Selective assembly of cyclodextrins on poly(ethylene oxide)-poly(propylene oxide) block copolymers

被引:35
作者
Mayer, B
Klein, CT
Topchieva, IN
Köhler, G
机构
[1] Univ Vienna, Inst Theoret Chem & Radiat Chem, UZAII, A-1090 Vienna, Austria
[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119899, Russia
关键词
host-guest complexes; molecular necklace; molecular recognition; molecular self-assembly; molecular solvation;
D O I
10.1023/A:1008095501870
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
This paper presents a computational study on the formation of a molecular necklace formed by specific threading of cyclodextrins (CDs) on block copolymers. Structural as well as energetic principles for the selective complexation of alpha- and beta-cyclodextrin with poly(ethylene oxide)-poly(propylene oxide) block copolymers (PEO-PPO) are elucidated considering a diblock copolymer of equimolecular composition (PEO)(4)-(PPO)(4) as guest. A non-statistical distribution of CDs, i.e. alpha-CDs primarily located on the PEO chain and beta-CDs on PPO blocks of the polymer, is based on a variety of structural features and energetic preferences considering both potential as well as solvation energies. This selectivity becomes already obvious considering 1:1 complexes between PEO and PPO monomers and the two CDs, but is increasingly evident when calculating higher order ensembles. Besides the host-guest interaction, docking between CDs themselves is an important, also non-statistical, prerequisite for the self-assembly of highly ordered tubes. The formation of intermolecular hydrogen bonds between adjacent CDs in a tubular aggregate gives an important contribution to the overall stability of the molecular necklace. The net effect, based on the preferential interaction between host and guest as well as between the host molecules themselves, results in the formation of a stable, highly ordered macromolecular, multicomponent aggregate.
引用
收藏
页码:373 / 383
页数:11
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