大分子自组装研究的进展(精)

1、大分子自组装研究的进展 Studies on Macromolecular Self-assembly 江明 复旦大学壽分子科学糸 分子组装是最普遍的物理化学现象，是构廷生 命体系的基本途径 细胞膜的络构 0TOE , 蹴胎幻y 礙脳双By 大分子自组装是超分子化学和高分子科学的交 叉领域 Macromolecular self-assembly interdisciplinary research field Important Part of Supramolecular Chemistry and polymer science 大分子自组装是创造具有纳米或亚微米尺度的 结构新物质的简单

2、和清洁的途径 Simple and clean ways to create new，structured polymeric materials (soft matters) in nano or sub micro sizes 美国科学杂志于2005年出版专刊，提出了21世纪亟待解决的 25个重大科学问题，化学自组裝是其中堆一的化学问题。 Robert F. Service Science 2005,309、95iru 应gencz、new,、 c ph ax 心H for now. Bui chCTnKB lime co fkxlin creMhv nrw wiy lomtWAaik%

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7、embly : 大分子自组装的两重含义： 以大分子为组装单元构建组装体 Macromolecules as building blocks to form structured assemblies 以小分子为组装单元构建超分子聚合物 Small molecules as building blocks to form Supramolecular Polymers Building blocks : small molecules with proton-donating and proton -accepting groups Bu1 Bul O H-N A -H B fH NH OR O

8、-H.NBU， I igur ynth) )z d by m *n of grafting Thg polynwr* can wrm tho DuckM-yed typ moaolayer at the aiiTwaUa inUtrfWccr. Their bahaviorv in monolayor* at tho a:r/watlicd. Tho rolationship botwtcn tho ehotnical fitxucturo of the polymers and their behavior at the ftirwour interface was discussed Th

9、e order and stcbility of monnUyrrfl wore determined by graft degree The UVvisible spectra of thm kmd of colymcr :n solution tnU in LB Gluts wrtr VApJtfiiMid b/ llir muivculAi t&uiUMi UK*UI j. The ui mi UBLIUII uf ivuj incorpariated in the LB film WAS utudied by mean* of polanzed UVvisible spectr

10、a, and th layer structure of LB films was studied by X-ray diHractSoa A pocsiblo schematic model WAS proposed to “scribe the relationship Mwxn tho structure af th LB Him and that of thin kind of po：ymor. 系列学术研讨会 长春夏季化学研讨会：有序功能体系 国际香山科学讨论会- 1994年 超分子体系 1998 年 超分子体系:从分子构筑到功能组装 2001 年 超分子体系：材料科学与生命科学间的

11、桥梁 2727 Introduction In the last few yeara. numerous methods co stabilize model membranes have b en developed mainly by using a polymenc system. The use of oligomcnc amphiphiles or die incurporat；un of apacer groups into the polymeric amphiphile s decouple the disordered poljnner chAin from the orde

12、red membrane allou*B the formation of membranes from prepolymenzec amphiphiles. In our previous works wc have studied a now type polymTic LB film caJliKi th。Duckwgd and Duckwcadjustiuent of the configuration of the network at the air/watcr interface. We think tha： the flexible network here might hav

13、e actd as & special apacer group. It is impoeaible for prepolymeric ampliiphileti to form extremely ordered structures at the aiD*waer interface. But. if we ignore the order of . _ _ _ 亠 _ 一. _ _ _亠_亠_4 亠 _ 1991 年 沈家斓 H. Ringsdorf Scbemo 1 Approach for the Synthesis of tho Amphiphilic Polymer NF

14、H 2004 年 超分子体系：从微米/纳米结构研究材料科学和生物技术的方法 杨柏，吉林大学 张希，清华大学 高长有，浙江大学 Supramolecular Layered Structure Multi-layer membrene Nano-pattering of surface Hollow micro-encapsules 基于高分子胶束的层状组装：偶氮苯分子的包覆与光 致异构化速率的提高 妙的利用高分子胶束结构所提供的微环境爲 使偶氮苯一般偶氮苯在固态膜中的光致异构化 0.15- 速率和效率常常比其在溶液中低。我们巧= Time (min) Number of cycles 光致异构

