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Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective

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Resumo:The universe of known biological FeS clusters is constantly enlarging. Besides the conventional, well described [2Fe–2S], [3Fe–4S] and cubane [4Fe–4S] clusters, novel, unprecedented structures are emerging. They include unusually coordinated clusters, with additional sulfur atoms, e.g., [4Fe–5S], [5Fe–5S], [4Fe–4S]-5S-[4Fe–4S], [8Fe–7S], [8Fe–9S] and [8Fe–8S–C] and heteronuclear clusters, e.g., [Ni–4Fe–4S], [2Ni–4Fe–4S], [4Fe–4S]-[2Ru], [Me–7Fe–9S–C–(homocitrate)] that undertake versatile physiological roles in the activation of small molecules (H2, CO2, CO and N2) and in the sulfuration of different compounds (e.g., t-RNAs, biotin and lipoic acid) in biology. A few structures are characterized by highly distorted geometries, e.g., the non-cubane [4Fe–4S] center and the hydrogenase-related [4Fe–3S] cluster, and contain atypical ligations or vacant coordination sites, which confer them novel functions far from the common electron transfer. Herein, we single out clusters found in i) hydrogenases that ensure sustainable hydrogen cycling, promising a clean fuel production in the future, ii) radical-SAM enzymes that can inspire applied catalysis due to an intrinsic flexibility of the radical chemistry, and iii) standard [4Fe–4S] cluster with still unknown function in DNA repair enzymes, which offer a possibility to interfere with DNA repair in pathogens or improve it in humans. Focusing on the abovementioned enzymes, we demonstrate the unique power of resonance Raman spectroscopy to unveil remarkable features in FeS centers, which has contributed to our understanding of unusual structures and disentangling of unknown functions.
Autores principais:Caserta, Giorgio
Outros Autores:Zuccarello, Lidia; Barbosa, Catarina; Silveira, Célia M.; Moe, Elin; Katz, Sagie; Hildebrandt, Peter; Zebger, Ingo; Todorovic, Smilja
Assunto:FeS clusters Glycosylase Hydrogenase Radical-SAM Resonance Raman spectroscopy Physical and Theoretical Chemistry Inorganic Chemistry Materials Chemistry SDG 7 - Affordable and Clean Energy
Ano:2022
País:Portugal
Tipo de documento:recensão
Tipo de acesso:acesso aberto
Instituição associada:Universidade Nova de Lisboa
Idioma:inglês
Origem:Repositório Institucional da UNL
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author Caserta, Giorgio
author2 Zuccarello, Lidia
Barbosa, Catarina
Silveira, Célia M.
Moe, Elin
Katz, Sagie
Hildebrandt, Peter
Zebger, Ingo
Todorovic, Smilja
author2_role author
author
author
author
author
author
author
author
author_facet Caserta, Giorgio
Zuccarello, Lidia
Barbosa, Catarina
Silveira, Célia M.
Moe, Elin
Katz, Sagie
Hildebrandt, Peter
Zebger, Ingo
Todorovic, Smilja
author_role author
contributor_name_str_mv Instituto de Tecnologia Química e Biológica António Xavier (ITQB)
Elsevier
RUN
country_str PT
creators_json_txt [{\"Person.name\":\"Caserta, Giorgio\"},{\"Person.name\":\"Zuccarello, Lidia\"},{\"Person.name\":\"Barbosa, Catarina\"},{\"Person.name\":\"Silveira, Célia M.\"},{\"Person.name\":\"Moe, Elin\"},{\"Person.name\":\"Katz, Sagie\"},{\"Person.name\":\"Hildebrandt, Peter\"},{\"Person.name\":\"Zebger, Ingo\"},{\"Person.name\":\"Todorovic, Smilja\"}]
datacite.contributors.contributor.contributorName.fl_str_mv Instituto de Tecnologia Química e Biológica António Xavier (ITQB)
Elsevier
RUN
datacite.creators.creator.creatorName.fl_str_mv Caserta, Giorgio
Zuccarello, Lidia
Barbosa, Catarina
Silveira, Célia M.
