高分子的设计与合成 洪春雁 潘才元. 聚合物的结构 Architectures of polymers...

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Transcript of 高分子的设计与合成 洪春雁 潘才元. 聚合物的结构 Architectures of polymers...

  • Architectures of polymers

    Linear polymersPE, PP, PS, PVC etc.

  • Nonlinear polymersGrafting PolymerComb Polymer

  • H- shaped and -shaped copolymers

  • Star polymers Miktoarm star polymers

  • Mono-Dispersed

    Nano-Sized

    Egg-Like High density of surface Functional groups

  • Hyperbranched polymersUmbrella CopolymerDumbbell-shaped copolymers

  • Atom Transfer Radical Polymerization, ATRP ATRP or Atom Transfer Radical Polymerization is a Polymerization reaction involving free radicals. It was introduced as an extension to ATRA or Atom Transfer Radical Addition by Jinshan Wang and Matyjaszewski, (1995) and Sawamoto (1994/5).

  • DrKrzysztof MatyjaszewskiJ.C. Warner Professor of Carnegie Mellon University Department of Chemistry 4400 Fifth Avenue Pittsburgh, PA 15213

    Dr. Mistuo Sawamoto Department of Polymer Chemistry Graduate School of Engineering Kyoto University, Kyoto

  • RAFT PolymerizationRAFT= Reversible Addition-Fragmentation Chain Transfer Polymerization

  • Dr. Graeme MoadCSIRO Molecular and Health Technologies, Bayview Avenue, Clayton, Victoria 3168, AustraliaHe joined CSIRO as a research scientist in 1979 and is currently a chief research scientist. Dr Moad is coauthor of the book The Chemistry of Free Radical Polymerization which appeared as a second edition in 2006. His research interests lie in the fields of polymer design and synthesis (free radical polymerization, reactive extrusion), polymerization kinetics and mechanism, and most recently polymer nanocomposites.

  • Dr. Ezio RizzardoCSIRO Molecular and Health Technologies, Bayview Avenue, Clayton, Victoria 3168, AustraliaEzio Rizzardo is a graduate of the University of New South Wales and received his Ph.D. from the University of Sydney for his studies on the photochemistry of nitro compounds. He joined CSIRO in 1976 after a postdoc at Rice University, RIMAC, and the Australian National University. His CSIRO research has focused on developing methods for controlling free radical polymerization. For this he has received a number of awards including the RACI Australian Polymer Medal and the CSIRO Chairmans Gold Medal. Currently he is a CSIRO Fellow and a Fellow of the Australian Academy of Science.

  • San H. Thang was born in Saigon, Vietnam, in 1954 and came to Australia in 1979 as a refugee. He completed his B.Sc.(Hons) degree in 1983 and Ph.D. in 1987 from Griffith University. He joined CSIRO in 1986 as a research fellow. He then moved to ICI Australia in late 1987 to undertake the challenge of industrial research. He returned to CSIRO in late 1990, and in 1995 he was co-inventor of the RAFT Process. He is currently a senior principal research scientist at CSIRO Molecular and Health Technologies where his research focuses on the interface between organic and polymer chemistry.CSIRO Molecular and Health Technologies, Bayview Avenue, Clayton, Victoria 3168, AustraliaDr.San H. Thang

  • Click Chemistry

  • Thiol-Click

  • Michael addition reactionArthur Michael (18551942), who discovered the Michael addition reaction. (b) Schematic depiction of the Michael addition reaction.

  • General carbon-Michael reaction mechanistic scheme.

  • Second Michael addition of acetoacetate group to methyl acrylate.Michael Addition involving an alkyne acceptor.

  • Higher reactivity of secondary amines in aza-Michael addition reactions.

  • Dendrimer

  • Side chain polarityAmino AcidHydropathy index

  • Synthesis of L-valine and L-leucine type Ib dendrimers: (a) Boc-Gly-OH, DCC, DMAP-DCM; (b) TFA-DCM; (c) active ester, HOBt, DIEA, DMF-DCM; (d) Ac2O, DIEA-DC

  • Is Dendrimer an Antenna?

