The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones

Autores
Guerra, Walter Damián; Odella, Emmanuel; Cui, Kai; Secor, Maxim; Dominguez, Rodrigo Ezequiel; Gonzalez Lopez, Edwin Javier; Moore, Thomas A.; Hammes Schiffer, Sharon; Moore, Ana L.
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A bioinspired naphthoquinone model of the quinones in photosynthetic reaction centers but bearing an intramolecular hydrogen-bonded carboxylic acid has been synthesized and characterized electrochemically, spectroscopically, and computationally to provide mechanistic insight into the role of proton-coupled electron transfer (PCET) of quinone reduction in photosynthesis. The reduction potential of this construct is 370 mV more positive than the unsubstituted naphthoquinone. In addition to the reversible cyclic voltammetry, infrared spectroelectrochemistry confirms that the naphthoquinone/naphthoquinone radical anion couple is fully reversible. Calculated redox potentials agree with the experimental trends arising from the intramolecular hydrogen bond. Molecular electrostatic potentials illustrate the reversible proton transfer driving forces, and analysis of the computed vibrational spectra supports the possibility of a combination of electron transfer and PCET processes. The significance of PCET, reversibility, and redox potential management relevant to the design of artificial photosynthetic assemblies involving PCET processes is discussed.
Fil: Guerra, Walter Damián. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Odella, Emmanuel. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Cui, Kai. University of Princeton; Estados Unidos
Fil: Secor, Maxim. University of Princeton; Estados Unidos
Fil: Dominguez, Rodrigo Ezequiel. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Gonzalez Lopez, Edwin Javier. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
Fil: Hammes Schiffer, Sharon. University of Princeton; Estados Unidos
Fil: Moore, Ana L.. Arizona State University; Estados Unidos
Materia
BIOINSPIRED NAPHTHOQUINONE
PROTON-COUPLED ELECTRON TRANSFER
INFRARED SPECTROELECTROCHEMISTRY
ARTIFICIAL PHOTOSYNTHETIC
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/263096
Acceder
id CONICETDig_ef0f0d6fdc68f53ed87e2e482ee20344
oai_identifier_str oai:ri.conicet.gov.ar:11336/263096
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinonesGuerra, Walter DamiánOdella, EmmanuelCui, KaiSecor, MaximDominguez, Rodrigo EzequielGonzalez Lopez, Edwin JavierMoore, Thomas A.Hammes Schiffer, SharonMoore, Ana L.BIOINSPIRED NAPHTHOQUINONEPROTON-COUPLED ELECTRON TRANSFERINFRARED SPECTROELECTROCHEMISTRYARTIFICIAL PHOTOSYNTHETIChttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A bioinspired naphthoquinone model of the quinones in photosynthetic reaction centers but bearing an intramolecular hydrogen-bonded carboxylic acid has been synthesized and characterized electrochemically, spectroscopically, and computationally to provide mechanistic insight into the role of proton-coupled electron transfer (PCET) of quinone reduction in photosynthesis. The reduction potential of this construct is 370 mV more positive than the unsubstituted naphthoquinone. In addition to the reversible cyclic voltammetry, infrared spectroelectrochemistry confirms that the naphthoquinone/naphthoquinone radical anion couple is fully reversible. Calculated redox potentials agree with the experimental trends arising from the intramolecular hydrogen bond. Molecular electrostatic potentials illustrate the reversible proton transfer driving forces, and analysis of the computed vibrational spectra supports the possibility of a combination of electron transfer and PCET processes. The significance of PCET, reversibility, and redox potential management relevant to the design of artificial photosynthetic assemblies involving PCET processes is discussed.Fil: Guerra, Walter Damián. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Odella, Emmanuel. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Cui, Kai. University of Princeton; Estados UnidosFil: Secor, Maxim. University of Princeton; Estados UnidosFil: Dominguez, Rodrigo Ezequiel. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Gonzalez Lopez, Edwin Javier. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Moore, Thomas A.. Arizona State University; Estados UnidosFil: Hammes Schiffer, Sharon. University of Princeton; Estados UnidosFil: Moore, Ana L.. Arizona State University; Estados UnidosRoyal Society of Chemistry2024-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/263096Guerra, Walter Damián; Odella, Emmanuel; Cui, Kai; Secor, Maxim; Dominguez, Rodrigo Ezequiel; et al.; The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones; Royal Society of Chemistry; Chemical Science; 15; 42; 9-2024; 17425-174342041-65202041-6539CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://xlink.rsc.org/?DOI=D4SC05277Cinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D4SC05277Cinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:15:56Zoai:ri.conicet.gov.ar:11336/263096instacron: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:34982025-09-10 13:15:57.21CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
title The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
spellingShingle The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
Guerra, Walter Damián
BIOINSPIRED NAPHTHOQUINONE
PROTON-COUPLED ELECTRON TRANSFER
INFRARED SPECTROELECTROCHEMISTRY
ARTIFICIAL PHOTOSYNTHETIC
title_short The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
title_full The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
title_fullStr The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
title_full_unstemmed The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
title_sort The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones
dc.creator.none.fl_str_mv Guerra, Walter Damián
Odella, Emmanuel
Cui, Kai
Secor, Maxim
Dominguez, Rodrigo Ezequiel
Gonzalez Lopez, Edwin Javier
Moore, Thomas A.
