title: A bioinspired redox relay that mimics radical interactions of the Tyr-His pairs of photosystem II.
abstract: In water-oxidizing photosynthetic organisms, light absorption generates a powerfully oxidizing chlorophyll complex (P680(•+)) in the photosystem II reaction centre. This is reduced via an electron transfer pathway from the manganese-containing water-oxidizing catalyst, which includes an electron transfer relay comprising a tyrosine (Tyr)-histidine (His) pair that features a hydrogen bond between a phenol group and an imidazole group. By rapidly reducing P680(•+), the relay is thought to mitigate recombination reactions, thereby ensuring a high quantum yield of water oxidation. Here, we show that an artificial reaction centre that features a benzimidazole-phenol model of the Tyr-His pair mimics both the short-internal hydrogen bond in photosystem II and, using electron paramagnetic resonance spectroscopy, the thermal relaxation that accompanies proton-coupled electron transfer. Although this artificial system is much less complex than the natural one, theory suggests that it captures the essential features that are important in the function of the relay.
authors.affiliation: 1] Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA [2].
authors.forename: Jackson D
authors.initials: JD
authors.lastname: Megiatto
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Dalvin D
authors.initials: DD
authors.lastname: Méndez-Hernández
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Marely E
authors.initials: ME
authors.lastname: Tejeda-Ferrari
authors.affiliation: 1] Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA [2] Laboratoire de Chimie Physique, Groupe d'Electrochimie et de Photoélectrochimie, UMR 8000, CNRS, Université Paris-Sud, Batiment 350, 91405 Orsay Cedex, France.
authors.forename: Anne-Lucie
authors.initials: AL
authors.lastname: Teillout
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Manuel J
authors.initials: MJ
authors.lastname: Llansola-Portolés
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Gerdenis
authors.initials: G
authors.lastname: Kodis
authors.affiliation: NanoBio Interface Group, Center for Nanoscale Materials and Chemical Sciences and Engineering Division, Argonne National Laboratory Argonne, Illinois 60439, USA.
authors.forename: Oleg G
authors.initials: OG
authors.lastname: Poluektov
authors.affiliation: NanoBio Interface Group, Center for Nanoscale Materials and Chemical Sciences and Engineering Division, Argonne National Laboratory Argonne, Illinois 60439, USA.
authors.forename: Tijana
authors.initials: T
authors.lastname: Rajh
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Vladimiro
authors.initials: V
authors.lastname: Mujica
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Thomas L
authors.initials: TL
authors.lastname: Groy
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Devens
authors.initials: D
authors.lastname: Gust
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Thomas A
authors.initials: TA
authors.lastname: Moore
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: Ana L
authors.initials: AL
authors.lastname: Moore
mesh_terms: D000097:Acetonitriles; D032701:Biomimetics; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry / Q000378:metabolism; D006639:Histidine / Q000737:chemistry / Q000378:metabolism*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D045332:Photosystem II Protein Complex / Q000737:chemistry* / Q000378:metabolism*; D014443:Tyrosine / Q000737:chemistry / Q000378:metabolism*
chemical_list: D000097:Acetonitriles; D005609:Free Radicals; D045332:Photosystem II Protein Complex; D014443:Tyrosine; D006639:Histidine; C032159:acetonitrile
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