大分子自組裝研究的進(jìn)展_江明

1、大分子自組裝研究的進(jìn)展大分子自組裝研究的進(jìn)展Studies on Macromolecular Self-assembly 江江 明明復(fù)旦大學(xué)高分子科學(xué)系復(fù)旦大學(xué)高分子科學(xué)系分子組裝是最普遍的物理化學(xué)現(xiàn)象，是構(gòu)建生命體系的基本途徑大分子自組裝是超分子化學(xué)和高分子科學(xué)的交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

2、米或亞微米尺度的大分子自組裝是創(chuàng)造具有納米或亞微米尺度的結(jié)構(gòu)新物質(zhì)的簡單和清潔的途徑結(jié)構(gòu)新物質(zhì)的簡單和清潔的途徑Simple and clean ways to create new , structured polymeric materials (soft matters) in nano or sub-micro sizes 美國科學(xué)雜志于美國科學(xué)雜志于20052005年出版?？?，提出了年出版專刊，提出了2121世紀(jì)亟待解決的世紀(jì)亟待解決的2525個重大科學(xué)問題，個重大科學(xué)問題，化學(xué)自組裝是其中唯一的化學(xué)問題化學(xué)自組裝是其中唯一的化學(xué)問題。Robert F. Service Scienc

3、e 2005, 309, 95.Macromolecular Self-assembly :大分子自組裝的兩重含義：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 A Ciferri, Macromolecular Rapid Commun

4、ications, 2002, 23, 511ABNNOOOHO4OOHBuilding blocks : small molecules with proton-donating and proton accepting groups NNOOOHO4OOHNNOHOABNOONOOORORNNNNNNButButButButHHHHNOONOOORORNNNNOOOOHHNOONOOORORNNNNNNButButButButHHHHNOONOOORORNNNNOOOOHHNNNNHHNNOONHButButSupramolecular PolymersA Little work in C

5、hina Macromolecules as building blocks to form structured assemblies Micellization of block copolymers in selective solvents Covalent bonds connecting the core and shellselective solvent for red blockselective solvent for blue blockCharacters:Size 10-200nmAmphiphilicity Applications:Encapsulation Dr

6、ug-delivery,Micro-reactor:Nano-metal particles,Nano-semi-conductor particlesCatalysis至至80年代末我國無系統(tǒng)性大分子自組裝研究年代末我國無系統(tǒng)性大分子自組裝研究先驅(qū)性的研究先驅(qū)性的研究Pioneer work 90 年代初年代初吉林大學(xué)吉林大學(xué) 沈家驄沈家驄, 張希等張希等 氣氣/ /液界面液界面“浮萍浮萍”與與“倒浮萍倒浮萍”膜組裝膜組裝微相分離微相分離間隔基效應(yīng)間隔基效應(yīng)兩親性聚合物兩親性聚合物 聚合物自組織層狀結(jié)構(gòu)聚合物自組織層狀結(jié)構(gòu)（有序性與穩(wěn)定性相結(jié)合）（有序性與穩(wěn)定性相結(jié)合）界面組裝界面組裝 提出

7、了類提出了類“浮萍浮萍”與與“倒浮萍倒浮萍”聚合物超薄膜的模型，利用親、疏水聚合物超薄膜的模型，利用親、疏水力進(jìn)行組裝，為解決聚合物膜的穩(wěn)定性與有序度相矛盾的問題提供了新思力進(jìn)行組裝，為解決聚合物膜的穩(wěn)定性與有序度相矛盾的問題提供了新思路。路。沈家驄、張希等沈家驄、張希等Langmuir, 1994, 10, 2727Thin Solid Films, 1992, 210, 625Macromolecules, 1991, 24, 4986 Macromolecules, 1990, 23, 5158浮萍浮萍倒浮萍倒浮萍airwaterairwater系列學(xué)術(shù)研討會系列學(xué)術(shù)研討會1991199

