Spectroscopic Analysis of a Biomimetic Model of Tyr sub(Z) Function in PSII

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 electro...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2015-09, Vol.119 (37), p.12156-12163
Main Authors: Ravensbergen, Janneke, Antoniuk-Pablant, Antaeres, Sherman, Benjamin D, Kodis, Gerdenis, Megiatto, Jackson D, Mendez-Hernandez, Dalvin D, Frese, Raoul N, Grondelle, Rienk van, Moore, Thomas A, Moore, Ana L, Gust, Devens, Kennis, John TM
Format: Article
Language:English
Subjects:
Biomimetics
Charge
Excitation
Porphyrins
Solvation
Spectroscopic analysis
Sunlight
Synthesis (chemistry)
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Summary: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 sub(Z)-D sub(1)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.
ISSN:1520-6106
1520-5207
DOI:10.1021/acs.jpcb.5b05298