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)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)的簡單和清潔的途徑 Simple and clean w

2、ays 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世紀亟待解決的25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。,Robert F. Service Science 2005, 309, 95.,Macromolecular Self-assembly : 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 structure

3、d 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,A Ciferri, Macromolecular Rapid Communications, 2002, 23, 511,A,B,Building blocks : small molecules with proton-donating and proton accepting groups,A,B,Supramolecular Polymers A Little work in China,Ma

4、cromolecules as building blocks to form structured assemblies,Micellization of block copolymers in selective solvents,Covalent bonds connecting the core and shell,selective solvent for red block,selective solvent for blue block,Characters: Size 10-200nm Amphiphilicity Applications: Encapsulation Dru

5、g-delivery, Micro-reactor: Nano-metal particles, Nano-semi-conductor particles Catalysis,至80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Pioneer work 90 年代初 吉林大學(xué) 沈家驄, 張希等,氣/液界面“浮萍”與“倒浮萍”膜組裝,提出了類“浮萍”與“倒浮萍”聚合物超薄膜的模型，利用親、疏水力進行組裝，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。,沈家驄、張希等 Langmuir, 1994, 10, 2727Thin Solid Films, 1992, 210, 625Ma

6、cromolecules, 1991, 24, 4986 Macromolecules, 1990, 23, 5158,系列學(xué)術(shù)研討會 1991年沈家驄 H. Ringsdorf 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)間的橋梁 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

7、-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,一般偶氮苯在固態(tài)膜中的光致異構(gòu)化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，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。,LbL 薄膜,甲苯溶液,張希 等 et al. Langmuir, 2006, 22, 3906,4.0710-3,9.0310-3,1.1410-2,復(fù)旦大學(xué) Fudan University Ming Jiang （江明） Daoyong Chen （陳道勇） Ping Y

8、ao （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,PS(OH)-X X 8mol% PMMA,大分子絡(luò)合物 驅(qū)動力：氫鍵 自發(fā)過程 分子組裝？,Each A chain interacts with many B chains and vice versa,無規(guī)則的聚集體,separated coils,+,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” “Block-copolymer-free routes for polymeric micellization via interpoly

9、mer complexation ”,Interaction groups,將質(zhì)子給體基限于鏈的端基上 Restricting the reaction groups within certain positions along the chain,One of Approaches,hydrogen bonding leads to graftcopolymers and then 非共價鍵合膠束(NCCM),Proton donor ends,Proton acceptor,NCCM,In,obverse and reverse NCCM of CPB/ PVPy,PVPy,CPB,nit

10、romethane,In chloroform,Obverse NCCM,Reverse NCCM,hexane,polybutadiene with carboxyl groups at ends,PVPy-(CPB),(PVPy)-CPB,Hydrodynamic Diameter (Dh) Distribution,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-containing polymers JACS ,123, 12097, 2001; J Phys Chem B, 108,

11、 550, 2004; 108, 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) Langmuir ,17,6122, 2001 PCL/ PMAA-g-PCL Angew Chem Intl

12、 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,Great interest in obtaining polymeric hollow spheres: Liu G, Wooley K,degradable,crosslinkable,block copolymer,selective solvent,crosslinking,photo-degradation,chemical-degradation,From NCCM to Hollow Spheres,TEM Image of Hollow Sphere obtained by cor

13、e dissolution from NCCM of (PCL)-PAA,環(huán)境響應(yīng)膠束：pH, 溫度，光，離子強度等,Hydroethyl Cellulose (HEC) g Poly(Acrylic Acid) HEC-g-PAA,Self-assembly of Double Hydrophilic Graft Copolymer,Dou HJ, Jiang M et al. Angew Chem Intl Ed 42, 1516, 2003,Ce()/H+,HEC-g-PAA,Preparation of graft coplymer,接枝共聚物分子量的表征,Characteristic

14、 data of HEC-g-PAA copolymers,Cellulase,+,PAA grafts,AGU,Table 2-2 LLS Characteristic data of CAA-1 and CAA-2,/=1.50 Means random coil,Radius of Gyration Rg Hydrodynamic Radius Rh,The solution at pH range of 2-3 was unstable: the apparent increased with time. The values measured 20 min after the sol

15、ution preparation were used.,Figure 3-2 of HEC-g-PAA copolymers as a function of pH. The concentration was 1mg/ml.,pH 3, molecularly dissolved pH3, micelles formed,pH decrease,pH induced micellization,Micelle,(pH3),-COOH of PAA at pH3 can complex with HEC and form the “core” of micelles Uncomplexed

16、HEC segments form the “shell” of micelles,(pH3),pH 3, molecularly dissolved At low pH, PAA protonated, forming complex with HEC main chain core; HEC without PAA branches formed shell pH-controlled complexation-induced micellization (low grafting density is necessary!),COOH COO- + H+,pH,pH,At low pH,