15、化的速率在固态膜中比 2011： 其在溶液中还快一倍。 I 0.09- C 0.07 - 张希等 et aL Langmuir, 2006, 22, 3906 21世紀科学总化学专原列 复旦丸学 Fudan University Ming Jiang （江明） Daoyong Chen （陈道勇） Ping Yao （姚萍）90 年代初，研究兴趣在高分子 氢键相互作用和相容性问题 大分子络合物 驱动力：氢键 自发过程 分子组装？ ？ 我们反复思考的问题是： 能否通过高分子间的络合作用实现 “规则组装，？ 我们提出并成功地实现了 “高分 子胶束化的非嵌段共聚物路线” u Block-copoly

16、mer-free routes for polymeric micellization via interpolymer complexation One of Approaches 将质子给体基限于链的端 基上 Restricting the reaction groups fvithin certain positions llong the chain hydrogen bonding leads to raffcopolymers and then Proton donor ends Interaction O groups In 十Proton acceptor H-bonding

17、nCTi afn copolymer lit selective solvein non-coialently connected micelles NCCM 0 PVPy-(CPB) J； :(PVPy)-CPB obverse7 and reverseNCCM of CPB/ PVPy Hydrodynamic Diameter (Dh) Distribution 2 JZ n 1 0 10 101 102 103 Dh (nm) 多种途径实现“非嵌段共聚物胶 束化” 均聚物，离聚物，齐聚物，接枝 共聚物等均可用为组装单元 这是具有普遍意义的路线： Polyimide / PVPy-con

18、talnlng polymers JACS J23, 12097, 2001; J Phys Chem B. 108, 550, 2004; 10& 5225,2004 Carboxyl-end polybutadiene (CPB) / Poly(vinyl alcohol)(PVA)- Macromolecules ,37, 1537, 2004 Poly(carprolactone)(PCL) / Poly(acrylic Acid) (PAA), Langmuir 21, 1531,2005 Poly(styrene-co-MAA) / Poly(vinlpyrollidone

19、) Langmuir, 17,6122, 2001 PCL/ PMAA-g-PCL Angew Chem Inti Edi, 41, 2950, 2002 利用核壳“非共价”连接，通 过壳交联和核溶解获得空心球 crosslinkable selective solvent crosslinking block copolymer Great interest in obtaining polymeric hollow spheres: Liu G, Wooley K photo-degradation chemical-degradation From NCCM to Hollow Sphe

20、res crossinking PVPy shell by 1,4 -dibromobutane in CH3NO2 CH3NO2 Cavitation in DMF DMF 200nm 200nm TEM Image of Hollow Sphere obtained by core dissolution from NCCM of (PCL)-PAA 环境响应胶束：pH，温度, 光，离子强度等 Self-assembly of Double Hydrophilic Graft Copolymer Hydroethyl Cellulose (HEC) -g -Poly(Acrylic Aci

21、d) HEC-g-PAA 5 P Dou HJf Jiang M et al. Angew Chem I nt! Ed 42f 1516, 2003 Preparation of graft coplymer HEC-g-PAA COM I PAA graft COOT (IICH.-I- 1 接枝共聚物分子量的表征 Radius of Gyration Rg Hydrodynamic Radius RhSample MWX1O 5 a b/ nm / nm /Rh No. (HEC-g-PAA) CAA-1 1.67 53.8 40 1.49 Table 2-2 LLS Characteristic data of CAA-l and CAA-2 CAA-2 3.33 75.6 59.6 1.58 PAA grafts Sampl AA:AG (molar M X105 e No. Ua radio) (HEC Feed Polymer backbone) compos compositi ition on CAA-0 0.23:1 0.25:1 0.9 CAA-1 1.17:1 1.28:1 0.9 CAA-2 3.50:1 2.54:1 0.9 /=1.50 Means random coil AGU Characteristic data of