8、1年年沈家驄沈家驄 H. Ringsdorf長春夏季化學(xué)研討會：有序功能體系長春夏季化學(xué)研討會：有序功能體系國際香山科學(xué)討論會國際香山科學(xué)討論會- -1994年年 超分子體系1998年年 超分子體系超分子體系: :從分子構(gòu)筑到功能組裝從分子構(gòu)筑到功能組裝20012001年年超分子體系：材料科學(xué)與生命科學(xué)間的橋梁超分子體系：材料科學(xué)與生命科學(xué)間的橋梁20042004年年超分子體系：從微米超分子體系：從微米/ /納米結(jié)構(gòu)研究材料科學(xué)和生物技術(shù)的方法納米結(jié)構(gòu)研究材料科學(xué)和生物技術(shù)的方法 楊柏楊柏, 吉林大學(xué)吉林大學(xué)張希張希, 清華大學(xué)清華大學(xué)高長有高長有, 浙江大學(xué)浙江大學(xué)Supramolecula

9、r Layered Structure Multi-layer membreneNano-pattering of surface Hollow micro-encapsulesNNNNUV Vis01234567801234ln(A0-Aeq)/(At-Aeq)Time (min)01234560.070.090.110.130.15Abs at 320 nmNumber of cycles基于高分子膠束的層狀組裝：偶氮苯分子的包覆與光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)化速率的提高致異構(gòu)化速率的提高 一般偶氮苯在固態(tài)膜中的光致異構(gòu)化一般偶氮苯在固態(tài)膜中的光致異構(gòu)化速率和效率

10、常常比其在溶液中低。我們巧速率和效率常常比其在溶液中低。我們巧妙的利用高分子膠束結(jié)構(gòu)所提供的微環(huán)境，妙的利用高分子膠束結(jié)構(gòu)所提供的微環(huán)境，使偶氮苯光致異構(gòu)化的速率在固態(tài)膜中比使偶氮苯光致異構(gòu)化的速率在固態(tài)膜中比其在溶液中還快一倍。其在溶液中還快一倍。 LbL 薄膜薄膜甲苯溶液甲苯溶液張希張希 等等 et al. Langmuir, 2006, 22, 39064.0710-3 9.0310-3 1.1410-2 復(fù)旦大學(xué)復(fù)旦大學(xué) Fudan UniversityMing Jiang （江明）（江明）Daoyong Chen （陳道勇）（陳道勇）Ping Yao （姚萍）（姚萍）90年代初，年代

11、初， 研究興趣在高分子研究興趣在高分子氫鍵相互作用和相容性問題氫鍵相互作用和相容性問題C CF3F3COHCH CH2CH CH2nmCH2CO=COCH3CH3nPS(OH)-X X 8mol% PMMAABsegment pairing interpolymer complex 大分子絡(luò)合物大分子絡(luò)合物 驅(qū)動力：氫鍵驅(qū)動力：氫鍵 自發(fā)過程自發(fā)過程 分子組裝？分子組裝？Each A chain interacts with many B chains and vice versa 無規(guī)則的聚集體無規(guī)則的聚集體separated coils +common solvent我們反復(fù)思考的問題是：

12、能否通過高分子間的絡(luò)合作用實(shí)現(xiàn)能否通過高分子間的絡(luò)合作用實(shí)現(xiàn)規(guī)則組裝規(guī)則組裝？我們提出并成功地實(shí)現(xiàn)了我們提出并成功地實(shí)現(xiàn)了 “高分高分子膠束化的非嵌段共聚物路線子膠束化的非嵌段共聚物路線”“Block-copolymer-free routes for polymeric micellization via interpolymer complexation ”Interaction groups將質(zhì)子給體基限于鏈的端將質(zhì)子給體基限于鏈的端基上基上Restricting the reaction groups within certain positions along the chainOn

13、e of Approacheshydrogen bonding leads to graftcopolymers and then 非共價鍵合膠束非共價鍵合膠束(NCCM)Proton donor endsProton acceptorNCCMInobverse and reverse NCCM of CPB/ PVPyPVPyCPBnitromethaneIn chloroformObverse NCCMNCCMReverse NCCMNCCMhexaneNpolybutadiene with carboxyl groups at ends1001011021030123 f(Dh)Dh (

