 K. The significant modifications of the geometrical parameters for sulfate anion and two symmetrically independent ammonium cations as well as for the hydrogen bonds formed between them, were disscused in the view of previously discovered effects. We hope that the newly detected structural features will help to resolve the nature of the phase transition in ammonium sulfate.

13:10 Lunch break    
Authors : Lee Cronin
Affiliations : WestCHEM, School of Chemistry, University of Glasgow

Resume : How do high nuclearity inorganic and supramolecular assemblies form? Can understanding the minimal information content of the structures help us understand their assembly? Is there a general route to explore the mechanism and how can one given compound dominate from a combinatorial explosion of possibilities? In our current work we are using new approaches to probability theory and template design to explore the possibility of using high probability templates to assemble low probability structures with 1000s of atoms in a single molecule. Take the example of a recent molecule discovered in our laboratory: A palladium oxometalate {Pd84}-ring cluster 3.3 nm in diameter; [Pd84O42(OAc)28(PO4)42] water just by mixing two reagents at room temperature and can be observed in solution within a few days mixing and crystallised with a week, see Figure 1. The key question is how could a ring as large as the {Pd84} spontaneously form and crystallize within the period of days. Indeed the state space for the molecule, just considering the unique arrangements of distinct 84 Pd atoms, ignoring symmetry, gives an upper limit on the combinatorial space of 84! = 3.3 ? 10126. It is therefore perhaps safe to assume that the structure therefore did not ?spontaneously? form by random chance, but a series of templating events, combined with the correct kinetics, 70- ({Pd84} ≡ {Pd12}7) which is formed inallowed this cluster to be selected from the vast envelope of possible structures available in solution. In this lecture I will propose a new theory that may explain the mechanism of self-assembly of gigantic systems, as well as an approach to understand and use the information content of complex molecular structures.

Authors : Christopher W. Bielawski
Affiliations : University of Texas in Austin, Department of Chemistry and Biochemistry

Resume : This presentation will be divided into two parts. The first part will describe the use of various stimuli, including light and redox processes, to externally control various chemical transformations and polymerization reactions. These efforts have included the design and deployment of specially designed catalysts that contain photo and/or redox responsive units and are expected to facilitate access to polymeric materials with tailored structures, properties and functions. The second part of the presentation will focus on the synthesis and applications of contemporary carbon-based materials. We and others have found that the chemical potential intrinsic to graphite oxide (GO) and other forms of functionalized carbons may be harnessed to facilitate a wide range of useful transformation including oxidations, hydrations, and dehydrations, as well as various ionic oxidative, and acid-catalyzed polymerizations. In addition to displaying such broad reactivity, carbon-based catalysts also often offers a number of practical advantages as their heterogeneous nature can facilitate separation and purification procedures. The development of GO and related materials as catalysts for use in various synthetic transformations will be discussed, including those of potential commercial importance. Portions of the work to be described were supported by the Office of Naval Research and the Institute for Basic Science (IBS-R019-D1).

Authors : Fatima GARCIA MELO, Maarten M. J. SMULDERS
Affiliations : Laboratory of Organic Chemistry Wageningen University PO Box 8026, 6700EG Wageningen The Netherlands

Resume : In this contribution the synthesis of dynamic supramolecular polymeric assemblies is presented. The preparation of these assemblies relies on dynamic-covalent, metal-stabilised imine bonds in combination with coordination chemistry. The latter type of chemistry has proven especially useful in supramolecular material chemistry, as coordination bonds are highly directional and their relative strength and exchange kinetics can be tuned. In addition, dynamic-covalent bonds combine the robustness of covalent bonds with the reversibility of non-covalent bonds. As these polymeric materials are prepared by coordination chemistry and dynamic-covalent chemistry, they are inherently sensitive to their environment, which opens up possibilities of controlling the polymer’s properties and behaviour by external stimuli. The development of these materials is guided by a detailed understanding of the intermolecular interactions between the assembly’s constituents, which are obtained by physical-organic characterisation methods. Such ‘Systems Materials’ approach creates pathways for the development of new, structurally dynamic systems comprised of multiple interacting components that are designed to work in concert and can lead to new, increasingly more complex functions and materials, such as self-healing materials and surfaces, sensors, drug delivery, adaptive materials or tuneable catalysis.

