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对映体螺旋聚合物的可逆组装:从纤维到凝胶

Reversible assembly of enantiomeric helical polymers: from fibers to gels.

作者信息

Leiras Seila, Freire Félix, Quiñoá Emilio, Riguera Ricardo

机构信息

Department of Organic Chemistry and Center for Research in Biological Chemistry and Molecular Materials (CIQUS) , University of Santiago de Compostela , E-15782 Santiago de Compostela , Spain . Email:

出版信息

Chem Sci. 2015 Jan 1;6(1):246-253. doi: 10.1039/c4sc02401j. Epub 2014 Sep 2.

DOI:10.1039/c4sc02401j
PMID:28553473
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5433055/
Abstract

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 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 - 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.

摘要

一类新型的立体复合物是由带有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)之间的相互作用所描述的。立体复合物的形成需要聚合物外部嵴上存在酰胺键,以在匹配的对映体螺旋结构之间提供有效的协同超分子氢键。链的互锁产生超分子纤维状聚集体,在较高浓度下会形成凝胶。侧基处酰胺构象的改变由于分子间和分子内氢键相互作用之间的显著变化而允许立体复合物的可控形成和解离。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/7b66db42194b/c4sc02401j-f10.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9c9d1d6d4f0b/c4sc02401j-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/ac1345752f2c/c4sc02401j-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/3c79590071b3/c4sc02401j-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/7535626f31f4/c4sc02401j-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9bc92c01705b/c4sc02401j-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/4d3877f2c9f4/c4sc02401j-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9a9445aef43e/c4sc02401j-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9a4a22adeecb/c4sc02401j-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/97ee15f3ae2c/c4sc02401j-f9.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/7b66db42194b/c4sc02401j-f10.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9c9d1d6d4f0b/c4sc02401j-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/ac1345752f2c/c4sc02401j-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/3c79590071b3/c4sc02401j-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/7535626f31f4/c4sc02401j-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9bc92c01705b/c4sc02401j-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/4d3877f2c9f4/c4sc02401j-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9a9445aef43e/c4sc02401j-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/9a4a22adeecb/c4sc02401j-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/97ee15f3ae2c/c4sc02401j-f9.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/46e9/5433055/7b66db42194b/c4sc02401j-f10.jpg

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本文引用的文献

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