14、nm)PVPy-(CPB)(PVPy)-CPBHydrodynamic Diameter (Dh) Distribution多種途徑實(shí)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：這是具有普遍意義的路線：Polyimide / PVPy-containing polymersJACS ,123, 12097, 2001; J Phys Chem B, 108, 550, 2004; 108, 5225, 2004Carboxyl-end polybutadiene (CPB) / Poly(vinyl alcohol)(PVA) - Mac

15、romolecules ,37, 1537, 2004Poly(carprolactone)(PCL) / Poly(acrylic Acid) (PAA) , Langmuir 21, 1531 , 2005Poly(styrene-co-MAA) / Poly(vinlpyrollidone)Langmuir ,17,6122, 2001PCL/ PMAA-g-PCLAngew Chem Intl Edi, 41, 2950, 2002利用核利用核-殼殼“非共價非共價”連接，通連接，通過殼交聯(lián)和核溶解獲得空心球過殼交聯(lián)和核溶解獲得空心球Great interest in obtaining

16、polymeric hollow spheres:Liu G, Wooley Kdegradablecrosslinkableblock copolymerselective solventcrosslinkingphoto-degradationchemical-degradationFrom NCCM to Hollow Spheres crosslnking PVPy shell by 1,4 dibromobutane in CH3NO2Cavitation in DMF CH3NO2PS(OH)PVPyDMFTEM Image of Hollow Sphere obtained by

17、 core dissolution from NCCM of (PCL)-PAA環(huán)境響應(yīng)膠束：環(huán)境響應(yīng)膠束：pH, 溫度，溫度，光，離子強(qiáng)度等光，離子強(qiáng)度等Hydroethyl Cellulose (HEC) g Poly(Acrylic Acid) HEC-g-PAASelf-assembly of Double Hydrophilic Graft CopolymerDou HJ, Jiang M et al. Angew Chem Intl Ed 42, 1516, 2003Ce()/H+CHCH2COOHmPAA graftOHHHOHHOHCH2OCH2CH2OCH2CH2OHHOHH

18、CH2OCH2CH2OCH2CH2OHHOCH2CH2OHHOHHOOnHEC backboneHEC-g-PAAOHHHOHHOHCH2OCH2CH2OCH2CH2OHHOHHCH2OCH2CH2OCH2CH2OHHOCH2CH2OHHOHHOOn+CHCH2COOHPreparation of graft coplymer接枝共聚物分子量的表征接枝共聚物分子量的表征Characteristic data of HEC-g-PAA copolymersSample No.AA:AGU a (molar radio)M10-5(HEC backbone)M10-5 b(PAA grafts)A

19、veragegraft pointFeed compositionPolymer compositionCAA-00.23:10.25:10.9CAA-11.17:11.28:10.90.1751.58CAA-23.50:12.54:10.90.2102.61Cellulase+PAA graftsAGUTable 2-2 LLS Characteristic data of CAA-1 and CAA-2Sample No.Mw10-5 a(HEC-g-PAA)b/ nm/ nm/CAA-11.6753.8401.49CAA-23.3375.659.61.58/=1.50Means rand

20、om coilRadius of Gyration RgHydrodynamic Radius Rh02468101214100200300400500 /nmpH CAA-2 CAA-1The solution at pH range of 2-3 was unstable: the apparent increased with time. The values measured 20 min after the solution preparation were used. Figure 3-2 of HEC-g-PAA copolymers as a function of pH. T

21、he concentration was 1mg/ml. HEC-g-PAAMicellespH 3, molecularly dissolvedpH3)-COOH of PAA at pH3 can complex with HEC and form the “core” of micellesUncomplexed HEC segments form the “shell” of micelles (pH 3, molecularly dissolvedAt low pH, PAA protonated, forming complex with HEC main chain core;

