Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation

Autores
Megiatto, Jackson D.; Antoniuk Pablant, Antaeres; Sherman, Benjamin D.; Kodis, Gerdenis; Gervaldo, Miguel Andres; Moore, Thomas A.; Moore, Ana L.; Gust, Devens
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In the photosynthetic photosystem II, electrons are transferred from the manganese-containing oxygen evolving complex (OEC) to the oxidized primary electron-donor chlorophyll P680•+ by a proton-coupled electron transfer process involving a tyrosine-histidine pair. Proton transfer from the tyrosine phenolic group to a histidine nitrogen positions the redox potential of the tyrosine between those of P680•+ and the OEC. We report the synthesis and time-resolved spectroscopic study of a molecular triad that models this electron transfer. The triad consists of a high-potential porphyrin bearing two pentafluorophenyl groups (PF10), a tetracyanoporphyrin electron acceptor (TCNP), and a benzimidazole-phenol secondary electron-donor (Bi-PhOH). Excitation of PF10 in benzonitrile is followed by singlet energy transfer to TCNP (τ = 41 ps), whose excited state decays by photoinduced electron transfer (τ = 830 ps) to yield Bi-PhOH-PF 10•+-TCNP•-. A second electron transfer reaction follows (τ < 12 ps), giving a final state postulated as BiH+-PhO•-PF10-TCNP•-, in which the phenolic proton now resides on benzimidazole. This final state decays with a time constant of 3.8 μs. The triad thus functionally mimics the electron transfers involving the tyrosine-histidine pair in PSII. The final charge-separated state is thermodynamically capable of water oxidation, and its long lifetime suggests the possibility of coupling systems such as this system to water oxidation catalysts for use in artificial photosynthetic fuel production.
Fil: Megiatto, Jackson D.. Arizona State University; Estados Unidos
Fil: Antoniuk Pablant, Antaeres. Arizona State University; Estados Unidos
Fil: Sherman, Benjamin D.. Arizona State University; Estados Unidos
Fil: Kodis, Gerdenis. Arizona State University; Estados Unidos
Fil: Gervaldo, Miguel Andres. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
Fil: Moore, Ana L.. Arizona State University; Estados Unidos
Fil: Gust, Devens. Arizona State University; Estados Unidos
Materia
BIOMIMICRY
PHOTOCHEMISTRY
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:11336/194735
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/194735
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidationMegiatto, Jackson D.Antoniuk Pablant, AntaeresSherman, Benjamin D.Kodis, GerdenisGervaldo, Miguel AndresMoore, Thomas A.Moore, Ana L.Gust, DevensBIOMIMICRYPHOTOCHEMISTRYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In the photosynthetic photosystem II, electrons are transferred from the manganese-containing oxygen evolving complex (OEC) to the oxidized primary electron-donor chlorophyll P680•+ by a proton-coupled electron transfer process involving a tyrosine-histidine pair. Proton transfer from the tyrosine phenolic group to a histidine nitrogen positions the redox potential of the tyrosine between those of P680•+ and the OEC. We report the synthesis and time-resolved spectroscopic study of a molecular triad that models this electron transfer. The triad consists of a high-potential porphyrin bearing two pentafluorophenyl groups (PF10), a tetracyanoporphyrin electron acceptor (TCNP), and a benzimidazole-phenol secondary electron-donor (Bi-PhOH). Excitation of PF10 in benzonitrile is followed by singlet energy transfer to TCNP (τ = 41 ps), whose excited state decays by photoinduced electron transfer (τ = 830 ps) to yield Bi-PhOH-PF 10•+-TCNP•-. A second electron transfer reaction follows (τ < 12 ps), giving a final state postulated as BiH+-PhO•-PF10-TCNP•-, in which the phenolic proton now resides on benzimidazole. This final state decays with a time constant of 3.8 μs. The triad thus functionally mimics the electron transfers involving the tyrosine-histidine pair in PSII. The final charge-separated state is thermodynamically capable of water oxidation, and its long lifetime suggests the possibility of coupling systems such as this system to water oxidation catalysts for use in artificial photosynthetic fuel production.Fil: Megiatto, Jackson D.. Arizona State University; Estados UnidosFil: Antoniuk Pablant, Antaeres. Arizona State University; Estados UnidosFil: Sherman, Benjamin D.. Arizona State University; Estados UnidosFil: Kodis, Gerdenis. Arizona State University; Estados UnidosFil: Gervaldo, Miguel Andres. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Moore, Thomas A.. Arizona State University; Estados UnidosFil: Moore, Ana L.. Arizona State University; Estados UnidosFil: Gust, Devens. Arizona State University; Estados UnidosNational Academy of Sciences2012-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/194735Megiatto, Jackson D.; Antoniuk Pablant, Antaeres; Sherman, Benjamin D.; Kodis, Gerdenis; Gervaldo, Miguel Andres; et al.; Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation; National Academy of Sciences; Proceedings of the National Academy of Sciences of The United States of America; 109; 39; 3-2012; 15578-155830027-8424CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.pnas.org/doi/10.1073/pnas.1118348109info:eu-repo/semantics/altIdentifier/doi/10.1073/pnas.1118348109info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:54:41Zoai:ri.conicet.gov.ar:11336/194735instacron: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 09:54:42.143CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
title Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
spellingShingle Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
Megiatto, Jackson D.
BIOMIMICRY
PHOTOCHEMISTRY
title_short Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
title_full Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
title_fullStr Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
title_full_unstemmed Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
title_sort Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation
dc.creator.none.fl_str_mv Megiatto, Jackson D.
