Reversible assembly of enantiomeric helical polymers: from fibers to gels.
Reversible assembly of enantiomeric helical polymers: from fibers to gels.
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DOI：
10.1039/c4sc02401j
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发表时间：
2015-01-01
期刊：
影响因子：
8.4
通讯作者：
Riguera R
中科院分区：
文献类型：
--
作者：
Leiras S;Freire F;Quiñoá E;Riguera R
本文报道了一类新型的带有α-甲氧基-α-三氟甲基苯乙酰胺侧基的螺旋互补聚苯乙炔（PPA）的相互作用。本文报道了一类新型的带有α-甲氧基-α-三氟甲基苯乙酰胺侧基的螺旋互补聚苯乙炔（PPA）的相互作用。立体复合物的形成需要在聚合物的外峰上存在顺式酰胺键，以在匹配的对映体螺旋结构之间提供有效的合作超分子氢键。链的互锁产生超分子纤维状聚集体，其在较高浓度下导致凝胶。在侧基处的顺-反酰胺构象的修饰允许由于分子间和分子内氢键相互作用之间的显著变化而控制立体复合物的形成和裂解。
A novel class of stereocomplexes is described by the interaction of helically complementary poly(phenylacetylene)s (PPAs) carrying an α-methoxy-α-trifluoromethylphenylacetamide pendant group. A novel class of stereocomplexes is described by the interaction of helically complementary poly(phenylacetylene)s (PPAs) carrying an α-methoxy-α-trifluoromethylphenylacetamide pendant group. The formation of the stereocomplex requires the presence of cis amide bonds on the external crest of the polymer to provide efficient cooperative supramolecular hydrogen bonding between matching enantiomeric helical structures. The interlocking of the chains gives rise to supramolecular fiber-like aggregates that, at higher concentrations, result in gels. The modification of the cis–trans amide conformation at the pendant groups allows the controlled formation and cleavage of the stereocomplex due to a dramatic change between the intermolecular and intramolecular hydrogen bond interactions.