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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...

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Autores principales: de Graaf, Freek V., Jansen, Stef A. H., Schnitzer, Tobias, Meijer, E. W., Vantomme, Ghislaine
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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.
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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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