Moe, Elin
Katz, Sagie
Hildebrandt, Peter
Zebger, Ingo
Todorovic, Smilja
datacite.date.Accepted.fl_str_mv 2022-02-01T00:00:00Z
datacite.date.available.fl_str_mv 2022-07-20T22:30:47Z
datacite.date.embargoed.fl_str_mv 2022-07-20T22:30:47Z
datacite.rights.fl_str_mv http://purl.org/coar/access_right/c_abf2
datacite.subjects.subject.fl_str_mv FeS clusters
Glycosylase
Hydrogenase
Radical-SAM
Resonance Raman spectroscopy
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry
SDG 7 - Affordable and Clean Energy
datacite.titles.title.fl_str_mv Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
dc.contributor.none.fl_str_mv Instituto de Tecnologia Química e Biológica António Xavier (ITQB)
Elsevier
RUN
dc.creator.none.fl_str_mv Caserta, Giorgio
Zuccarello, Lidia
Barbosa, Catarina
Silveira, Célia M.
Moe, Elin
Katz, Sagie
Hildebrandt, Peter
Zebger, Ingo
Todorovic, Smilja
dc.date.Accepted.fl_str_mv 2022-02-01T00:00:00Z
dc.date.available.fl_str_mv 2022-07-20T22:30:47Z
dc.date.embargoed.fl_str_mv 2022-07-20T22:30:47Z
dc.format.none.fl_str_mv application/pdf
dc.identifier.none.fl_str_mv http://hdl.handle.net/10362/142219
dc.language.none.fl_str_mv eng
dc.rights.none.fl_str_mv http://purl.org/coar/access_right/c_abf2
dc.subject.none.fl_str_mv FeS clusters
Glycosylase
Hydrogenase
Radical-SAM
Resonance Raman spectroscopy
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry
SDG 7 - Affordable and Clean Energy
dc.title.fl_str_mv Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
dc.type.none.fl_str_mv http://purl.org/coar/resource_type/c_efa0
description The universe of known biological FeS clusters is constantly enlarging. Besides the conventional, well described [2Fe–2S], [3Fe–4S] and cubane [4Fe–4S] clusters, novel, unprecedented structures are emerging. They include unusually coordinated clusters, with additional sulfur atoms, e.g., [4Fe–5S], [5Fe–5S], [4Fe–4S]-5S-[4Fe–4S], [8Fe–7S], [8Fe–9S] and [8Fe–8S–C] and heteronuclear clusters, e.g., [Ni–4Fe–4S], [2Ni–4Fe–4S], [4Fe–4S]-[2Ru], [Me–7Fe–9S–C–(homocitrate)] that undertake versatile physiological roles in the activation of small molecules (H2, CO2, CO and N2) and in the sulfuration of different compounds (e.g., t-RNAs, biotin and lipoic acid) in biology. A few structures are characterized by highly distorted geometries, e.g., the non-cubane [4Fe–4S] center and the hydrogenase-related [4Fe–3S] cluster, and contain atypical ligations or vacant coordination sites, which confer them novel functions far from the common electron transfer. Herein, we single out clusters found in i) hydrogenases that ensure sustainable hydrogen cycling, promising a clean fuel production in the future, ii) radical-SAM enzymes that can inspire applied catalysis due to an intrinsic flexibility of the radical chemistry, and iii) standard [4Fe–4S] cluster with still unknown function in DNA repair enzymes, which offer a possibility to interfere with DNA repair in pathogens or improve it in humans. Focusing on the abovementioned enzymes, we demonstrate the unique power of resonance Raman spectroscopy to unveil remarkable features in FeS centers, which has contributed to our understanding of unusual structures and disentangling of unknown functions.
dirty 0
eu_rights_str_mv openAccess
format review
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inst_facet_str urn:organizationAcronym:unl{{{_:::_}}}Universidade Nova de Lisboa
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language eng
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oai_identifier_str oai:run.unl.pt:10362/142219
organization_str_mv urn:organizationAcronym:unl
person_str_mv Caserta, Giorgio
Zuccarello, Lidia
Barbosa, Catarina
Silveira, Célia M.
