报告题目: Topological Polymer Chemistry: ConstructingComplex Macromolecular Graph Architectures
报告人: Yasuyuki Tezuka
Department of Organic andPolymeric Materials, Tokyo Institute of Technology
Meguro-ku, Tokyo 152-8552, Japan, ytezuka@o.cc.titech.ac.jp
报告时间：2016年10月23日（周日）上午8点30分
报告地点：苏州大学独墅湖校区一期907号楼1101室
Abstract:
Topologically intriguing polymer chain architectures have continuouslybeen an attractive research subject [1]. A class of multicyclic polymertopologies, including three subclasses of fused, spiro and bridged forms, are particularly unique not only from thetopological geometry viewpoint but also from their programmed foldingstructures of biopolymer relevance. We have developed an electrostatic self-assembly and covalent fixation (ESA-CF) protocol[1], in which ion-paired polymer self-assemblies are employed as keyintermediates. In addition to all three types of dicyclicconstructions, i.e., θ (fused), 8 (spiro) and manacle (bridged) forms, a variety of tri-, tetra- and even hexacyclicpolymer topologies of spiro- and bridged-forms and three doubly-fused tricycle (-, - and δ-graph)forms, as well as a triply-fused tetracyclic and a quadruply-fused pentacyclic forms (unfolded tetrahedron-graph, and “shippo”-form, respectively)were subsequently constructed through the ESA-CF protocol in conjunction with atandem alkyne-azide addition, i.e., click,and olefin metathesis, i.e., clip,reactions [2].
We have constructed, in particular, a triply-fused tetracyclic macromolecular K3,3 graph [3], whichis known as a prototypical non-planar graph in topological geometry, andremarkably, moreover, has been identified in cyclic polypeptides (cyclotides)produced through the intramolecular S-S bridging with cysteine residues. An electrostatic polymer self-assemblyconsisting of a uniform-size dendritic polymer precursor having six cyclicammonium salt end groups carrying two units of a trifunctional carboxylatecounteranions was subjected to the covalent conversion under dilution. The K3,3 graph product wassubsequently separated and isolated from a constitutional isomer of the ladderform by means of a recycling SEC technique.
[1] Topological Polymer Chemistry: Progress of cyclic polymers insynthesis, properties and functions, Y. Tezuka ed., World Scientific,Singapore, 2013. [2] Heguri H, YamamotoT, and Tezuka Y, Angwew. Chem. Int. Ed.., 54, 8688 (2015); [3] Suzuki T,Yamamoto T, and Tezuka Y, J. Am. Chem.Soc., 136, 10148 (2014).
Biography
Yasuyuki Tezuka, born on August 22, 1953 inKyoto, Japan, is currently Professorof Tokyo Institute of Technology. Heobtained a BS (1976) and a MS (1978) degree in synthetic chemistry at TheUniversity of Tokyo. He continued hisdoctorate course with Teiji Tsuruta as a promoter at The University of Tokyo,while he moved to Ghent University (Belgium) in 1979 as a fellowship student ofBelgian (Flemish) government. Hecompleted his doctorate study in Belgium in 1982 on the subject ofpoly(THF)-based telechelic polymers with Eric Goethals as a promoter. He then returned to Japanto start an academic carrier as an assistant professorat Nagaoka University of Technology. After the promotion to an associate professor in 1991,he moved to Tokyo Institute of Technology (Departmentof Organic and Polymeric Materials) in 1994, where he has been a full professor since 2003. He served as an editor/coeditor of several books, including Topological Polymer Chemistry (WorldScientific, 2013) and ComplexMacromolecular Architectures, Synthesis, Characterization and Self-Assembly (Wiley, 2011). He has published about 230 original papers and review articles. He received Tokyo Tech Awardof Best Teacher, 2004, and The Award of the Societyof Polymer Science, Japan (2010). He has currently served as an Editor of Reactive and FunctionalPolymers in succession to an Asian Editor during 2006-2011. His current research isfocused on topological polymer chemistry,in particular on the design of topologically unique macromoleculararchitectures, and of novel polymer materials by theirtopology effects.
Homepage;http://www.op.titech.ac.jp/lab/tezuka/ytsite/sub0e.html
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