Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals

Abstract Flavocoenzymes are nearly ubiquitous cofactors that are involved in the catalysis and regulation of a wide range of biological processes including some light-induced ones, such as the photolyase-mediated DNA repair, magnetoreception of migratory birds, and the blue-light driven phototropism...

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Autores principales:	Erik Schleicher, Stephan Rein, Boris Illarionov, Ariane Lehmann, Tarek Al Said, Sylwia Kacprzak, Robert Bittl, Adelbert Bacher, Markus Fischer, Stefan Weber
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/900180dd7052427f8b4c6df1281a971c
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spelling	oai:doaj.org-article:900180dd7052427f8b4c6df1281a971c2021-12-02T15:33:23ZSelective 13C labelling reveals the electronic structure of flavocoenzyme radicals10.1038/s41598-021-97588-72045-2322https://doaj.org/article/900180dd7052427f8b4c6df1281a971c2021-09-01T00:00:00Zhttps://doi.org/10.1038/s41598-021-97588-7https://doaj.org/toc/2045-2322Abstract Flavocoenzymes are nearly ubiquitous cofactors that are involved in the catalysis and regulation of a wide range of biological processes including some light-induced ones, such as the photolyase-mediated DNA repair, magnetoreception of migratory birds, and the blue-light driven phototropism in plants. One of the factors that enable versatile flavin-coenzyme biochemistry and biophysics is the fine-tuning of the cofactor’s frontier orbital by interactions with the protein environment. Probing the singly-occupied molecular orbital (SOMO) of the intermediate radical state of flavins is therefore a prerequisite for a thorough understanding of the diverse functions of the flavoprotein family. This may be ultimately achieved by unravelling the hyperfine structure of a flavin by electron paramagnetic resonance. In this contribution we present a rigorous approach to obtaining a hyperfine map of the flavin’s chromophoric 7,8-dimethyl isoalloxazine unit at an as yet unprecedented level of resolution and accuracy. We combine powerful high-microwave-frequency/high-magnetic-field electron–nuclear double resonance (ENDOR) with 13C isotopologue editing as well as spectral simulations and density functional theory calculations to measure and analyse 13C hyperfine couplings of the flavin cofactor in DNA photolyase. Our data will provide the basis for electronic structure considerations for a number of flavin radical intermediates occurring in blue-light photoreceptor proteins.Erik SchleicherStephan ReinBoris IllarionovAriane LehmannTarek Al SaidSylwia KacprzakRobert BittlAdelbert BacherMarkus FischerStefan WeberNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 11, Iss 1, Pp 1-9 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Erik Schleicher Stephan Rein Boris Illarionov Ariane Lehmann Tarek Al Said Sylwia Kacprzak Robert Bittl Adelbert Bacher Markus Fischer Stefan Weber Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals
description	Abstract Flavocoenzymes are nearly ubiquitous cofactors that are involved in the catalysis and regulation of a wide range of biological processes including some light-induced ones, such as the photolyase-mediated DNA repair, magnetoreception of migratory birds, and the blue-light driven phototropism in plants. One of the factors that enable versatile flavin-coenzyme biochemistry and biophysics is the fine-tuning of the cofactor’s frontier orbital by interactions with the protein environment. Probing the singly-occupied molecular orbital (SOMO) of the intermediate radical state of flavins is therefore a prerequisite for a thorough understanding of the diverse functions of the flavoprotein family. This may be ultimately achieved by unravelling the hyperfine structure of a flavin by electron paramagnetic resonance. In this contribution we present a rigorous approach to obtaining a hyperfine map of the flavin’s chromophoric 7,8-dimethyl isoalloxazine unit at an as yet unprecedented level of resolution and accuracy. We combine powerful high-microwave-frequency/high-magnetic-field electron–nuclear double resonance (ENDOR) with 13C isotopologue editing as well as spectral simulations and density functional theory calculations to measure and analyse 13C hyperfine couplings of the flavin cofactor in DNA photolyase. Our data will provide the basis for electronic structure considerations for a number of flavin radical intermediates occurring in blue-light photoreceptor proteins.
format	article
author	Erik Schleicher Stephan Rein Boris Illarionov Ariane Lehmann Tarek Al Said Sylwia Kacprzak Robert Bittl Adelbert Bacher Markus Fischer Stefan Weber
author_facet	Erik Schleicher Stephan Rein Boris Illarionov Ariane Lehmann Tarek Al Said Sylwia Kacprzak Robert Bittl Adelbert Bacher Markus Fischer Stefan Weber
author_sort	Erik Schleicher
title	Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals
title_short	Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals
title_full	Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals
title_fullStr	Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals
title_full_unstemmed	Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals
title_sort	selective 13c labelling reveals the electronic structure of flavocoenzyme radicals
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/900180dd7052427f8b4c6df1281a971c
work_keys_str_mv	AT erikschleicher selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT stephanrein selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT borisillarionov selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT arianelehmann selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT tarekalsaid selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT sylwiakacprzak selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT robertbittl selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT adelbertbacher selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT markusfischer selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals AT stefanweber selective13clabellingrevealstheelectronicstructureofflavocoenzymeradicals
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Selective 13C labelling reveals the electronic structure of flavocoenzyme radicals

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