Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII

Janneke Ravensbergen, Antaeres Antoniuk-Pablant, Benjamin D. Sherman, Gerdenis Kodis, Jackson D. Megiatto, Dalvin D. Méndez-Hernández, Raoul N. Frese, Rienk Van Grondelle, Thomas A. Moore, Ana L. Moore, Devens Gust, John T M Kennis

Research output: Research - peer-reviewArticle

Abstract

Using natural photosynthesis as a model, bio-inspired constructs for fuel generation from sunlight are being developed. Here we report the synthesis and time-resolved spectroscopic analysis of a molecular triad in which a porphyrin electron donor is covalently linked to both a cyanoporphyrin electron acceptor and a benzimidazole-phenol model for the Tyr<inf>Z</inf>-D<inf>1</inf>His190 pair of PSII. A dual-laser setup enabled us to record the ultrafast kinetics and long-living species in a single experiment. From this data, the photophysical relaxation pathways were elucidated for the triad and reference compounds. For the triad, quenching of the cyanoporphyrin singlet excited state lifetime was interpreted as photoinduced electron transfer from the porphyrin to the excited cyanoporphyrin. In contrast to a previous study of a related molecule, we were unable to observe subsequent formation of a long-lived charge separated state involving the benzimidazole-phenol moiety. The lack of detection of a long-lived charge separated state is attributed to a change in energetic landscape for charge separation/recombination due to small differences in structure and solvation of the new triad.

LanguageEnglish (US)
Pages12156-12163
Number of pages8
JournalJournal of Physical Chemistry B
Volume119
Issue number37
DOIs
StatePublished - Sep 1 2015

Fingerprint

biomimetics
spectroscopic analysis
porphyrins
phenols
electrons
Spectroscopic analysis
Biomimetics
Electrons
Porphyrins
Phenol
benzimidazole
Phenols
photosynthesis
polarization (charge separation)
sunlight
solvation
electron transfer
quenching
life (durability)
kinetics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

Ravensbergen, J., Antoniuk-Pablant, A., Sherman, B. D., Kodis, G., Megiatto, J. D., Méndez-Hernández, D. D., ... Kennis, J. T. M. (2015). Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII. Journal of Physical Chemistry B, 119(37), 12156-12163. DOI: 10.1021/acs.jpcb.5b05298

Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII. / Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D.; Kodis, Gerdenis; Megiatto, Jackson D.; Méndez-Hernández, Dalvin D.; Frese, Raoul N.; Van Grondelle, Rienk; Moore, Thomas A.; Moore, Ana L.; Gust, Devens; Kennis, John T M.

In: Journal of Physical Chemistry B, Vol. 119, No. 37, 01.09.2015, p. 12156-12163.

Research output: Research - peer-reviewArticle

Ravensbergen, J, Antoniuk-Pablant, A, Sherman, BD, Kodis, G, Megiatto, JD, Méndez-Hernández, DD, Frese, RN, Van Grondelle, R, Moore, TA, Moore, AL, Gust, D & Kennis, JTM 2015, 'Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII' Journal of Physical Chemistry B, vol 119, no. 37, pp. 12156-12163. DOI: 10.1021/acs.jpcb.5b05298
Ravensbergen J, Antoniuk-Pablant A, Sherman BD, Kodis G, Megiatto JD, Méndez-Hernández DD et al. Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII. Journal of Physical Chemistry B. 2015 Sep 1;119(37):12156-12163. Available from, DOI: 10.1021/acs.jpcb.5b05298
Ravensbergen, Janneke ; Antoniuk-Pablant, Antaeres ; Sherman, Benjamin D. ; Kodis, Gerdenis ; Megiatto, Jackson D. ; Méndez-Hernández, Dalvin D. ; Frese, Raoul N. ; Van Grondelle, Rienk ; Moore, Thomas A. ; Moore, Ana L. ; Gust, Devens ; Kennis, John T M. / Spectroscopic Analysis of a Biomimetic Model of Tyr<inf>Z</inf> Function in PSII. In: Journal of Physical Chemistry B. 2015 ; Vol. 119, No. 37. pp. 12156-12163
@article{78318d4f195e455c843bc40987e845ce,
title = "Spectroscopic Analysis of a Biomimetic Model of TyrZ Function in PSII",
abstract = "Using natural photosynthesis as a model, bio-inspired constructs for fuel generation from sunlight are being developed. Here we report the synthesis and time-resolved spectroscopic analysis of a molecular triad in which a porphyrin electron donor is covalently linked to both a cyanoporphyrin electron acceptor and a benzimidazole-phenol model for the TyrZ-D1His190 pair of PSII. A dual-laser setup enabled us to record the ultrafast kinetics and long-living species in a single experiment. From this data, the photophysical relaxation pathways were elucidated for the triad and reference compounds. For the triad, quenching of the cyanoporphyrin singlet excited state lifetime was interpreted as photoinduced electron transfer from the porphyrin to the excited cyanoporphyrin. In contrast to a previous study of a related molecule, we were unable to observe subsequent formation of a long-lived charge separated state involving the benzimidazole-phenol moiety. The lack of detection of a long-lived charge separated state is attributed to a change in energetic landscape for charge separation/recombination due to small differences in structure and solvation of the new triad.",
author = "Janneke Ravensbergen and Antaeres Antoniuk-Pablant and Sherman, {Benjamin D.} and Gerdenis Kodis and Megiatto, {Jackson D.} and Méndez-Hernández, {Dalvin D.} and Frese, {Raoul N.} and {Van Grondelle}, Rienk and Moore, {Thomas A.} and Moore, {Ana L.} and Devens Gust and Kennis, {John T M}",
year = "2015",
month = "9",
doi = "10.1021/acs.jpcb.5b05298",
volume = "119",
pages = "12156--12163",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "37",

