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Abstracts for IC'13 Oral Presentations Abstracts for IC’13 Oral Presentations 1 Plenary Lecture 1 The studies of selective metal recognition and metal-mediated oxidative demethylation Chuan He Department of Chemistry and Institute for Biophysical Dynamics, University of Chicago, Chicago 60637, USA. Email: [email protected] . Transition metal ions are essential for many life processes. Various organisms have evolved delicate systems to control cellular metal levels and metal homeostasis. I will present our recent efforts to develop genetically encoded probes that can monitor and image cellular distributions and fluctuations of metal ions. We have also developed small molecules that specifically target cellular metal trafficking pathways. We found that these molecules exhibit remarkable activity in inhibiting cancer cell proliferation and tumor growth. The underlying mechanism will be discussed. In addition, we design proteins that can selective recognize “unnatural” metal ions. For instance, a protein selectively recognizes uranyl with exceedingly high affinity and selectivity has been developed. This protein is capable of sequestering uranyl directly from seawater. Lastly, we study iron-catalyzed oxidative demethylation in biological regulation. I will present our recent efforts to study DNA and RNA demethylation catalyzed by the mononuclear iron- and 2-ketoglutarate-containing TET family and FTO/ALKBH5 proteins, with a focus on the new RNA demethylation in biological regulation established recently in my laboratory. 2 Plenary Lecture 2 Molecular Photovoltaics and Mesoscopic Solar Cells Michael Graetzel, Institute of Chemical Science and Engineering Ecole Polytechnique Fédérale Lausanne CH-1015 SwitzerlandSchool of Chemistr Email: [email protected] . Learning from the concepts used by green plants photosynthesis, we have developed nanostructured systems affording efficient solar light harvesting and conversion to electricity and fuels. Solar cells using dyes or semiconducting pigment particles as light harvesters supported by mesoscopic oxide scaffolds have emerged as credible contenders to conventional p-n junction photovoltaics. Dye sensitized mesoscopic solar cells (DSSCs) were the first to employ a nanocrystalline junction and achieve currently a solar to electric power conversion efficiency (PCE) of 13%. Recently, the use of perovskite pigments as light harvesters in solid state mesoscopic photovoltaics has allowed increasing the PCE to 15 %. This impressive performance, along with excellent long-term stability has fostered first commercial applications. Some 40 companies are currently involved in industrial production serving new markets in building integrated PV and producing light-weight flexible photovoltaics. Figure 1. left: schematic representation of a dye sensitized solar cell (DSC), right application of DSC glass panels in building facades References 1. M. Grätzel Nature 2001,414,338. 2. A.Yella, H.-W. Lee, H. N. Tsao,1 C. Yi, A.Kumar Chandiran, Md.K. Nazeeruddin, E. W-G Diau,,C.-Y Yeh, S. M. Zakeeruddin and M. Grätzel, Science 2011 334, 629. 3. J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao, M. K. Nazeeruddin,and M. Grätzel Nature 2013 499, DOI 10.1038/nature12340. 3 Plenary Lecture 3 Activation of Small Molecules by Main Group Compounds Philip P. Power Department of Chemistry, University of California, Davis One Shields Avenue. Davis, CA 95616, USA Email: [email protected] . The main theme of the lecture will be focused on how compounds derived from main group elements can effect the activation of H-H, C-H, N-H, and C-C bonds, as well as reversibly binding unsaturated molecules such as olefins or isocyanides. The lecture will focus on the reactions of a series of stable acyclic silylenes and their heavier-element congeners with ethylene (eq. 1), propene, tert-butylethylene, styrene, and norbornadiene, and the measurement of reaction energetics. In addition, the mechanism of C-H activation by germanium and tin alkyne analogues, and by isocyanide complexes of germylenes, will be described. It will be shown that the σ-donor/π-acceptor ratio of germylenes uniquely favor the C-H activation over their silicon or tin congeners. The long-term objective of such work is the development of catalysts based on inexpensive main group elements such as silicon or aluminum. 