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Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification
[Image: see text] Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective met...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10326880/ https://www.ncbi.nlm.nih.gov/pubmed/37342902 http://dx.doi.org/10.1021/jacs.3c03411 |
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author | de Graaf, Freek V. Jansen, Stef A. H. Schnitzer, Tobias Meijer, E. W. Vantomme, Ghislaine |
author_facet | de Graaf, Freek V. Jansen, Stef A. H. Schnitzer, Tobias Meijer, E. W. Vantomme, Ghislaine |
author_sort | de Graaf, Freek V. |
collection | PubMed |
description | [Image: see text] Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials. |
format | Online Article Text |
id | pubmed-10326880 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-103268802023-07-08 Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification de Graaf, Freek V. Jansen, Stef A. H. Schnitzer, Tobias Meijer, E. W. Vantomme, Ghislaine J Am Chem Soc [Image: see text] Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials. American Chemical Society 2023-06-21 /pmc/articles/PMC10326880/ /pubmed/37342902 http://dx.doi.org/10.1021/jacs.3c03411 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | de Graaf, Freek V. Jansen, Stef A. H. Schnitzer, Tobias Meijer, E. W. Vantomme, Ghislaine Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification |
title | Controlling Helical
Asymmetry in Supramolecular Copolymers
by In Situ Chemical Modification |
title_full | Controlling Helical
Asymmetry in Supramolecular Copolymers
by In Situ Chemical Modification |
title_fullStr | Controlling Helical
Asymmetry in Supramolecular Copolymers
by In Situ Chemical Modification |
title_full_unstemmed | Controlling Helical
Asymmetry in Supramolecular Copolymers
by In Situ Chemical Modification |
title_short | Controlling Helical
Asymmetry in Supramolecular Copolymers
by In Situ Chemical Modification |
title_sort | controlling helical
asymmetry in supramolecular copolymers
by in situ chemical modification |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10326880/ https://www.ncbi.nlm.nih.gov/pubmed/37342902 http://dx.doi.org/10.1021/jacs.3c03411 |
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