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Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment

Ultrafast charge, energy and structural dynamics in molecules are driven by the topology of the multidimensional potential energy surfaces that determines the coordinated electronic and nuclear motion. These processes are also strongly influenced by the interaction with the molecular environment, ma...

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Autores principales: Hervé, Marius, Boyer, Alexie, Brédy, Richard, Compagnon, Isabelle, Allouche, Abdul-Rahman, Lépine, Franck
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814788/
https://www.ncbi.nlm.nih.gov/pubmed/36697624
http://dx.doi.org/10.1038/s42004-021-00557-4
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author Hervé, Marius
Boyer, Alexie
Brédy, Richard
Compagnon, Isabelle
Allouche, Abdul-Rahman
Lépine, Franck
author_facet Hervé, Marius
Boyer, Alexie
Brédy, Richard
Compagnon, Isabelle
Allouche, Abdul-Rahman
Lépine, Franck
author_sort Hervé, Marius
collection PubMed
description Ultrafast charge, energy and structural dynamics in molecules are driven by the topology of the multidimensional potential energy surfaces that determines the coordinated electronic and nuclear motion. These processes are also strongly influenced by the interaction with the molecular environment, making very challenging a general understanding of these dynamics on a microscopic level. Here we use electrospray and mass spectrometry technologies to produce isolated molecular ions with a controlled micro-environment. We measure ultrafast photo-induced ππ*-πσ* dynamics in tryptophan species in the presence of a single, charged adduct. A striking increase of the timescale by more than one order of magnitude is observed when changing the added adduct atom. A model is proposed to rationalize the results, based on the localized and delocalized effects of the adduct on the electronic structure of the molecule. These results offer perspectives to control ultrafast molecular processes by designing the micro-environment on the Angström length scale.
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spelling pubmed-98147882023-01-10 Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment Hervé, Marius Boyer, Alexie Brédy, Richard Compagnon, Isabelle Allouche, Abdul-Rahman Lépine, Franck Commun Chem Article Ultrafast charge, energy and structural dynamics in molecules are driven by the topology of the multidimensional potential energy surfaces that determines the coordinated electronic and nuclear motion. These processes are also strongly influenced by the interaction with the molecular environment, making very challenging a general understanding of these dynamics on a microscopic level. Here we use electrospray and mass spectrometry technologies to produce isolated molecular ions with a controlled micro-environment. We measure ultrafast photo-induced ππ*-πσ* dynamics in tryptophan species in the presence of a single, charged adduct. A striking increase of the timescale by more than one order of magnitude is observed when changing the added adduct atom. A model is proposed to rationalize the results, based on the localized and delocalized effects of the adduct on the electronic structure of the molecule. These results offer perspectives to control ultrafast molecular processes by designing the micro-environment on the Angström length scale. Nature Publishing Group UK 2021-08-31 /pmc/articles/PMC9814788/ /pubmed/36697624 http://dx.doi.org/10.1038/s42004-021-00557-4 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Hervé, Marius
Boyer, Alexie
Brédy, Richard
Compagnon, Isabelle
Allouche, Abdul-Rahman
Lépine, Franck
Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment
title Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment
title_full Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment
title_fullStr Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment
title_full_unstemmed Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment
title_short Controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment
title_sort controlled ultrafast ππ*-πσ* dynamics in tryptophan-based peptides with tailored micro-environment
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814788/
https://www.ncbi.nlm.nih.gov/pubmed/36697624
http://dx.doi.org/10.1038/s42004-021-00557-4
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