Authors : Bengi Özkahraman
Affiliations : Hitit University, Faculty of Engineering, Department of Polymer Engineering, 19030, Çorum, Turkey

Resume : In this study, the copolymer has been synthesized and used drug release of poly(N-isopropylacrylamide-co-2-acrylamide-2-methyl propane sulfonic acid) nanogels having thermosensitive behavior. The measured amounts of NIPAM, AMPS and N’N methylene bis-acrylamide (NMBA) as crosslinker were disseolved in distilled water and the reaction was allowed to proceed for 6 h and 400 rpm. After synthesis the microgel was purfication by dialysis kit (Pur-A-Lyzer maxi 3500) with distilled water for several days. The chemical structure of the prepared nanogels was determined by FTIR analyses. The morphologies of the prepared nanogels were determined by SEM. Zeta potantial, polydispersity index and particle size analysis of the nanogels were determined. The results exhibit that this nanogel will be convenient that this nanogel will be for further studies such as controlled drug delivery.

Poster Session : -
Authors : Simas Rackauskas1, Andrei V. Alaferdov1, Raluca Savu1, Yulia A. Gromova2, Stanislav A. Moshkalev1
Affiliations : 1CCS UNICAMP, 13083-870, Campinas, Brazil; 2ITMO University, Kronverkskiy 49, Saint Petersburg, Russia;

Resume : Recently, semiconductor quantum dots (QDs), such as PbS, PbSe and CdSe, have become the subject of intense research due to ability to absorb or emit light with high efficiency, with widely tunable bandgaps that depend on the dimensions. These unique optical properties make colloidal QDs very attractive for applications in many areas including effective infrared photodetectors, organic light-emitting diodes and photovoltaic devices, as well as solar cell technology. In this work hybrid photosensors made from Single Walled Carbon Nanotube (SWCNT) with CdSe/ZnS QDs were investigated. SWCNTs were deposited by press transfer, metal contacts deposited, and QDs deposited by Langmuir-Blodgett method, controlling the thickness of layer. Devices were made in phototransistor configuration, which gives ability to apply a gate voltage on the channel and therefore tailor the photoresponse intensity. In order get a high performance of hybrid phototransistors, the thickness of QD layer should be optimized. SWCNT-QD phototransistor performance can be further increased by improving the process of charge transfer in QD layer. For the preparation of QD, as well as for its deposition, different long chain organics such as TOPO or oleic acid are used and remain in the end device. TOPO cannot be removed before deposition process as QDs tend to agglomerate, therefore it can be removed only after QDs deposition on the final device. In this work we demonstrate a preparation technique for hybrid SWCNT-QD photosensors, how the photoresponse of device can be varied by the thickness of QDs and gate voltage, also how the photoresponse can be further increased by heat treatment. We also investigate photogating effect, fast and slow photoresponse mechanisms, and processes of charge transfer between SWCNTs and QDs.

Authors : E. Yalaz, E.Pesen, O. Ukelge, M.Gunes, O.Erken, C. Gumus, B. Arpapay, U.Serincan, M.Henini
Affiliations :;;;; ozgerken@adı;;;;

Resume : We report on the optical properties of dilute magnetic semiconductor GaAs1-xMnx/AlAs and GaAs/AlAs quantum well structures grown on (100), (110), (311B) and (411B) orientations by Molecular Beam Epitaxy (MBE). We compared the optical emission of the Mn free and Mn containing 2nm quantum well structures. Temperature dependent spectral photoluminescence (PL) was performed on GaAs1-xMnx/AlAs and GaAs/AlAs structures having different orientations at temperatures between 15 K and 300K. The PL measurements showed that the band gap of the alloy decreases with increasing lattice temperature regardless of the growth orientations. This