Hammes Schiffer, Sharon
Moore, Ana L.
author Guerra, Walter Damián
author_facet Guerra, Walter Damián
Odella, Emmanuel
Cui, Kai
Secor, Maxim
Dominguez, Rodrigo Ezequiel
Gonzalez Lopez, Edwin Javier
Moore, Thomas A.
Hammes Schiffer, Sharon
Moore, Ana L.
author_role author
author2 Odella, Emmanuel
Cui, Kai
Secor, Maxim
Dominguez, Rodrigo Ezequiel
Gonzalez Lopez, Edwin Javier
Moore, Thomas A.
Hammes Schiffer, Sharon
Moore, Ana L.
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv BIOINSPIRED NAPHTHOQUINONE
PROTON-COUPLED ELECTRON TRANSFER
INFRARED SPECTROELECTROCHEMISTRY
ARTIFICIAL PHOTOSYNTHETIC
topic BIOINSPIRED NAPHTHOQUINONE
PROTON-COUPLED ELECTRON TRANSFER
INFRARED SPECTROELECTROCHEMISTRY
ARTIFICIAL PHOTOSYNTHETIC
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A bioinspired naphthoquinone model of the quinones in photosynthetic reaction centers but bearing an intramolecular hydrogen-bonded carboxylic acid has been synthesized and characterized electrochemically, spectroscopically, and computationally to provide mechanistic insight into the role of proton-coupled electron transfer (PCET) of quinone reduction in photosynthesis. The reduction potential of this construct is 370 mV more positive than the unsubstituted naphthoquinone. In addition to the reversible cyclic voltammetry, infrared spectroelectrochemistry confirms that the naphthoquinone/naphthoquinone radical anion couple is fully reversible. Calculated redox potentials agree with the experimental trends arising from the intramolecular hydrogen bond. Molecular electrostatic potentials illustrate the reversible proton transfer driving forces, and analysis of the computed vibrational spectra supports the possibility of a combination of electron transfer and PCET processes. The significance of PCET, reversibility, and redox potential management relevant to the design of artificial photosynthetic assemblies involving PCET processes is discussed.
Fil: Guerra, Walter Damián. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Odella, Emmanuel. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Cui, Kai. University of Princeton; Estados Unidos
Fil: Secor, Maxim. University of Princeton; Estados Unidos
Fil: Dominguez, Rodrigo Ezequiel. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Gonzalez Lopez, Edwin Javier. Arizona State University; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
Fil: Hammes Schiffer, Sharon. University of Princeton; Estados Unidos
Fil: Moore, Ana L.. Arizona State University; Estados Unidos
description A bioinspired naphthoquinone model of the quinones in photosynthetic reaction centers but bearing an intramolecular hydrogen-bonded carboxylic acid has been synthesized and characterized electrochemically, spectroscopically, and computationally to provide mechanistic insight into the role of proton-coupled electron transfer (PCET) of quinone reduction in photosynthesis. The reduction potential of this construct is 370 mV more positive than the unsubstituted naphthoquinone. In addition to the reversible cyclic voltammetry, infrared spectroelectrochemistry confirms that the naphthoquinone/naphthoquinone radical anion couple is fully reversible. Calculated redox potentials agree with the experimental trends arising from the intramolecular hydrogen bond. Molecular electrostatic potentials illustrate the reversible proton transfer driving forces, and analysis of the computed vibrational spectra supports the possibility of a combination of electron transfer and PCET processes. The significance of PCET, reversibility, and redox potential management relevant to the design of artificial photosynthetic assemblies involving PCET processes is discussed.
publishDate 2024
dc.date.none.fl_str_mv 2024-09
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/11336/263096
Guerra, Walter Damián; Odella, Emmanuel; Cui, Kai; Secor, Maxim; Dominguez, Rodrigo Ezequiel; et al.; The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones; Royal Society of Chemistry; Chemical Science; 15; 42; 9-2024; 17425-17434
2041-6520
2041-6539
CONICET Digital
CONICET
url http://hdl.handle.net/11336/263096
identifier_str_mv Guerra, Walter Damián; Odella, Emmanuel; Cui, Kai; Secor, Maxim; Dominguez, Rodrigo Ezequiel; et al.; The role of an intramolecular hydrogen bond in the redox properties of carboxylic acid naphthoquinones; Royal Society of Chemistry; Chemical Science; 15; 42; 9-2024; 17425-17434
2041-6520
2041-6539
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://xlink.rsc.org/?DOI=D4SC05277C
info:eu-repo/semantics/altIdentifier/doi/10.1039/D4SC05277C
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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
_version_ 1842980863881510912
score 12.993085

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