17、 Crosslinking of PAA grafts - to lock the structure,Dialysis against water, pH 3 7: DLS: size 350nm 650nm TEM: micelles hollow spheres,At pH 7, Hollow Spheres Form!,pH 3-7: pH-dependent micelle-hollow- sphere transition,pH1.3交聯(lián)PAA,pH increase,Core-crosslinked miclle,Low crosslinking density is neces

18、sary !,pH=1.3 Stable micelle,交聯(lián)劑： 2,2-(ethylenedioxy)bis(ethylamine),Dialysis,pH=7 PAA+HEC decomplexation,Reversible ?,pH 3, protonation, complexation,pH7, deprotonation, de-complexation, disintergaration,Reversibility of the transition,pH 3-7: pH-dependent micelle-hollow- sphere transition,TEM obse

19、rvations（CAA2）,pH=1.3 pH induced micelles,pH=7 Hollow spheres,pH=1.3 pH-induced micelles after one pH cycle,PNIPAM (Polyisopropyl acrylamide) -based reversible thermo-sensitivity Adv Funct Mat 15, 695 (2005),PAA-based pH 4.5 8.5, volume increases by 130 times Langmuir 21, 1531 (2005),Building block

20、: linear polymers Architectural effect ? Dendrimer and Dendron as building blocks,Preparation of Dendron G3,H-Bonding Dendronized Polymers,Formation of nanoparticles from G3/PVP in common solvent , ultrasonic treatment,Hollow spheres?,Collapsed thin-layer hollow spheres ?,Crosslinked hollow spheres

21、- much high strength,G3/PVP23 Thick wall hollow spheres,Self-assembly driven by H-Bonding Other driving forces? Inclusion complexation ?, 環(huán)糊精cyclodextrin,7,hydrophilicity,hydrophobicity,Structures and properties of Adamantane (ADA),d 7 7 V 180 3 262 3,Adamantane,Complex stable constant 105,The -CD c

22、avity apparently has the optimum dimensions for interaction with adamantane derivate.,7 ,Adamantane,CD,環(huán)糊精 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 -CD / PEO,如何將環(huán)糊精的包結(jié)絡(luò)合用于構(gòu)建高分子膠束？,通過inclusion complexation 構(gòu)建高分子膠束 基本思路： 合成分別帶CD和ADA的親水和疏水高分子， 在水中形成通過inclusion interaction 連接的核殼膠束（NCCM）,ATRP,Mn =1.67 x 104,Mw/Mn =1.

23、21,Mn =1.87 x 104,Mw/Mn =1.28,CD-containing monomer GMA-CD,PGMA-CD MW 10,400,Characters: Double-scale hydrophobic regions : 100nm and 0.7nm Cavities available for surface modification,NH2,-COOH,negatively charged,positively charged,Micelle surface modification,Hollow sphere of crosslinked PGMA-CD,Do

24、uble 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: 表面活性劑; 納米金屬粒子; 光響應(yīng)有機分子; 催化,陳道勇等： 聚合反應(yīng)/組裝同步法合成納米結(jié)構(gòu) Macromolecules 2005, 38 , 3550,Most-Accessed Articles: 2005 1.Nanoporous Polystyrene Containing Hydrophilic Pores from an ABC Triblock Copolymer PrecursorRzayev, J.; Hillmyer, M. A.Macromolecules 2005, 3

25、8(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 Block Copolymers Composed of Different Macromolecular ArchitecturesPyun, J

26、.; 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-Emitting Diodes and Photovoltaic DevicesYang, R.; Tian, R.; Yan, J.; Zha

27、ng, 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， 江明 Account of Chemical Research , 38, 494, 2005 Strategies for Constructing Polymeric Micelles and Hollow Spheres in Solution via Specific Intermolecular Interactions,新挑戰(zhàn)：從合成高分子到天然大分子

28、 Target Materials : Micelles or Nano core-shell hydrogel made of proteins and polysacchrids biocompatible, biodegradable, non-toxic and even eatable （可食用性） Ping Yao (姚萍）， Fudan University,Ovalbumin(白蛋白） and Lysozyme（溶菌酶）,Ovalbumin: 385 aa, Mw 47000 Da Isoelectric Point 4.7, 7 nm 4.5 nm 5 nm,Lysozyme

29、: 129 aa, Mw 14351 Da Isoelectric Point 10.7, 3.8 nm 2.4 nm 2.2 nm,5.3,4.7,10.7,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,Globular + Globular:Ovalbumin and LysozymeBovine Serum Albumin and LysozymeOvalbumin and Overtransferrin Linear + Globular:as-Casein + Overtransferrin(as,beta,kappa-)Casein + Lysozyme Globular proteins + PolysaccharideOvalbumin + Chitosan Yao et al: Langmuir 22, 2754, 2006 Biopolymers 81, 29, 2006 J Collois Interface Sci., i