Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution

Fluorescent labelling of macromolecular samples, including using the green fluorescent protein (GFP), has revolutionised the field of bioimaging. The ongoing development of fluorescent proteins require a detailed understanding of the photophysics of the biochromophore, and how chemical derivatisatio...

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Autores: Ashworth, Eleanor K., Kao, Min-Hsien, Anstöter, Cate S., Riesco-Llach, Gerard, Blancafort San José, Lluís, Solntsev, Kyril M., Meech, Stephen R., Verlet, Jan R. R., Bull, James N.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/23931
Acceso en línea:http://hdl.handle.net/10256/23931
Access Level:acceso abierto
Palabra clave:Alquilació
Alkylation
Química de l'estat excitat
Excited state chemistry
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spelling Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solutionAshworth, Eleanor K.Kao, Min-HsienAnstöter, Cate S.Riesco-Llach, GerardBlancafort San José, LluísSolntsev, Kyril M.Meech, Stephen R.Verlet, Jan R. R.Bull, James N.AlquilacióAlkylationQuímica de l'estat excitatExcited state chemistryFluorescent labelling of macromolecular samples, including using the green fluorescent protein (GFP), has revolutionised the field of bioimaging. The ongoing development of fluorescent proteins require a detailed understanding of the photophysics of the biochromophore, and how chemical derivatisation influences the excited state dynamics. Here, we investigate the photophysical properties associated with the S1 state of three alkylated derivatives of the chromophore in GFP, in the gas phase using time-resolved photoelectron imaging, and in water using femtosecond fluorescence upconversion. The gas-phase lifetimes (1.6–10 ps), which are associated with the intrinsic (environment independent) dynamics, are substantially longer than the lifetimes in water (0.06–3 ps), attributed to stabilisation of both twisted intermediate structures and conical intersection seams in the condensed phase. In the gas phase, alkylation on the 3 and 5 positions of the phenyl ring slows the dynamics due to inertial effects, while a ‘pre-twist’ of the methine bridge through alkylation on the 2 and 6 positions significantly shortens the excited state lifetimes. Formation of a minor, long-lived (≫ 40 ps) excited state population in the gas phase is attributed to intersystem crossing to a triplet state, accessed because of a T1/S1 degeneracy in the so-called P-trap potential energy minimum associated with torsion of the single-bond in the bridging unit connecting to the phenoxide ring. A small amount of intersystem crossing is supported through TD-DFT molecular dynamics trajectories and MS-CASPT2 calculations. No such intersystem crossing occurs in water at T = 300 K or in ethanol at T ≈ 77 K, due to a significantly altered potential energy surface and P-trap geometryFunding was provided by a start-up grant at University of East Anglia and an EPSRC New Investigator Award (EP/W018691) to JNB. LB and GRL thank the Ministerio de Ciencia, Innovación y Universidades (Spain) for project PID-2019-104654GB-I00 and the Red Española de Supercomputación for computational time (project QSB-2018-1-0040)Royal Society of Chemistry (RSC)Agencia Estatal de Investigación2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/23931http://hdl.handle.net/10256/23931Physical Chemistry Chemical Physics, 2023, vol. 25, núm. 35, p. 23626-23636Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D3CP03250Ginfo:eu-repo/semantics/altIdentifier/issn/1463-9076info:eu-repo/semantics/altIdentifier/eissn/1463-9084PID2019-104654GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104654GB-I00Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/239312026-05-29T05:05:01Z
dc.title.none.fl_str_mv Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
title Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
spellingShingle Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
Ashworth, Eleanor K.
Alquilació
Alkylation
Química de l'estat excitat
Excited state chemistry
title_short Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
title_full Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
title_fullStr Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
title_full_unstemmed Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
title_sort Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution
dc.creator.none.fl_str_mv Ashworth, Eleanor K.
Kao, Min-Hsien
Anstöter, Cate S.
Riesco-Llach, Gerard
Blancafort San José, Lluís
Solntsev, Kyril M.
Meech, Stephen R.
Verlet, Jan R. R.
Bull, James N.
author Ashworth, Eleanor K.
author_facet Ashworth, Eleanor K.
Kao, Min-Hsien
Anstöter, Cate S.
Riesco-Llach, Gerard
Blancafort San José, Lluís
Solntsev, Kyril M.
Meech, Stephen R.
Verlet, Jan R. R.
Bull, James N.
author_role author
author2 Kao, Min-Hsien
Anstöter, Cate S.
Riesco-Llach, Gerard
Blancafort San José, Lluís
Solntsev, Kyril M.
Meech, Stephen R.
Verlet, Jan R. R.
Bull, James N.
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Alquilació
Alkylation
Química de l'estat excitat
Excited state chemistry
topic Alquilació
Alkylation
Química de l'estat excitat
Excited state chemistry
description Fluorescent labelling of macromolecular samples, including using the green fluorescent protein (GFP), has revolutionised the field of bioimaging. The ongoing development of fluorescent proteins require a detailed understanding of the photophysics of the biochromophore, and how chemical derivatisation influences the excited state dynamics. Here, we investigate the photophysical properties associated with the S1 state of three alkylated derivatives of the chromophore in GFP, in the gas phase using time-resolved photoelectron imaging, and in water using femtosecond fluorescence upconversion. The gas-phase lifetimes (1.6–10 ps), which are associated with the intrinsic (environment independent) dynamics, are substantially longer than the lifetimes in water (0.06–3 ps), attributed to stabilisation of both twisted intermediate structures and conical intersection seams in the condensed phase. In the gas phase, alkylation on the 3 and 5 positions of the phenyl ring slows the dynamics due to inertial effects, while a ‘pre-twist’ of the methine bridge through alkylation on the 2 and 6 positions significantly shortens the excited state lifetimes. Formation of a minor, long-lived (≫ 40 ps) excited state population in the gas phase is attributed to intersystem crossing to a triplet state, accessed because of a T1/S1 degeneracy in the so-called P-trap potential energy minimum associated with torsion of the single-bond in the bridging unit connecting to the phenoxide ring. A small amount of intersystem crossing is supported through TD-DFT molecular dynamics trajectories and MS-CASPT2 calculations. No such intersystem crossing occurs in water at T = 300 K or in ethanol at T ≈ 77 K, due to a significantly altered potential energy surface and P-trap geometry
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/23931
http://hdl.handle.net/10256/23931
url http://hdl.handle.net/10256/23931
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/D3CP03250G
info:eu-repo/semantics/altIdentifier/issn/1463-9076
info:eu-repo/semantics/altIdentifier/eissn/1463-9084
PID2019-104654GB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104654GB-I00
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry (RSC)
publisher.none.fl_str_mv Royal Society of Chemistry (RSC)
dc.source.none.fl_str_mv Physical Chemistry Chemical Physics, 2023, vol. 25, núm. 35, p. 23626-23636
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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