Biomimetic ketone reduction by disulfide radical anion

Autores
Barata Vallejo, Sebastian; Skotnicki, Konrad; Ferreri, Carla; Marciniak, Bronislaw; Bobrowski, Krzysztof; Chatgilialoglu, Chryssostomos
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The conversion of ribonucleosides to 2′-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3′-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSR•−) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)•− in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)•− transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)•− at λmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104–105 M−1s−1 at ~22◦C.
Fil: Barata Vallejo, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina
Fil: Skotnicki, Konrad. Institute of Nuclear Chemistry and Technology; Polonia
Fil: Ferreri, Carla. Centre National de la Recherche Scientifique; Francia
Fil: Marciniak, Bronislaw. Adam Mickiewicz University; Polonia
Fil: Bobrowski, Krzysztof. Institute of Nuclear Chemistry and Technology; Polonia
Fil: Chatgilialoglu, Chryssostomos. Centre National de la Recherche Scientifique; Francia. Adam Mickiewicz University; Polonia
Materia
BIOMIMETIC CHEMISTRY
CYSTEINE
FREE RADICALS
KETONE REDUCTION
KINETICS
PULSE RADIOLYSIS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/149796
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Biomimetic ketone reduction by disulfide radical anionBarata Vallejo, SebastianSkotnicki, KonradFerreri, CarlaMarciniak, BronislawBobrowski, KrzysztofChatgilialoglu, ChryssostomosBIOMIMETIC CHEMISTRYCYSTEINEFREE RADICALSKETONE REDUCTIONKINETICSPULSE RADIOLYSIShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The conversion of ribonucleosides to 2′-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3′-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSR•−) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)•− in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)•− transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)•− at λmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104–105 M−1s−1 at ~22◦C.Fil: Barata Vallejo, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; ArgentinaFil: Skotnicki, Konrad. Institute of Nuclear Chemistry and Technology; PoloniaFil: Ferreri, Carla. Centre National de la Recherche Scientifique; FranciaFil: Marciniak, Bronislaw. Adam Mickiewicz University; PoloniaFil: Bobrowski, Krzysztof. Institute of Nuclear Chemistry and Technology; PoloniaFil: Chatgilialoglu, Chryssostomos. Centre National de la Recherche Scientifique; Francia. Adam Mickiewicz University; PoloniaMolecular Diversity Preservation International2021-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/149796Barata Vallejo, Sebastian; Skotnicki, Konrad; Ferreri, Carla; Marciniak, Bronislaw; Bobrowski, Krzysztof; et al.; Biomimetic ketone reduction by disulfide radical anion; Molecular Diversity Preservation International; Molecules; 26; 18; 9-2021; 1-121420-3049CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/1420-3049/26/18/5429info:eu-repo/semantics/altIdentifier/doi/10.3390/molecules26185429info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:52:58Zoai:ri.conicet.gov.ar:11336/149796instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:52:59.029CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Biomimetic ketone reduction by disulfide radical anion
title Biomimetic ketone reduction by disulfide radical anion
spellingShingle Biomimetic ketone reduction by disulfide radical anion
Barata Vallejo, Sebastian
BIOMIMETIC CHEMISTRY
CYSTEINE
FREE RADICALS
KETONE REDUCTION
KINETICS
PULSE RADIOLYSIS
title_short Biomimetic ketone reduction by disulfide radical anion
title_full Biomimetic ketone reduction by disulfide radical anion
title_fullStr Biomimetic ketone reduction by disulfide radical anion
title_full_unstemmed Biomimetic ketone reduction by disulfide radical anion
title_sort Biomimetic ketone reduction by disulfide radical anion
dc.creator.none.fl_str_mv Barata Vallejo, Sebastian
Skotnicki, Konrad
Ferreri, Carla
Marciniak, Bronislaw
Bobrowski, Krzysztof
Chatgilialoglu, Chryssostomos
author Barata Vallejo, Sebastian
author_facet Barata Vallejo, Sebastian
Skotnicki, Konrad
Ferreri, Carla
Marciniak, Bronislaw
Bobrowski, Krzysztof
Chatgilialoglu, Chryssostomos
author_role author
author2 Skotnicki, Konrad
Ferreri, Carla
Marciniak, Bronislaw
Bobrowski, Krzysztof
Chatgilialoglu, Chryssostomos
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv BIOMIMETIC CHEMISTRY
CYSTEINE
FREE RADICALS
KETONE REDUCTION
KINETICS
PULSE RADIOLYSIS
topic BIOMIMETIC CHEMISTRY
CYSTEINE
FREE RADICALS
KETONE REDUCTION
KINETICS
PULSE RADIOLYSIS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The conversion of ribonucleosides to 2′-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3′-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSR•−) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)•− in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)•− transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)•− at λmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104–105 M−1s−1 at ~22◦C.
Fil: Barata Vallejo, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina
Fil: Skotnicki, Konrad. Institute of Nuclear Chemistry and Technology; Polonia
Fil: Ferreri, Carla. Centre National de la Recherche Scientifique; Francia
Fil: Marciniak, Bronislaw. Adam Mickiewicz University; Polonia
Fil: Bobrowski, Krzysztof. Institute of Nuclear Chemistry and Technology; Polonia
Fil: Chatgilialoglu, Chryssostomos. Centre National de la Recherche Scientifique; Francia. Adam Mickiewicz University; Polonia
description The conversion of ribonucleosides to 2′-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3′-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSR•−) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)•− in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)•− transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)•− at λmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104–105 M−1s−1 at ~22◦C.
publishDate 2021
dc.date.none.fl_str_mv 2021-09
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/149796
Barata Vallejo, Sebastian; Skotnicki, Konrad; Ferreri, Carla; Marciniak, Bronislaw; Bobrowski, Krzysztof; et al.; Biomimetic ketone reduction by disulfide radical anion; Molecular Diversity Preservation International; Molecules; 26; 18; 9-2021; 1-12
1420-3049
CONICET Digital
CONICET
url http://hdl.handle.net/11336/149796
identifier_str_mv Barata Vallejo, Sebastian; Skotnicki, Konrad; Ferreri, Carla; Marciniak, Bronislaw; Bobrowski, Krzysztof; et al.; Biomimetic ketone reduction by disulfide radical anion; Molecular Diversity Preservation International; Molecules; 26; 18; 9-2021; 1-12
1420-3049
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/1420-3049/26/18/5429
info:eu-repo/semantics/altIdentifier/doi/10.3390/molecules26185429
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Molecular Diversity Preservation International
publisher.none.fl_str_mv Molecular Diversity Preservation International
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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