Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å

Photosystem II is the site of photosynthetic water oxidation and contains 20 subunits with a total molecular mass of 350 kDa. The structure of photosystem II has been reported at resolutions from 3.8 to 2.9 angstrom. These resolutions have provided much information on the arrangement of protein subunits and cofactors but are insufficient to reveal the detailed structure of the catalytic centre of water splitting. Here we report the crystal structure of photosystem II at a resolution of 1.9 angstrom. From our electron density map, we located all of the metal atoms of the Mn(4)CaO(5) cluster, together with all of their ligands. We found that five oxygen atoms served as oxo bridges linking the five metal atoms, and that four water molecules were bound to the Mn(4)CaO(5) cluster; some of them may therefore serve as substrates for dioxygen formation. We identified more than 1,300 water molecules in each photosystem II monomer. Some of them formed extensive hydrogen-bonding networks that may serve as channels for protons, water or oxygen molecules. The determination of the high-resolution structure of photosystem II will allow us to analyse and understand its functions in great detail

Resonant inelastic X-ray scattering (RIXS) spectroscopy at the MnK absorption pre-edge - a direct probe of the 3d orbitals

A study of the Mn K absorption pre-edges in oxides using resonant inelastic X-ray scattering (RIXS) spectroscopy is presented. The energy transfer dimension enhances the separation of the pre-edge (predominantly 1s to 3d transitions) from the main K-edge and a detailed analysis is thus possible. The RIXS spectra are sensitive to the Mn spin state. The technique thus yields detailed information on the electronic structure that is not accessible in conventional K-edge absorption spectroscopy. The line splittings can be understood within a ligand field multiplet model, showing the importance of (2p,3d) two-electron interactions that give rise to the spin-sensitivity. (c) 2005 Elsevier Ltd. All rights reserved

Resonant inelastic X-ray scattering (RIXS) spectroscopy at the MnK absorption pre-edge - a direct probe of the 3d orbitals

A study of the Mn K absorption pre-edges in oxides using resonant inelastic X-ray scattering (RIXS) spectroscopy is presented. The energy transfer dimension enhances the separation of the pre-edge (predominantly 1s to 3d transitions) from the main K-edge and a detailed analysis is thus possible. The RIXS spectra are sensitive to the Mn spin state. The technique thus yields detailed information on the electronic structure that is not accessible in conventional K-edge absorption spectroscopy. The line splittings can be understood within a ligand field multiplet model, showing the importance of (2p,3d) two-electron interactions that give rise to the spin-sensitivity. (c) 2005 Elsevier Ltd. All rights reserved

The electronic structure of Mn in oxides, coordination complexes, and the oxygen-evolving complex of photosystem II studied by resonant inelastic X-ray scattering

Resonant inelastic X-ray scattering (RIXS) was used to collect Mn K pre-edge spectra and to study the electronic structure in oxides, molecular coordination complexes, as well as the S-1 and S-2 states of the oxygen-evolving complex (OEC) of photosystem II (PS II). The RIXS data yield two-dimensional plots that can be interpreted along the incident (absorption) energy or the energy transfer axis. The second energy dimension separates the pre-edge (predominantly 1s to 3d transitions) from the main K-edge, and a detailed analysis is thus possible. The 1s2p RIXS final-state electron configuration along the energy transfer axis is identical to conventional L-edge absorption spectroscopy, and the RIXS spectra are therefore sensitive to the Mn spin state. This new technique thus yields information on the electronic structure that is not accessible in conventional K-edge absorption spectroscopy. The line splittings can be understood within a ligand field multiplet model, i.e., (3d,3d) and (2p,3d) two-electron interactions are crucial to describe the spectral shapes in all systems. We propose to explain the shift of the K pre-edge absorption energy upon Mn oxidation in terms of the effective number of 3d electrons (fractional 3d orbital population). The spectral changes in the Mn 1s2p(3/2) RIXS spectra between the PS II S, and S2 states are small compared to that of the oxides and two of the coordination complexes (Mn-III(acac)(3) and Mn-IV(sal)(2)(bipy)). We conclude that the electron in the step from S-1 to S-2 is transferred from a strongly delocalized orbital

Diel behaviour and trophic ecology of Scolopsis bilineatus (Nemipteridae)

Nemipterids are ubiquitous mid-sized fishes on Indo-Pacific reefs. We investigated the trophic ecology of the nemipterid species Scolopsis bilineatus at two locations on the Great Barrier Reef: One Tree Island and Orpheus Island. Fish ate a variety of benthic invertebrate taxa represented by rank: polychaetes, ophuiroids, sipunculids, nemerteans and small crustaceans. Polychaetes dominated the diet of fish of all sizes. Feeding behaviour and habitat utilization varied with the size of fish. Juveniles fed diurnally and adults nocturnally. Most juveniles fed rapidly in sand and rubble habitat during the day. In contrast, adults occupied shelter sites during the day, but dispersed onto sand to feed at night. A manipulative experiment demonstrated that small adult S. bilineatus exhibit opportunistic behaviour by responding to disturbance of the substratum for the purposes of feeding. Diurnal opportunistic feeding probably has a minimal influence on overall dietary intake. Identification of nocturnal feeding for adult S. bilineatus is of significant ecological importance, as nocturnal fishes often play unique and important roles in energy and nutrient cycling on reefs