Micellization of copolymers via noncovalent interaction with TPPS and aggregation of TPPS  

作　　者：ZHAO LiZhi XIANG Rui ZHANG LiYan WU ChengLin MA RuJiang AN YingLi SHI LinQi 

机构地区：[1]Key Laboratory of Functional Polymer Materials,Ministry of Education,Institute of Polymer Chemistry,Nankai University,Tianjin 300071,China

出　　处：《Science China Chemistry》2011年第2期343-350,共8页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China (50830103 & 20904025);National Basic Research Program of China (973 Program,2011CB932500);the Open Research Fund Program of ChangChun Institute of Applied Chemistry Chinese Academy of Sciences

摘　　要：Aggregation of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (TPPS) was investigated in complex micelles composed of poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG-b-P4VP) and poly(2-(dimethylamino)ethyl methylacrylate)-b-poly(Nisopropylacrylamide) (PDMAEMA-b-PNIPAM) in aqueous solutions.The resultant complex micelles had a complex P4VP/ PDMAEMA/TPPS core and a mixed PEG/PNIPAM shell.Different noncovalent interaction modes between the porphyrin and each copolymer accomplished a co-effect on the aggregation of TPPS.The formation of aggregates was pH-dependent.At pH 3.2–6.5,TPPS existed as a mixture of H-aggregates and monomers because of the aromatic-aromatic interaction with P4VP and electrostatic interaction with PDMAEMA.The monomers translated into J-aggregates,stabilized by electrostatic interaction with the both polyelectrolyte blocks,upon decreasing the pH to 1.6.The free-base monomer was the one and only form for the dye at pH 11.0 due to aromatic stacking with the pyridyl rings.Aggregation of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin (TPPS) was investigated in complex micelles composed of poly(ethylene glycol)-block-poly(4-vinylpyridine) (PEG-b-P4VP) and poly(2-(dimethylamino)ethyl methylacrylate)-b-poly(Nisopropylacrylamide) (PDMAEMA-b-PNIPAM) in aqueous solutions. The resultant complex micelles had a complex P4VP/ PDMAEMA/TPPS core and a mixed PEG/PNIPAM shell. Different noncovalent interaction modes between the porphyrin and each copolymer accomplished a co-effect on the aggregation of TPPS. The formation of aggregates was pH-dependent. At pH 3.2-6.5, TPPS existed as a mixture of H-aggregates and monomers because of the aromatic-aromatic interaction with P4VP and electrostatic interaction with PDMAEMA. The monomers translated into J-aggregates, stabilized by electrostatic interaction with the both polyelectrolyte blocks, upon decreasing the pH to 1.6. The free-base monomer was the one and only form for the dye at pH 11.0 due to aromatic stacking with the pyridyl rings.

关 键 词：block copolymer TPPS H-AGGREGATES J-AGGREGATES 

分 类 号：TQ320.1[化学工程—合成树脂塑料工业]