This Article describes the electron transfer (ET) kinetics in complexes of CdS nanorods (CdS NRs) and [FeFe]-hydrogenase I from Clostridium acetobutylicum (CaI). In the presence of an electron donor, these complexes produce H2 photochemically with quantum yields of up to 20%. Kinetics of ET from CdS NRs to CaI play a critical role in the overall photochemical reactivity, as the quantum efficiency of ET defines the upper limit on the quantum yield of H2 generation. We investigated the competitiveness of ET with the electron relaxation pathways in CdS NRs by directly measuring the rate and quantum efficiency of ET from photoexcited CdS NRs to CaI using transient absorption spectroscopy. This technique is uniquely suited to decouple CdS→CaI ET from the processes occurring in the enzyme during H2 production. We found that the ET rate constant (k(ET)) and the electron relaxation rate constant in CdS NRs (k(CdS)) were comparable, with values of 10(7) s(-1), resulting in a quantum efficiency of ET of 42% for complexes with the average CaI:CdS NR molar ratio of 1:1. Given the direct competition between the two processes that occur with similar rates, we propose that gains in efficiencies of H2 production could be achieved by increasing k(ET) and/or decreasing k(CdS) through structural modifications of the nanocrystals. When catalytically inactive forms of CaI were used in CdS-CaI complexes, ET behavior was akin to that observed with active CaI, demonstrating that electron injection occurs at a distal iron-sulfur cluster and is followed by transport through a series of accessory iron-sulfur clusters to the active site of CaI. Using insights from this time-resolved spectroscopic study, we discuss the intricate kinetic pathways involved in photochemical H2 generation in CdS-CaI complexes, and we examine how the relationship between the electron injection rate and the other kinetic processes relates to the overall H2 production efficiency.

Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H 2 O) (terpy)Mn(μ-O) 2 Mn(terpy)(H 2 O)](NO 3 ) 3 [terpy = 2,2′:6′,2″-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments will show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen. IntroductionIn the past ten years, a number of manganese-based water oxidation catalysts have been identified. 1-4 All of these new manganese catalysts are dimeric and all use two-electron oxygen-donor oxidants for catalytic turnover. [5][6][7] The necessity of such oxidants as well as the need for multiple manganese atoms have been issues of interest due to the tendency of manganese complexes to disproportionate peroxides to give O 2 via a catalase pathway rather than by water oxidation, 8 and due to the complexity inherent in multi-metal systems. To firmly establish the ability of manganese to oxidize water to oxygen, catalysis must be carried out using either a nonoxygen-donor oxidant or electrochemically, and a greater understanding of the necessary design elements must be reached.The oxidation of water to oxygen using nonoxygen-donor oxidants such as Ce(IV) has been well established in the ruthenium literature. [9][10][11] Due to the lack of any oxygen atom in the oxidant, O 2 must be formed from water. Unfortunately, in the history of manganese-based water oxidation, Ce(IV), and other similar oxidants, have generally failed to give catalytic O 2 . The most recent attempts to use Ce(IV) as an oxidant have at best yielded no more than a single turnover of oxygen. 6,12,13 It appears that oxidants such as Ce(IV) are often too acidic to be compatible with the basic oxo bridges of manganese dimers. 12 Figure 1) in aqueous solution. Previous electrochemical studies of water-oxidizing manganese complexes have been hindered by both the scarcity of such complexes and the ubiquitous background oxidation of water to oxygen at the electrode. Past efforts to study 1 by electrochemical methods have characterized the main redox features of 1. 14 By studying the previouslycharacterized redox behavior of 1 as a function of pH and with different ligands bound in place of the terminal water(s), we aim to gain a better understanding of the factors that influence water oxidation using manganese. These electrochemical studies also provide insight into the differing...

This paper reports computational studies of substrate water binding to the oxygen-evolving centre (OEC) of photosystem II (PSII ), completely ligated by amino acid residues, water, hydroxide and chloride. The calculations are based on quantum mechanics/molecular mechanics hybrid models of the OEC of PSII, recently developed in conjunction with the X-ray crystal structure of PSII from the cyanobacterium Thermosynechococcus elongatus. The model OEC involves a cuboidal Mn 3 CaO 4 Mn metal cluster with three closely associated manganese ions linked to a single m 4 -oxo-ligated Mn ion, often called the 'dangling manganese'. Two water molecules bound to calcium and the dangling manganese are postulated to be substrate molecules, responsible for dioxygen formation. It is found that the energy barriers for the Mn(4)-bound water agree nicely with those of model complexes. However, the barriers for Ca-bound waters are substantially larger. Water binding is not simply correlated to the formal oxidation states of the metal centres but rather to their corresponding electrostatic potential atomic charges as modulated by charge-transfer interactions. The calculations of structural rearrangements during water exchange provide support for the experimental finding that the exchange rates with bulk 18 O-labelled water should be smaller for water molecules coordinated to calcium than for water molecules attached to the dangling manganese. The models also predict that the S 1 /S 2 transition should produce opposite effects on the two waterexchange rates.

Cytochrome b₅₅₉ (Cyt b₅₅₉), β-carotene (Car), and chlorophyll (Chl) cofactors participate in the secondary electron-transfer pathways in photosystem II (PSII), which are believed to protect PSII from photodamage under conditions in which the primary electron-donation pathway leading to water oxidation is inhibited. Among these cofactors, Cyt b₅₅₉ is preferentially photooxidized under conditions in which the primary electron-donation pathway is blocked. When Cyt b₅₅₉ is preoxidized, the photooxidation of several of the 11 Car and 35 Chl molecules present per PSII is observed. In this review, the discovery of the secondary electron donors, their structures and electron-transfer properties, and progress in the characterization of the secondary electron-transfer pathways are discussed. This article is part of a Special Issue entitled: Photosystem II.

β-carotene radicals produced in the hexagonal pores of the molecular sieve Cu(II)-MCM-41 were studied by ENDOR and visible/near IR spectroscopies. ENDOR studies showed that neutral radicals of β-carotene were produced in humid air under ambient fluorescent light. The maximum absorption wavelengths of the neutral radicals were measured and were additionally predicted by using time-dependent density functional theory (TD-DFT) calculations. An absorption peak at 750 nm, assigned to the neutral radical with a proton loss from the 4(4') position of the β-carotene radical cation in Cu(II)-MCM-41, was also observed in photosystem II (PS II) samples using near-IR spectroscopy after illumination at 20 K. This peak was previously unassigned in PS II samples. The intensity of the absorption peak at 750 nm relative to the absorption of chlorophyll radical cations and β-carotene radical cations increased with increasing pH of the PS II sample, providing further evidence that the absorption peak is due to the deprotonation of the β-carotene radical cation. Based on a consideration of possible proton acceptors that are adjacent to β-carotene molecules in photosystem II, as modeled in the X-ray crystal structure of Guskov et al. Nat. Struct. Mol. Biol. 2009, 16, 334-342, an electron-transfer pathway from a β-carotene molecule with an adjacent proton acceptor to P680•+ is proposed.