22、HEC without PAA branches formed shell pH-controlled complexation-induced micellization (low grafting density is necessary!)COOH COO- + H+pH pH At low pH, Crosslinking of PAA grafts - to lock the structureDialysis against water, pH 3 7: DLS: size 350nm 650nmTEM: micelles hollow spheresAt pH 7, Hollow

23、 Spheres Form! pH 3-7:pH-dependent micelle-hollow- sphere transition pH1.3交聯(lián)交聯(lián)PAApH increaseCore-crosslinked miclle Low crosslinking density is necessary !pH=1.3Stable micelle交聯(lián)劑：交聯(lián)劑：2,2-(ethylenedioxy)bis(ethylamine) Dialysis pH=7PAA+HECdecomplexationReversible ?pH 3, protonation,complexation pH7,

24、deprotonation, de-complexation, disintergaration 1234567300350400450500550600650700pH increasepH decrease DialysisDialysisDhpHReversibility of the transition pH 3-7:pH-dependent micelle-hollow- sphere transition TEM observationsTEM observations（CAA2CAA2）pH=1.3pH induced micellespH=7Hollow spherespH=

25、1.3pH-induced micelles after one pH cycle15202530354045200250300350400450 / nmTempeature / oC H10-5, heating H10-5, cooling PNIPAM (Polyisopropyl acrylamide) -based reversible thermo-sensitivityAdv Funct Mat 15, 695 (2005)456789100200300400500dialysisdialysis / nmpH5.88.54.5PAA-based pH 4.5 8.5, vol

26、ume increases by 130 timesLangmuir 21, 1531 (2005)Building block : linear polymersArchitectural effect ?Dendrimer and Dendron as building blocks Preparation of Dendron G3H-Bonding Dendronized Polymers Formation of nanoparticles from G3/PVP in common solvent , ultrasonic treatment Hollow spheres? Col

27、lapsed thin-layer hollow spheres ?Crosslinked hollow spheres - much high strength G3/PVP23Thick wall hollow spheres Self-assembly driven by H-BondingOther driving forces? Inclusion complexation ?- CD- CD- CDNo. of glucose units 678cavity diameter, 5.3 8.3height of torus, 7.9 diameter of outher perip

28、hery, 14.615.4 17.5 approx volume of cavity, 3174 262 427 環(huán)糊精環(huán)糊精cyclodextrin 7OHOOHOH*O* hydrophilicityhydrophobicityStructures and properties of Adamantane (ADA)d 7 7 V 180 3 262 3Adamantane Complex stable constant 105The -CD cavity apparently has the optimum dimensions for interaction with adamant

29、ane derivate.7 Adamantane CD環(huán)糊精環(huán)糊精 是研究的最多的作用主體是研究的最多的作用主體在高分子方面主要是用于多聚輪烷在高分子方面主要是用于多聚輪烷-CD / PEO-CD / PEO如何將環(huán)糊精的包結(jié)絡(luò)合用于構(gòu)建高分如何將環(huán)糊精的包結(jié)絡(luò)合用于構(gòu)建高分子膠束？子膠束？ 通過通過inclusion complexation 構(gòu)建高分子膠束構(gòu)建高分子膠束基本思路：基本思路： 合成分別帶合成分別帶CD和和ADA的親水和疏水高分子，的親水和疏水高分子， 在水中形成通過在水中形成通過inclusion interaction 連接的核連接的核殼膠束（殼膠束（NCCM） ATRP

30、Mn =1.67 x 104Mw/Mn =1.21Mn =1.87 x 104Mw/Mn =1.28CD-containing monomer GMA-CDPGMA-CD MW 10,400Characters:Double-scale hydrophobic regions : 100nm and 0.7nmCavities available for surface modification NH2-COOHnegatively chargedpositively chargedMicelle surface modification Hollow sphere of crosslinke