Authors : N.Kalanda(1), A.Petrov(1), S.Demyanov(1), L.Kovalev(1), A.Blokhin(2)
Affiliations : (1) Scientific-Practical Materials Research Centre, NAS of Belarus, 19 P. Brovka Str., 220072 Minsk, Belarus (2) Belarusian State University, 14 Leningradskaya Str., 220050 Minsk, Belarus

Resume : The Sr2-хBaxFeMoO6-d system of a variable composition with a Curie temperature (Тс) higher than 300 K and almost 100% degree of spin polarization have been studied. A comparison of the results of magnetic and thermodynamic measurements data has made it possible to explain the phase transformations type. The investigations have been carried out in the mode of the discrete heat input on five samples having compositions Sr2-хBaхFeMoO6-d with х = 0; 0.4; 1.0; 1.6 and 2.0. Temperature dependences of the magnetization (М) for samples of all compositions are qualitatively identical. The value of М linearly decreases down to the paramagnetic state transition. The decrease of Тс is observed with an increase of Ba fraction which is caused by the change of the spin-spin interaction character. The revealed heat capacity anomalies relate to the second-order phase transitions of the λ-type, and the heat capacity does not obey the Debye Т3 – law in the temperature region 5 – 80 K. According to the magnetization measurements data, the anomalies of magnetic transformations correspond to the large enthalpy values. A considerably larger sensitivity of the adiabatic calorimetry method as compared with the magnetic measurements, makes it possible to detect the stated above phase transformations and confirms the existence of magnetically inhomogeneous areas in the compounds.

Authors : Yong-Kwang Jeong, Seok Min Yoon, Bartosz A. Grzybowski*
Affiliations : IBS Center for Soft and Living Matter, Department of Chemistry UNIST

Resume : Rhenium oxides and borides are among the hardest materials known and also exhibit physico-chemical properties interesting in the context of catalysis [1], high conductivity, tunable optical band gap [2], super-hardness [3] and more. It is unknown, however, how these super-hard materials behave when confined to non-equilibrium and nanoscopic dimensions. There are only a few reports on the synthesis of rhenium-based nanomaterials by thermal decomposition, gamma irradiation and so on. [4] The current work describes new synthetic routes to various types of rhenium oxide and rhenium boride nanostructures. These nanostructures are characterized by characterization methods including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), scanning electron microscopy (SEM), UV-VIS-NIR absorption, and photo-luminescence spectrometry. Interestingly, rhenium oxide nanostructures exhibit photoluminescence and bandshifts that depend on their morphologies and were not observed in the corresponding bulk states. Furthermore, the rhenium oxide nanostructures act as a catalyst synthesizing super-hard rhenium borides materials.

Authors : Michał Bajczyk, Sara Szymkuć, Prof Bartosz Grzybowski
Affiliations : Polish Academy of Sciences, Institute of Organic Chemistry

Resume : While the synthesis of traditional materials typically involves only one or only few types of components, biological entities use large collections of chemicals connected into networks to synthesize a whole range of materials they need for living. Chemistry and biochemistry have made enormous progress in understanding how biochemical networks work but we are still very far from being able to construct any similar systems that would be based on ex vivo reactions. The encouraging news, however, is that chemistry has created an enormous amount of reaction data that it has recently been able to connect this knowledge into one gigantic chemical network, called the NOC for the Network of Organic Chemistry. In my talk, I will discuss the architecture of this network and then the specific sub-motifs (e.g., cycles or autocatalytic motifs) that can be extracted from it using advanced computer science algorithms. I wil then ask whether the motifs we identified could be used “in the flask” to create small ex vivo chemical systems capable of synthesizing various molecules and materials in a concerted and more efficient ways than via traditional methods. I will argue that the discovery of such artificial chemical systems holds great promise for the chemistry and materials science of the 21st century.

