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中国梦 每个人都应该有梦想成真的机会 每个人都应该有共同出彩的机会 平等与奋斗 我曾经有一个梦 你的梦是什么 ? 梦要如何实现?
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RAFT polymerization Reversible addition-fragmentation chain transfer polymerization ATRP polymerization Atom transfer radical polymerization NMRP polymerization nitroxide mediated radical polymerization Living Radical Polymerization 活性自由基聚合
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Introduction Reversible Addition Fragmentation Chain-Transfer (RAFT) Polymerisation b.RAFT polymerization Polymerize more versatile monomers in more flexible reaction conditions for a wide range of polymeric architectures Get rid of the metal catalyst which might complex with some functional groups on proteins and damage the protein bioactivity. a. Atom transfer radical polymerization (ATRP) Synthesize well-defined polymeric architectures with predictable MW and PDI Supply a good technique to prepare well-defined protein-polymer conjugate
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RAFT Agents and Functionalization ( C )
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关于 RAFT 聚合应掌握如下几点 : 1.RAFT 试剂都是二硫酯或三硫脂 2.RAFT 试剂都有一个 R 和 Z 基团 3. 所有的链增长都发生在 R 和 S 之间 4. 相对较活泼的基团是 R 基团 5. 一般来说,取代较多的基团是 R 基团
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Reaction Conditions – Monomers and RAFT Agents Typical RAFT Agents and their structural variety (CSIRO) Leaving group Stabilizing group
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Generally accepted mechanism for a RAFT polymerization
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Reaction Conditions – Monomers and RAFT Agents Typical RAFT Agents and their structural variety (CSIRO) Leaving group Stabilizing group
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Reaction Conditions – Monomers and RAFT Agents The RAFT agent and monomer have to be carefully selected for an efficiently functioning RAFT process: Well chosen Poorly chosen
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Reaction Conditions – Monomers and RAFT Agents The RAFT agent and monomer have to be carefully selected for an efficiently functioning RAFT process: Well chosen Poorly chosen
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RAFT 试剂的合成 Synthesis of RAFT agents using free thiol
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Scheme. Different peptide-macroRAFT agents.
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Chemical modification of ester activated RAFT agent by biocompounds, such as phospholipid, biotin, carbohydrate
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Post-polymerization functionalization of poly(NIPAAm) with biotin via NHS-ester activation.
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Synthesis of BSA-macroRAFT agent by two different routes: thiol-maleimide addition and thiol-pyridyl disulfide exchange
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RAFT 聚合物的进一步改造
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Reaction Conditions – Monomers and RAFT Agents Typical RAFT reaction conditions are identical to those of the associated conventional FRP Nearly all monomers can be polymerized in a living fashion via the RAFT process – provided the RAFT agent is judiciously chosen Purification of the resulting polymers is simple – they are however coloured (red, yellow, pink)
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各种各样的单体
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反应温度 : 常温引发 ( 常温引发剂, 光引发, 微波引发, 辐射引发 ; 热引发 反应介质 : 水相, 有机相, 本体 高分子分离纯化 : 分离纯化简单, 沉淀法, 透析法等 反应温和易控 :
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Block Copolymers, Nano/Micro-spheres, Micelles and Stars (CSIRO) ABA triblock copolymers via difunctional RAFT agents
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Introduction Methods to Prepare Biomolecule -polymer Conjugates In situ polymerization Advantages Less steps Easy to control b) In situ polymerization Less-purification High yield Biomolecule Biomolecule -polymer conjugate
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5. pH-Detachable Polymer Brushes Formed Using Titanium-diol Coordination Chemistry and RAFT Polymerization Jingquan Liu *, Wenrong Yang, Hadi M. Zareie, J. Justin Gooding and Thomas P. Davis, Macromolecules, 2009, 42 (8), pp 2931–2939.
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7. Biodegradable Three-armed Star Polymeric Architectures Jingquan Liu *, Huiyun Liu, Zhongfan Jia, Volga Bulmus and Thomas P. Davis, Chemical Communications, 2008, 6582-6584.
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8. Biodegradable Star Polymers Functionalized With β - Cyclodextrin Inclusion Complexes
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Tailoring the end groups and cleavage tests
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Eki Setijadi, Lei Tao, Jingquan Liu *, Cyrille Boyer, Zhongfan Jia and Thomas P. Davis, Biomacromolecules, 2009, 10 (9), pp 2699–2707. Cholesterol Attachment and cyclodextrIn Complex
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9. Synthesis of six-armed biodegradable star polymers Jingquan Liu *, Lei Tao, Jiangtao Xu, Zhongfan Jia, Cyrille Boyer and Thomas P. Davis, Polymer, 2009, 50, 4455–4463..
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10. Thermosensitive graphene-polymer composites
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Jingquan Liu, Wenrong Yang, Lei Tao, Dan Li, Cyrille Boyer and Thomas P. Davis, Journal of Polymer Science Part A: Polymer Chemistry, 2010, 48, 425-433. ( IF , 3.821 ). Characterization of thermosensitive graphene- polymer composites
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11. pH sensitive graphene-polymer composites and self-assembly
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pH sensitivity of the graphene-polymer composites of PDMAEA (a) and PAA (b) at different pH. Jingquan Liu, Lei Tao, Wenrong Yang, and Thomas P. Davis, Langmuir, 2010, 26, 10068-10075. ( IF , 4.079 )
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Boyer C., Bulmus, V., Davis T. P., Ladmiral V., Liu J., Perrier S. Chemical Review 2009, 109, 5402-5436. ( 作者按姓氏字母顺序排列。本人负责 Bioconjugates 部分的编写 ) 12. Highlight of RAFT polymerization
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