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？

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

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

RAFT Agents and Functionalization ( C )

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

Reaction Conditions – Monomers and RAFT Agents Typical RAFT Agents and their structural variety (CSIRO) Leaving group Stabilizing group

Generally accepted mechanism for a RAFT polymerization

Reaction Conditions – Monomers and RAFT Agents Typical RAFT Agents and their structural variety (CSIRO) Leaving group Stabilizing group

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

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

RAFT 试剂的合成 Synthesis of RAFT agents using free thiol

Scheme. Different peptide-macroRAFT agents.

Chemical modification of ester activated RAFT agent by biocompounds, such as phospholipid, biotin, carbohydrate

Post-polymerization functionalization of poly(NIPAAm) with biotin via NHS-ester activation.

Synthesis of BSA-macroRAFT agent by two different routes: thiol-maleimide addition and thiol-pyridyl disulfide exchange

RAFT 聚合物的进一步改造

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)

各种各样的单体

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 :

Block Copolymers, Nano/Micro-spheres, Micelles and Stars (CSIRO) ABA triblock copolymers via difunctional RAFT agents

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

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.

7. Biodegradable Three-armed Star Polymeric Architectures Jingquan Liu *, Huiyun Liu, Zhongfan Jia, Volga Bulmus and Thomas P. Davis, Chemical Communications, 2008,

8. Biodegradable Star Polymers Functionalized With β - Cyclodextrin Inclusion Complexes

Tailoring the end groups and cleavage tests

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

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..

10. Thermosensitive graphene-polymer composites

Jingquan Liu, Wenrong Yang, Lei Tao, Dan Li, Cyrille Boyer and Thomas P. Davis, Journal of Polymer Science Part A: Polymer Chemistry, 2010, 48, （ IF ， ）. Characterization of thermosensitive graphene- polymer composites

11. pH sensitive graphene-polymer composites and self-assembly

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, （ IF ， ）

Boyer C., Bulmus, V., Davis T. P., Ladmiral V., Liu J., Perrier S. Chemical Review 2009, 109, ( 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