Authors : W.Nogaś (a), R. Podgajny (a), S.Chorąży (c), M.Rams (b) , Anna M. Majcher (b), B. Sieklucka (a), K. Nakabayashi (c), S. Ohkoshi (c)
Affiliations : (a) Faculty of Chemistry, Jagiellonian Univ., Kraków, 30-060, Poland; (b) M. Smoluchowski Institute of Physics, Jagiellonian Univ., Kraków, 30-059, Poland; (c) Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 Japan

Resume : Polymetallic M9W6(M=Fe,Co,Ni,Mn) type clusters are currently extensively researched for the possibility of tuning their physical properties by varying the metal composition and organic ligand decoration. By rational choice of metallic composition, a multitude of mono- and polymetallic clusters has been obtained, with Fe9W6 and the FexCo9-xW6 series being the most prominent and unique by their temperature driven CTIST and spin state transition. Among other examples, SMM like behavior has been observed for Ni9W6(tetramethylphenanthroline)6 clusters and superparamagnetism in 1D cluster chains of Mn9W6 linked with di(pyridyl)ethylene ligands. The transitions in Fe9W6 and FexCo9-xW6 are reversible and accompanied by cluster and crystallographic cell compression and a thermal hysteresis loop, whose characteristics depend on cluster’s composition.

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Authors : Sijbren Otto
Affiliations : University of Groningen

Resume : Nature is proof that self-assembly is a powerful tool for constructing materials of impressive complexity and function. Chemists have taken inspiration from Nature and many self-assembled materials have been developed. Most of these methods rely on thermodynamic control, resulting in formation of the most stable self-assembled product. However, self-assembly in Nature is in most cases controlled by kinetics rather than thermodynamics, giving much richer behavior in terms of function and dynamics of the biomaterials. We have recently developed a new approach to self-assembling materials based on peptides that, like in Nature, relies on kinetics rather than thermodynamics. We use autocatalytic self-assembly processes, where the assembly of drives the synthesis of the very molecules that self-assemble. By mixing relatively simple building blocks that can form reversible covalent bonds with each other, we initially produce a complex mixture of many interconverting molecules. Self-assembly then shifts the product distribution to the self-assembling molecules, in many cases quantitatively. In this way, the self-assembling molecules self-replicate. Where different self-assembling self-replicating products compete it was found that the fittest prevail. We are now extending these studies with the aim of achieving Darwinian evolution of fully synthetic materials, by applying selection pressures in a regime where self-assembly and destruction occur concurrently. As selection is primarily driven by the kinetics of self-replication, the challenge is to link efficiency of replication to desired functional properties. Such methodology is potentially highly powerful for the development of new synthetic functional materials that complement current biomaterials.

Authors : Wilhelm Huck
Affiliations : Institute for Molecules and Materials Radboud University, Nijmegen

Resume : System-level functions of living systems, such as homeostasis, bistability, and temporal pattern formation, are controlled by complex chemical reaction networks (CRNs) whose characteristics transcend the properties of individual molecules and reactions. Despite substantial efforts in the engineering of complex molecular systems, the construction of functional out-of-equilibrium networks that take advantage of the versatility of synthetic chemistry remains a major challenge. Recently,1 we presented a versatile strategy for ?synthesizing? programmable enzymatic reaction networks in microfluidic flow reactors that exhibit sustained oscillations. The production of an oscillatory concentration of an active enzyme holds considerable potential for coupling to stimuli-responsive gels and other smart materials, which opens up applications in tissue engineering and soft robotics. Our work forms the basis of a bottom-up synthetic biology approach to the development of complex synthetic systems that operate according to the principles of life. In this lecture I will outline how such CRNs could become the controlling elements in ?living materials?. 1) S.N. Semenov, A.S.Y. Wong, R.M. van der Made, S.G.J. Postma, J. Groen, H.W.H. van Roekel, T.F.A. de Greef and W.T.S. Huck Rational design of functional and tunable oscillating enzymatic networks Nature Chemistry, 2015, 7, 160-165