31、d PGMA-CDDouble Scale Cavities 環(huán)糊精的包結(jié)絡(luò)合在大分子組裝研究中有很大的發(fā)展空間環(huán)糊精的包結(jié)絡(luò)合在大分子組裝研究中有很大的發(fā)展空間:表面活性劑表面活性劑; 納米金屬粒子納米金屬粒子; 光響應(yīng)有機(jī)分子光響應(yīng)有機(jī)分子; 催化催化陳道勇等：陳道勇等： 聚合反應(yīng)聚合反應(yīng)/組裝同步法組裝同步法合成合成納米納米結(jié)構(gòu)結(jié)構(gòu)Macromolecules 2005, 38 , 3550 Most-Accessed Articles: 20051.Nanoporous Polystyrene Containing Hydrophilic Pores from an ABC Tribl

32、ock Copolymer PrecursorRzayev, J.; Hillmyer, M. A.Macromolecules 2005, 38(1), pp 3-5. 2.A One-Pot Approach to the Preparation of Organic Core-Shell Nanoobjects with Different MorphologiesPeng, H.; Chen, D.; Jiang, M.Macromolecules 2005, 38(9), pp 3550-3553. 3.Synthesis and Direct Visualization of Bl

33、ock Copolymers Composed of Different Macromolecular ArchitecturesPyun, J.; Tang, C.; Kowalewski, T.; Frechet, J. M. J.; Hawker, C. J.Macromolecules 2005, 38(7), pp 2674-2685. 4.Deep-Red Electroluminescent Polymers: 4.Synthesis and Characterization of New Low-Band-Gap Conjugated Copolymers for Light-

34、Emitting Diodes and Photovoltaic DevicesYang, R.; Tian, R.; Yan, J.; Zhang, Y.; Yang, J.; Hou, Q.; Yang, W.; Zhang, C.; Cao, Y.Macromolecules 2005, 38(2), pp 244-253. 2005 據(jù)2005 全年第二陳道勇，陳道勇， 江明江明 Account of Chemical Research , 38, 494, 2005Strategies for Constructing Polymeric Micelles and Hollow Sp

35、heres in Solution via SpecificIntermolecular Interactions新挑戰(zhàn)：從合成高分子到天然大分子Target Materials : Micelles or Nano core-shell hydrogel made of proteins and polysacchrids biocompatible, biodegradable, non-toxic and even eatable （可食用性）（可食用性）Ping Yao (姚萍）， Fudan UniversityOvalbumin(白蛋白） and Lysozyme（溶菌酶）Oval

36、bumin: 385 aa, Mw 47000 DaIsoelectric Point 4.7, 7 nm 4.5 nm 5 nmLysozyme: 129 aa, Mw 14351 Da Isoelectric Point 10.7, 3.8 nm 2.4 nm 2.2 nm5.34.710.7已尋求到合適途徑獲得核殼納米微凝膠已尋求到合適途徑獲得核殼納米微凝膠Mixing at pH 5.3, weak interaction Adjust pH 10.3, Lys aggregates, Oval Protection Heat denatured具有普遍意義的途徑具有普遍意義的途徑 G

37、lobular + Globular:Ovalbumin and LysozymeBovine Serum Albumin and LysozymeOvalbumin and Overtransferrin Linear + Globular:as-Casein + Overtransferrin(as,beta,kappa-)Casein + Lysozyme Globular proteins + PolysaccharideOvalbumin + ChitosanYao et al: Langmuir 22, 2754, 2006 Biopolymers 81, 29, 2006 J Collois Interface Sci., in press Biopolymers in press 其他研究小組的成果其他研究小組的成果傳統(tǒng)的嵌段共聚物在選擇性溶劑中的傳統(tǒng)的嵌段共聚物在選擇性溶劑中的自組裝的研究已很少自組裝的研究已很少興趣集中于新的組裝單元，新組裝途興趣集中于新的組裝單元，新組裝途徑，新驅(qū)動力，聚電解質(zhì)等徑，新驅(qū)動力，聚電解質(zhì)等顏德岳等顏德岳等上海交