1、大分子自組裝研究的進展 Studies on Macromolecular Self-assembly 江明 復(fù)旦大學(xué)壽分子科學(xué)糸 分子組裝是最普遍的物理化學(xué)現(xiàn)象，是構(gòu)廷生 命體系的基本途徑 細(xì)胞膜的絡(luò)構(gòu) 0TOE , 蹴胎幻y 礙脳雙By 大分子自組裝是超分子化學(xué)和高分子科學(xué)的交 叉領(lǐng)域 Macromolecular self-assembly interdisciplinary research field Important Part of Supramolecular Chemistry and polymer science 大分子自組裝是創(chuàng)造具有納米或亞微米尺度的 結(jié)構(gòu)新物質(zhì)的簡單

2、和清潔的途徑 Simple and clean ways to create new，structured polymeric materials (soft matters) in nano or sub micro sizes 美國科學(xué)雜志于2005年出版?？?，提出了21世紀(jì)亟待解決的 25個重大科學(xué)問題，化學(xué)自組裝是其中堆一的化學(xué)問題。 Robert F. Service Science 2005,309、95iru 應(yīng)gencz、new,、 c ph ax 心H for now. Bui chCTnKB lime co fkxlin creMhv nrw wiy lomtWAaik%

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6、a wide variety of BjnKKiruLturvK. *1 出big wire the cnfnpo- Mnu ihm*olc- u”can k irfifd in undeutablt ivuid. Auy new Mci ibat rclic on 5df-a e tiH inuM be iHc Ciilxi Io lvlc dcfccte ut tepAtr them. Atai. bmBugy offer* an ID DMA. H IKS How Far Can We Push Chemical Self-Assembly Macromolecular Self-ass

7、embly : 大分子自組裝的兩重含義： 以大分子為組裝單元構(gòu)建組裝體 Macromolecules as building blocks to form structured assemblies 以小分子為組裝單元構(gòu)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. 系列學(xué)術(shù)研討會 長春夏季化學(xué)研討會：有序功能體系 國際香山科學(xué)討論會- 1994年 超分子體系 1998 年 超分子體系:從分子構(gòu)筑到功能組裝 2001 年 超分子體系：材料科學(xué)與生命科學(xué)間的

11、橋梁 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 沈家斕 H. Ringsdorf Scbemo 1 Approach for the Synthesis of tho Amphiphilic Polymer NF

14、H 2004 年 超分子體系：從微米/納米結(jié)構(gòu)研究材料科學(xué)和生物技術(shù)的方法 楊柏，吉林大學(xué) 張希，清華大學(xué) 高長有，浙江大學(xué) Supramolecular Layered Structure Multi-layer membrene Nano-pattering of surface Hollow micro-encapsules 基于高分子膠束的層狀組裝：偶氮苯分子的包覆與光 致異構(gòu)化速率的提高 妙的利用高分子膠束結(jié)構(gòu)所提供的微環(huán)境爲(wèi) 使偶氮苯一般偶氮苯在固態(tài)膜中的光致異構(gòu)化 0.15- 速率和效率常常比其在溶液中低。我們巧= Time (min) Number of cycles 光致異構(gòu)

15、化的速率在固態(tài)膜中比 2011： 其在溶液中還快一倍。 I 0.09- C 0.07 - 張希等 et aL Langmuir, 2006, 22, 3906 21世紀(jì)科學(xué)總化學(xué)專原列 復(fù)旦丸學(xué) Fudan University Ming Jiang （江明） Daoyong Chen （陳道勇） Ping Yao （姚萍）90 年代初，研究興趣在高分子 氫鍵相互作用和相容性問題 大分子絡(luò)合物 驅(qū)動力：氫鍵 自發(fā)過程 分子組裝？ ？ 我們反復(fù)思考的問題是： 能否通過高分子間的絡(luò)合作用實現(xiàn) “規(guī)則組裝，？ 我們提出并成功地實現(xiàn)了 “高分 子膠束化的非嵌段共聚物路線” u Block-copoly

16、mer-free routes for polymeric micellization via interpolymer complexation One of Approaches 將質(zhì)子給體基限于鏈的端 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) 多種途徑實現(xiàn)“非嵌段共聚物膠 束化” 均聚物，離聚物，齊聚物，接枝 共聚物等均可用為組裝單元 這是具有普遍意義的路線： 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 利用核殼“非共價”連接，通 過殼交聯(lián)和核溶解獲得空心球 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 環(huán)境響應(yīng)膠束：pH，溫度, 光，離子強度等 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