Authors : Sara Szymkuć, Michał Bajczyk, Prof Bartosz Grzybowski
Affiliations : Insitute of Organic Chemistry, Polish Academy of Sciences

Resume : Traditional chemistry relies mostly on reactions that use one or two distinct substrates. For several decades, however, there has been a growing interest in reactions that can take three or more different substrates and convert them in just one synthetic step into a complex product. While such modes of one-step molecular assembly offer conceptual elegance and economic benefits, the problem with multicomponent reactions, MCRs, is that only few classes are known and are typically discovered by serendipity. In my talk, I will illustrate computational methods that allow for rational discovery of MCRs. The success of this approach also has implications for multicomponent self-assembly at scales larger than molecular and can lead to new, more efficient methods of fabrication on scales up to colloidal.

12:00 Lunch break    
Authors : Minjoong Yoon
Affiliations : Molecular/Nano Photochemistry and Photonics Lab, Department of Chemistry, Chungnam National University; KD Chemical-JNTInc Ltd, Moonpyung-dong

Resume : Broad visible light-responsive hybrid zeolites of polyoxometalate (POM)-encapsulated zeolite-supported AgNTiO2 nanochains (AgNTiO2@POM/Zeolite Y) were fabricated by binding AgNTiO2 nanochains on the outer surface of POM-encapsulated zeolite Y, and they were fully characterized by XRD, FESEM, TEM, XPS, DRS, and ICPAES analysis. Their photocatalytic activities for CO2 reduction with water were investigated under simulated solar illumination, and it was found that the solar photocatalytic reduction of CO2 produced CH3OH selectively with much higher conversion rate (240μmol/gcat/h) than that’s been reported to date. The photocatalytic water splitting over the hybrid zeolites was also observed to produce O2 with little H2. The incident-photon-to-electron conversion efficiency (IPCE) of the thin films of AgNTiO2@POM-Zeolite Y was enhanced, and its spectrum shiftstoward longer wavelength to be well resolved into two bands (450 nm, 650 nm) in contrast to the natural two photosynthetic systems competing for the nearly same photons. These results indicate that the hybrid zeolites are non-adiabatic systems harvesting two photons efficiently to induce the proton-coupled electron transfer by stepwise excitation of AgNTiO2 nanochains and POM. To the best of our knowledge, these hybrid zeolites provide a first case of totally inorganic artificial photosynthetic membrane with long-term photostability to fix CO2 selectively as CH3OH by a modified Z-schematic cooperative transport of [...]

14:00 Coffee break    
Authors : Bilge Baytekin‡§, H. Tarık Baytekin‡, Bartosz A. Grzybowski†
Affiliations : ‡UNAM-Materials Science and Nanotechnology Institute, Bilkent University; §Department of Chemistry, Bilkent University; †Department of Chemistry, Ulsan National Institute of Science and Technology, UNIST

Resume : One of the distinctive features of living systems is that they can follow external cues: cells, bacteria and some organisms exhibit chemotaxis, animals swarm and flock, while plants turn their flowers or leaves in the direction of the sun. This last process is called phototropism (or heliotropism, when sun is being tracked) and is associated with the mechanical deformation of the some plant cells upon sun exposure. Inspired by this mechanism, several technologies have been developed that use computer-controlled motorized systems to position solar panels towards the sun and thus harness maximum amount of light energy possible. Here, we also mimic key features of plants’ heliotropism but do so without using computer controllers/pre-programming, motors, or gears. Instead, we drive heliotropic motions by stimuli-responsive materials – in the designs we describe, these systems contain of a shape memory alloy, nitinol, and known materials such as solar panels. Finally, we achieve to get pronounced changes in response to light stimuli and the systems are capable of maintaining themselves in non-equilibrium dissipative states, in which they maximize light energy.