}

TY - JOUR

T1 - Spectroscopic Analysis of a Biomimetic Model of TyrZ Function in PSII

AU - Ravensbergen,Janneke

AU - Antoniuk-Pablant,Antaeres

AU - Sherman,Benjamin D.

AU - Kodis,Gerdenis

AU - Megiatto,Jackson D.

AU - Méndez-Hernández,Dalvin D.

AU - Frese,Raoul N.

AU - Van Grondelle,Rienk

AU - Moore,Thomas A.

AU - Moore,Ana L.

AU - Gust,Devens

AU - Kennis,John T M

PY - 2015/9/1

Y1 - 2015/9/1

N2 - Using natural photosynthesis as a model, bio-inspired constructs for fuel generation from sunlight are being developed. Here we report the synthesis and time-resolved spectroscopic analysis of a molecular triad in which a porphyrin electron donor is covalently linked to both a cyanoporphyrin electron acceptor and a benzimidazole-phenol model for the TyrZ-D1His190 pair of PSII. A dual-laser setup enabled us to record the ultrafast kinetics and long-living species in a single experiment. From this data, the photophysical relaxation pathways were elucidated for the triad and reference compounds. For the triad, quenching of the cyanoporphyrin singlet excited state lifetime was interpreted as photoinduced electron transfer from the porphyrin to the excited cyanoporphyrin. In contrast to a previous study of a related molecule, we were unable to observe subsequent formation of a long-lived charge separated state involving the benzimidazole-phenol moiety. The lack of detection of a long-lived charge separated state is attributed to a change in energetic landscape for charge separation/recombination due to small differences in structure and solvation of the new triad.

AB - Using natural photosynthesis as a model, bio-inspired constructs for fuel generation from sunlight are being developed. Here we report the synthesis and time-resolved spectroscopic analysis of a molecular triad in which a porphyrin electron donor is covalently linked to both a cyanoporphyrin electron acceptor and a benzimidazole-phenol model for the TyrZ-D1His190 pair of PSII. A dual-laser setup enabled us to record the ultrafast kinetics and long-living species in a single experiment. From this data, the photophysical relaxation pathways were elucidated for the triad and reference compounds. For the triad, quenching of the cyanoporphyrin singlet excited state lifetime was interpreted as photoinduced electron transfer from the porphyrin to the excited cyanoporphyrin. In contrast to a previous study of a related molecule, we were unable to observe subsequent formation of a long-lived charge separated state involving the benzimidazole-phenol moiety. The lack of detection of a long-lived charge separated state is attributed to a change in energetic landscape for charge separation/recombination due to small differences in structure and solvation of the new triad.

UR - http://www.scopus.com/inward/record.url?scp=84941910455&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84941910455&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcb.5b05298

DO - 10.1021/acs.jpcb.5b05298

M3 - Article

VL - 119

SP - 12156

EP - 12163

JO - Journal of Physical Chemistry B Materials

T2 - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 37

ER -