Antoniuk Pablant, Antaeres
Sherman, Benjamin D.
Kodis, Gerdenis
Gervaldo, Miguel Andres
Moore, Thomas A.
Moore, Ana L.
Gust, Devens
author Megiatto, Jackson D.
author_facet Megiatto, Jackson D.
Antoniuk Pablant, Antaeres
Sherman, Benjamin D.
Kodis, Gerdenis
Gervaldo, Miguel Andres
Moore, Thomas A.
Moore, Ana L.
Gust, Devens
author_role author
author2 Antoniuk Pablant, Antaeres
Sherman, Benjamin D.
Kodis, Gerdenis
Gervaldo, Miguel Andres
Moore, Thomas A.
Moore, Ana L.
Gust, Devens
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv BIOMIMICRY
PHOTOCHEMISTRY
topic BIOMIMICRY
PHOTOCHEMISTRY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In the photosynthetic photosystem II, electrons are transferred from the manganese-containing oxygen evolving complex (OEC) to the oxidized primary electron-donor chlorophyll P680•+ by a proton-coupled electron transfer process involving a tyrosine-histidine pair. Proton transfer from the tyrosine phenolic group to a histidine nitrogen positions the redox potential of the tyrosine between those of P680•+ and the OEC. We report the synthesis and time-resolved spectroscopic study of a molecular triad that models this electron transfer. The triad consists of a high-potential porphyrin bearing two pentafluorophenyl groups (PF10), a tetracyanoporphyrin electron acceptor (TCNP), and a benzimidazole-phenol secondary electron-donor (Bi-PhOH). Excitation of PF10 in benzonitrile is followed by singlet energy transfer to TCNP (τ = 41 ps), whose excited state decays by photoinduced electron transfer (τ = 830 ps) to yield Bi-PhOH-PF 10•+-TCNP•-. A second electron transfer reaction follows (τ < 12 ps), giving a final state postulated as BiH+-PhO•-PF10-TCNP•-, in which the phenolic proton now resides on benzimidazole. This final state decays with a time constant of 3.8 μs. The triad thus functionally mimics the electron transfers involving the tyrosine-histidine pair in PSII. The final charge-separated state is thermodynamically capable of water oxidation, and its long lifetime suggests the possibility of coupling systems such as this system to water oxidation catalysts for use in artificial photosynthetic fuel production.
Fil: Megiatto, Jackson D.. Arizona State University; Estados Unidos
Fil: Antoniuk Pablant, Antaeres. Arizona State University; Estados Unidos
Fil: Sherman, Benjamin D.. Arizona State University; Estados Unidos
Fil: Kodis, Gerdenis. Arizona State University; Estados Unidos
Fil: Gervaldo, Miguel Andres. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
Fil: Moore, Ana L.. Arizona State University; Estados Unidos
Fil: Gust, Devens. Arizona State University; Estados Unidos
description In the photosynthetic photosystem II, electrons are transferred from the manganese-containing oxygen evolving complex (OEC) to the oxidized primary electron-donor chlorophyll P680•+ by a proton-coupled electron transfer process involving a tyrosine-histidine pair. Proton transfer from the tyrosine phenolic group to a histidine nitrogen positions the redox potential of the tyrosine between those of P680•+ and the OEC. We report the synthesis and time-resolved spectroscopic study of a molecular triad that models this electron transfer. The triad consists of a high-potential porphyrin bearing two pentafluorophenyl groups (PF10), a tetracyanoporphyrin electron acceptor (TCNP), and a benzimidazole-phenol secondary electron-donor (Bi-PhOH). Excitation of PF10 in benzonitrile is followed by singlet energy transfer to TCNP (τ = 41 ps), whose excited state decays by photoinduced electron transfer (τ = 830 ps) to yield Bi-PhOH-PF 10•+-TCNP•-. A second electron transfer reaction follows (τ < 12 ps), giving a final state postulated as BiH+-PhO•-PF10-TCNP•-, in which the phenolic proton now resides on benzimidazole. This final state decays with a time constant of 3.8 μs. The triad thus functionally mimics the electron transfers involving the tyrosine-histidine pair in PSII. The final charge-separated state is thermodynamically capable of water oxidation, and its long lifetime suggests the possibility of coupling systems such as this system to water oxidation catalysts for use in artificial photosynthetic fuel production.
publishDate 2012
dc.date.none.fl_str_mv 2012-03
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/11336/194735
Megiatto, Jackson D.; Antoniuk Pablant, Antaeres; Sherman, Benjamin D.; Kodis, Gerdenis; Gervaldo, Miguel Andres; et al.; Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation; National Academy of Sciences; Proceedings of the National Academy of Sciences of The United States of America; 109; 39; 3-2012; 15578-15583
0027-8424
CONICET Digital
CONICET
url http://hdl.handle.net/11336/194735
identifier_str_mv Megiatto, Jackson D.; Antoniuk Pablant, Antaeres; Sherman, Benjamin D.; Kodis, Gerdenis; Gervaldo, Miguel Andres; et al.; Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation; National Academy of Sciences; Proceedings of the National Academy of Sciences of The United States of America; 109; 39; 3-2012; 15578-15583
0027-8424
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.pnas.org/doi/10.1073/pnas.1118348109
info:eu-repo/semantics/altIdentifier/doi/10.1073/pnas.1118348109
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 National Academy of Sciences
publisher.none.fl_str_mv National Academy of Sciences
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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