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

Science China Chemistry 2011年第2期54卷 343-350页

作者： ZhAO LiZhi XIANG Rui ZhANG LiYan WU ChengLin MA RuJiang AN YingLi ShI LinQi Key Laboratory of Functional Polymer Materials Ministry of EducationInstitute of Polymer ChemistryNankai UniversityTianjin 300071China

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 *** resultant complex micelles had a complex P4VP/ PDMAEMA/TPPS core and a mixed PEG/PNIPAM *** noncovalent interaction modes between the porphyrin and each copolymer accomplished a co-effect on the aggregation of *** formation of aggregates was *** 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 *** monomers translated into J-aggregates,stabilized by electrostatic interaction with the both polyelectrolyte blocks,upon decreasing the ph to *** 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

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AFM height Measurements of Molecular Layers of a Carbocyanine Dye

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World Journal of Nano Science and Engineering 2011年第3期1卷 67-72页

作者： Valery V. Prokhorov Sergey I. Pozin Dmitry A. Lypenko Olga M. Perelygina Eugene I. Mal’tsev Anatoly V. Vannikov Frumkin Institute of Electrochemistry of the Russian Academy of Sciences

Atomic force microscopy (AFM) was used for the morphological characterization and precise height meas-urements of two-dimensional molecular layers of carbocyanine dye 3,3’-di(r-sulfopropyl)-4,4’,5,5’-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt. The AFM measurements reveal three morphological types of molecular aggregates: leaves, stripes and spots. The leaves are stripes have same monolayer height ~1.4 nm and different crystal shapes: the leaves are monoloyers with the lens shape and the stripes are bilay-ers with the shape of extended rectangles. The monolayer height ~1.4 nm was interpreted as indicating the symmetrical packing arrangement of dye molecules. In the symmetrical monolayer, the sulfopropyl groups of all-trans monomer units are located on both monolayer sides whereas the adjacent stacked dye molecules have a lateral slippage providing the J-aggregate optical properties. The lower height of spots ~1 nm was explained by the model of an asymmetric monolayer with sulfopropyl groups of all-trans monomers occupy-ing the same position with respect to the monolayer plane. The packing arrangement of all-trans monomers in the asymmetric monolayer corresponds to h-aggregate. The alternative models of the packing arrange-ment in monolayers with mono-cis1 monomer configuration are discussed.

关键词： Atomic Force Microscopy J-aggregates h-aggregates Monolayers

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