4 Plenary Lecture 4 Synthesis and Applications of Ordered Mesoporous Materials Dongyuan Zhao Department of Chemistry, Fudan University, Shanghai 200433, P. R. China Email: [email protected] Here, we demonstrate a surfactant-templating approach to synthesize ordered mesoporous materials with high surface area, uniform large pore size and high pore volume for the applications in energy storage and generation, biosensor and drug delivery, catalysis and water treatment. Especially, we show we demonstrate the facile organic-organic assembly approaches to synthesize ordered mesoporous phenolic resin polymers and a direct transformation to homologous carbon frameworks. A family of ordered mesoporous organic polymers and carbons are simply achieved by using commercial available cheap phenol and formaldehyde as precursors, triblock followed with a carbonization process. The mesoporous carbons have a large uniform mesopore (2 ~ 20 nm), high surface areas (800 ~ 2400 m2/g) and large pore volume (0.8 ~ 2.4 cm3/g. The mesostructures can be easily tuned from hexagonal (space group p6mm) and cubic (Im3m, Ia3d, Fd3m, Fm3m). It is interesting that by using this hydrothermal method, single crystals, nanospheres, vesicles and monoliths can be easily synthesized. For example, mesoporous carbon nanospheres with uniform diameter of 20 ~ 140 nm are fabricated through a low-concentration route. All the mesoporoes (~ 2.6 nm) are open and accessible. It shows no cytotoxicity and easily penetrates into living cells. The derived carbons with thick walls are first example of molecular sieves which have ultra high stability. We have developed some large-scale synthesis approaches, based on them, 50 Kilogrammes of ordered mesoporous carbons are easily produced in a small factory, which show potential applications in catalysis, electrochemical supercapacitors and water-treatment. The mesoporous materials reveal an excellent catalyst for the hydrocracking of heavy oil in industry such as long life (5000 hours) and high selectivity for diesel (> 85%). The mesoporous carbon show a high capacity (~ 308 F/g) and long life (> 50,000 cycles) when used as the device in small car. The mesoporous materials can also used in water treatment in industry scale. References 1. F. Q. Zhang, Y. Meng, D. Gu, Y. Yan, C. Z. Yu, B. Tu, D. Y. Zhao, J. Am. Chem. Soc., 2005, 127, 13508; J. Am. Chem. Soc., 2007, 129, 7746; Chem. Mater., 2006, 18, 5279; Y. Huang, et al; Chem. Commun., 2008, 2641; Z. X. Wu et al, J. Am. Chem. Soc., 2010, 132, 12042; Z. X. Wu et al, Adv. Mater., 2012, 24, 458. 2. X. D. Huang, et al, Adv. Mater., 2010, 22, 833; Q. Yue et al. Angew. Chem. Int. Ed., 2012, 51, 10368-10372; Y. Wan, Y. F. Shi, D. Y. Zhao, Chem. Mater., 2008, 20, 933; D. Gu, et al, Adv. Mater., 2010, 22, 833; Y. Fang, et al, Angew. Chem. Int. Ed., 2010, 49, 7987–7991. Y. Zhai et al, Adv. Mater., 2011, 23, 4828. 5 Plenary Lecture 5 Coordination Chemistry – the Next Generation Annie K. Powell Institute of Inorganic Chemistry, Karölsruhe Institute of Technology, 76131 Karlsruhe Germany. Email: [email protected] . The coordination chemistry developed by Alfred Werner at the beginning of the 20th century has evolved dramatically in recent years, fuelled partly by efforts in biomimetic chemistry seeking to model metal sites in biological systems and partly through efforts directed towards producing molecular-based systems with defined physical or architectural properties. In our recent work we have been developing the idea of the “Coordination Cluster” as a central entity in many modern coordination chemistry systems. In this lecture this approach will be illustrated using examples taken from our work and it will be shown how coordination chemistry can be used to create a variety of nanostructured materials using a bottom-up approach.[1] For example, nanoscale coordination clusters based on paramagnetic metal ions can have very large magnetic spins and show properties such as Single-Molecule Magnet behavior.[2,3] On the other hand, small coordination clusters carrying highly functionalized ligands can be used to divide space into nanoscale organic and inorganic regions[4] (Fig 1a). Such systems can be processed and often produce structured materials of the relevant oxides which can be useful new battery materials.[5] Furthernore, large coordination clusters can be used as Super Secondary Building Units (SSBUs) which can be linked by bridging ligands to give Super Metal Organic Frameworks, or SMOFs[6] (Fig 1b). Finally, relatively small ligands influence the shape and phase of mineral structures mimicking biomineralization processes[7] (Fig 1c). Figure 1a 1b 1c References 1. G. E. Kostakis, I. J. Hewitt, A. M. Ako, V. Mereacre, A. K. Powell, Phil. Trans. R. Soc. A, 2010, 368, 1509. 2. A. K. Powell, S. L. Heath, D. Gatteschi, L. Pardi, R. Sessoli, G. Spina, F. Del Giallo, F. Pieralli, J. Am. Chem. Soc., 1995, 117, 2491 3. A. M. Ako, I. J. Hewitt, V. Mereacre, R. Clérac, W. Wernsdorfer, C. E. Anson, A. K. Powell, Angew. Chem. Int. Ed., 2006, 45, 4926 4. W. Schmitt, J. P. Hill, M. P. Juanico, A. Caneschi, F. Constantino, C. E. Anson, A. K. Powell, Angew. Chem. Int. Ed., 2005, 44, 4187 5. W. Schmitt, J. P. Hill, S. Malik, C. A. Volkert, C. E. Anson, A. K. Powell, Angew. Chem. Int. Ed., 2005, 44, 7048. 6. M.N. Akhtar, PhD Thesis, Karlsruhe Institute of Technology, 2011 and publications in preparation. 7. S. B. Mukkamala, C. E. Anson, A. K. Powell, J. Inorg. Biochem., 2006, 100, 1128. 6 Burrows Lecture Solar Energy Conversion – An Inorganic Chemistry ‘Wonderland’ Leone Spiccia School of Chemistry, Monash University, Victoria 3800, Australia Email: [email protected] . The provision of energy to the 10 billion people expected to inhabit Earth by the end of the 21st century is one of the major challenges facing the world today.
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