Authors : Seok Min Yoon, Bartosz A. Grzybowski
Affiliations : IBS Center for Soft and Living matter and the Department of Chemistry, UNIST, Ulsan

Resume : Dynamic nanostructured materials (DNMs) comprise nanoscopic building blocks whose properties can be changed by external stimuli such as mechanical stresses, electric fields, magnetic fields, light irradiation and so on. Such materials are often discovered by serendipity but it would be highly desirable to design them rational ways to achieve what can be termed as “Functionality by Design”. This capability requires development of various synthetic approaches and thorough understanding of physico-chemical properties across several length-scales – from individual nanocomponents all the way to macroscopic DNMs. In my talk I will discuss such rational strategies applied to materials from one- to three-dimensional and often based on hybrid architectures involving nanoparticles as well as metal organic frameworks. I will illustrate the applications of such DNMs in electronic, optoelectronic and energy-related devices , all of which follow well-defined structure-property relationships.

Authors : Kinga Matuła, Łukasz Richter, Jan Paczesny, Robert Hołyst
Affiliations : Institute of Physical Chemistry PAS, Kasprzaka 44/52, 01-224 Warsaw, Poland.

Resume : Bacteria are perfect example of flexible biomodels which respond to changes of external conditions. Here we present the results how bacteria become resistant and how they can adapt to nanomechanical stress. We exposed Escherichia coli to ZnO nanorods (ZnO NR) under stirring as an example of external stress. During cytotoxicity studies we observed that bacterial cells, which survived 24 hours of incubation with ZnO NR, acquired mechanical resistance. Such bacteria in second run of the experiment were almost unaffected by exposure to ZnO NR. Gram-negative E. coli bacterium appeared as a Gram-positive strain in standard Gram staining method after exposure to ZnO NR. Electron microscopy (TEM, SEM and Cryo-SEM with EDS) analysis revealed changes of morphology of survivor cells. Additional genetic and proteomic studies were performed.

Authors : Łukasz Richter, Kinga Matuła, Jan Paczesny, Monika Księżopolska-Gocalska, Robert Hołyst
Affiliations : Institute of Physical Chemistry Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

Resume : Nowadays the bacterial infections are main cause of death during hospitalization, resulting in 90 000 lethal cases per year. We can avoid such threats if we develop better and faster methods of pathogen detection. Currently used techniques can take up to a few days for the analysis. Another threatened area is the food industry, especially the products with short expiration date. Main goal of my research was to create sensor for fast and sensitive detection of bacteria, based on layer of properly oriented bacteriophages. There were attempts to utilize bacteriophages for bacteria detection. However, such approach encountered number of issues. For instance, in case of sensors with layer of phages attached to the surface, proper orientation of bacteriophages is still a challenge. Bacteria binding receptors are present only on one end of the phage virion. Thus only specific orientation of phages provides required access to bacteria present in the analyzed sample. I used electric potential to orient phages properly during phage deposition process at the gold surface of the sensor. Such approach enables to increase the sensitivity of prepared biosensors. Obtained sensitivity was comparable with the sensitivity of the best chemically modified biosensors described in literature. I designed and created the new experimental set-up for phage deposition in the electric field. Electric potential was also used for deposition of an analyte on surfaces for surface-enhanced spectroscopies.

18:00 Best Student Presentation Awards Ceremony and Reception (Main Hall)    

No abstract for this day

Symposium organizers
Bartosz A. GRZYBOWSKIDistinguished University Professor UNIST, Ulsan, South Korea and Institute of Organic Chemistry, Polish Academy of Sciences

ul. Kasprzaka 44/52 01-224 Warszawa Poland

+48 571 377 294 / +48 22 343 2077
Janusz LEWINSKIFaculty of Chemistry

Warsaw University of Technology Noakowskiego 3 00-664 Warszawa Poland