超分子化学与材料-复习1.ppt

* * * * * * * * * * * * * * * * * * * J. Am. Chem. Soc. , 2003, 125: 14710 Macromolecules, 2004, 37, 5710 Angew. Chem. Int. Ed. , 2004, 43:5084 复合胶束的形成和环境响应 环境敏感聚合物能对环境的微小变化，产生明显的响应。 PtBA-b-PNIPAM: 聚丙烯酸叔丁酯-聚异丙基丙烯酰胺嵌段共聚物 PtBA-b-P4VP: 聚丙烯酸叔丁酯-聚4-乙烯基吡啶 胶束的可调通道与生物膜通道的比较 普通胶束的药物释放 通道胶束的药物释放 普通胶束与带有可调通道胶束的比较 胶束的通道的效应 G. Li, L. Shi*, ??? Angew. Chem. Int. Ed. 2006,45,1 1.通道胶束 2.普通胶束 控制释放 分子开关 Supramolecular liquid-crystalline polymeric complexes Supramolecular liquid-crystalline side-chain polymer Discotic liquid crystals: photoconductive materials P.G. de Gennes: “The physics of liquid crystals” oxford, 1974 (1991, Nobel Prize Winner for Physics) S. Chandrasekhar: First discovery, 1977 The mesophase of discotic liquid crystalization Typical discotic LCs Photocurrent vs Temperature * * * * * * * * * * * * * * * * * * * * UV Vis 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 一般偶氮苯在固态膜中的光致异构化速率和效率常常比其在溶液中低。我们巧妙的利用高分子胶束结构所提供的微环境，使偶氮苯光致异构化的速率在固态膜中比其在溶液中还快一倍。 LbL 薄膜 甲苯溶液 张希 等 et al. Langmuir, 2006, 22, 3906 4.07×10-3 9.03×10-3 1.14×10-2 PS(OH)-X X 8mol% PMMA A B segment pairing interpolymer complex Each A chain interacts with many B chains and vice versa 无规则的聚集体 separated coils + common solvent Interaction groups 将质子给体基限于链的端基上 Restricting the reaction groups within certain positions along the chain One of Approaches hydrogen bonding leads to ‘graft’copolymers and then  非共价键合胶束(NCCM) Proton donor ends Proton acceptor NCCM In ‘obverse’ and ‘reverse’ NCCM of CPB/ PVPy PVPy CPB nitromethane In chloroform Obverse NCCM Reverse NCCM hexane polybutadiene with carboxyl groups at ends 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 crosslnking PVPy shell by 1,4 –dibromobutane in CH3NO2 Cavitation in DMF CH3NO2 PS(OH) PVPy DMF Hydroethyl Cellulose (HEC