Moe, Elin
Katz, Sagie
Hildebrandt, Peter
Zebger, Ingo
Todorovic, Smilja
publishDate 2022
repo_facet_str urn:repositoryAcronym:run{{{_:::_}}}Repositório Institucional da UNL
reponame_str Repositório Institucional da UNL
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service_str_mv urn:repositoryAcronym:run
spelling engenThe universe of known biological FeS clusters is constantly enlarging. Besides the conventional, well described [2Fe–2S], [3Fe–4S] and cubane [4Fe–4S] clusters, novel, unprecedented structures are emerging. They include unusually coordinated clusters, with additional sulfur atoms, e.g., [4Fe–5S], [5Fe–5S], [4Fe–4S]-5S-[4Fe–4S], [8Fe–7S], [8Fe–9S] and [8Fe–8S–C] and heteronuclear clusters, e.g., [Ni–4Fe–4S], [2Ni–4Fe–4S], [4Fe–4S]-[2Ru], [Me–7Fe–9S–C–(homocitrate)] that undertake versatile physiological roles in the activation of small molecules (H2, CO2, CO and N2) and in the sulfuration of different compounds (e.g., t-RNAs, biotin and lipoic acid) in biology. A few structures are characterized by highly distorted geometries, e.g., the non-cubane [4Fe–4S] center and the hydrogenase-related [4Fe–3S] cluster, and contain atypical ligations or vacant coordination sites, which confer them novel functions far from the common electron transfer. Herein, we single out clusters found in i) hydrogenases that ensure sustainable hydrogen cycling, promising a clean fuel production in the future, ii) radical-SAM enzymes that can inspire applied catalysis due to an intrinsic flexibility of the radical chemistry, and iii) standard [4Fe–4S] cluster with still unknown function in DNA repair enzymes, which offer a possibility to interfere with DNA repair in pathogens or improve it in humans. Focusing on the abovementioned enzymes, we demonstrate the unique power of resonance Raman spectroscopy to unveil remarkable features in FeS centers, which has contributed to our understanding of unusual structures and disentangling of unknown functions.application/pdfenUnusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspectiveCaserta, GiorgioZuccarello, LidiaBarbosa, CatarinaSilveira, Célia M.Moe, ElinKatz, SagieHildebrandt, PeterZebger, IngoTodorovic, SmiljaInstituto de Tecnologia Química e Biológica António Xavier (ITQB)ElsevierHostingInstitutionOrganizationalRUNe-mailmailto:run@unl.ptrun@unl.ptISSNIsPartOf0010-8545URNIsPartOfPURE: 43574064URNIsPartOfPURE UUID: 3a12ad12-ad2c-402b-a7e2-ee729e219d57URNIsPartOfScopus: 85118884484DOIIsPartOf10.1016/j.ccr.2021.2142872022-07-20T22:30:47Z2022-02-012022-02-01T00:00:00ZHandlehttp://hdl.handle.net/10362/142219http://purl.org/coar/access_right/c_abf2open accessFeS clustersGlycosylaseHydrogenaseRadical-SAMResonance Raman spectroscopyPhysical and Theoretical ChemistryInorganic ChemistryMaterials ChemistrySDG 7 - Affordable and Clean Energy2241708 bytesother research producthttp://purl.org/coar/resource_type/c_efa0reviewhttp://purl.org/coar/access_right/c_abf2application/pdffulltexthttps://run.unl.pt/bitstreams/01d0cd10-c880-42aa-9b17-d0815e4fa029/download
spellingShingle Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
Caserta, Giorgio
FeS clusters
Glycosylase
Hydrogenase
Radical-SAM
Resonance Raman spectroscopy
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry
SDG 7 - Affordable and Clean Energy
status SINGLETON
subject.fl_str_mv FeS clusters
Glycosylase
Hydrogenase
Radical-SAM
Resonance Raman spectroscopy
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry
SDG 7 - Affordable and Clean Energy
title Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
title_full Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
title_fullStr Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
title_full_unstemmed Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
title_short Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
title_sort Unusual structures and unknown roles of FeS clusters in metalloenzymes seen from a resonance Raman spectroscopic perspective
topic FeS clusters
Glycosylase
Hydrogenase
Radical-SAM
Resonance Raman spectroscopy
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry
SDG 7 - Affordable and Clean Energy
topic_facet FeS clusters
Glycosylase
Hydrogenase
Radical-SAM
Resonance Raman spectroscopy
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry
SDG 7 - Affordable and Clean Energy
url http://hdl.handle.net/10362/142219
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