  • Cis- and trans- transformation of azobenzeneIrradiation at 1600 cm-1 can make the transformation of cis- to trans-?

  • Photoisomerization of Azodendrimer by Harvesting of Low Energy PhotonsPhotons (1600 cm-1)

  • G2 dendrimers containing Coumarin-2 as an energy donor and Coumarin-343 as an energy acceptor (left) and dendrimers without Coumarin-343 chromophore (right) for relative rate study.

  • Organic Light Emitting Diodes

  • Catalysishttp://perceco2.chem.upenn.edu/~percec/inthenews/denx.htmlhttp://www3.interscience.wiley.com/cgi-bin/fulltext/106558159/PDFSTART

  • Nanowires

  • The dendrimer (blue and red) attaches to multiple receptors (pink) on cell membranes or other biological structures such as a virus.

    The dendrimers (blue and red) in VivaGel interact with protein structures (yellow) on the surface of HIV, blocking the interaction of HIV (purple) with healthy human cells (pink) that results in HIV infection.Illustrations courtesy of Starpharma Pooled Development, LtdDendrimers Fighting the Spread of Diseases

  • Dendrimer

  • Hyperbranched Polymer

  • Couple-monomer methodology (CMM)

  • No filterWU (330~385nm)WB (460~490nm)WG (510~550nm)

  • The EndThankYou

    ,,,, The excellent film-forming and unique encapsulation properties of many dendritic molecules can be combined to create multicolor, single-layer devices. Here, naphthyl dipheylamine terminated poly(benzyl ether) dendrimers with a coumarin laser dye or a pentathiophene core was used to prepare two-component (i.e. two-color), single layer devices. The dendrimers act as both hole transporters and emitters. Although a mixture of the two dyes only emitted light from the lowest band gap pentathiophene chromophore, dendritic encapsulation enabled simultaneous emissions from the two dyes.

    *A dendrimer can act as a support, displaying multiple copies of the catalyst at its periphery. In another approach, catalysis occurs within the dendrimer, offering possibities of encapsulation of the reactive site to avoid its deactivation, or the creation of a special nanoenvironment that assists and enhances the catalytic process.

    Here are 2 different representations of the same reactor. The amphiphilic design of the dendrimer catalyst leads to preferential accumulation of substrates and, in some instances, stabilization of transition states or intermediates in the interior, while the product is simultaneously expelled into the external medium, thereby preventing inhibition of the reactive site.

    *The researchers made the wires by attaching electrically-conductive molecules to the bases of branched polymers. Polymers are long, chain-like molecules that can easily be made to change shape.

    When the wedge-shaped dendrimers come together, they form cylinders around the conductive molecules attached to the points of the dendrimer wedges. The conductive molecules stack up, forming sets of four, five or seven columns encased within the dendrimer spiral. The dendrimers electrically insulate and keep moisture away from the electrically-conductive columns. The method could be used with many kinds of conductive materials, said Percec. "A large variety of electronically active molecules can be incorporated in the center of the cylinders." *Starpharma chose the application first because it takes advantage of the synthetic molecule with branching parts precise, nanoscale scaffolding upon which the right chemical compounds can be attached. Such tailored dendrimers can interact with viruses at multiple sites a concept called polyvalence in a manner that mimics proteins and other natural processes. Polyvalent pharmaceuticals are viewed by some drug researchers as more effective than conventional small molecule drugs.

    VivaGel also succeeded in preventing infection in monkey trials using a humanized strain of simian immunodeficiency virus. Studies conducted at University of Washington found that a single vaginal application of the gel protected 100 percent of the macaques exposed to the virus. The gel not only prevents adhesion to healthy cells, but also incapacitates the virus even if it gets into the cell.

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