| 1. |
- Mondal, Swastik, et al.
(författare)
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Electron-Deficient and Polycenter Bonds in the High-Pressure gamma-B-28 Phase of Boron
- 2011
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Ingår i: PHYSICAL REVIEW LETTERS. - : American Physical Society. - 0031-9007. ; 106:21, s. 215502-
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Tidskriftsartikel (refereegranskat)abstract
- The peculiar bonding situation in gamma boron is characterized on the basis of an experimental electron-density distribution which is obtained by multipole refinement against low-temperature single-crystal x-ray diffraction data. A topological analysis of the electron-density distribution reveals one-electron-two-center bonds connecting neighboring icosahedral B-12 clusters. A unique polar-covalent two-electron-three-center bond between a pair of atoms of an icosahedral cluster and one atom of the interstitial B-2 dumbbell explains the observed charge separation in this high-pressure high-temperature polymorph of boron.
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| 2. |
- Nikitina, Julia, et al.
(författare)
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Importance of a single disulfide bond for the PsbO protein of photosystem II : protein structure stability and soluble overexpression in Escherichia coli.
- 2008
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Ingår i: Photosynthesis Research. - : Springer Science and Business Media LLC. - 0166-8595 .- 1573-5079. ; 98, s. 391-403
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Tidskriftsartikel (refereegranskat)abstract
- PsbO protein is an important constituent of the water–oxidizing complex, located on the lumenal side of photosystem II. We report here the efficient expression of the spinach PsbO in E. coli where the solubility depends entirely on the formation of the disulfide bond. The PsbO protein purified from a pET32 system that includes thioredoxin fusion is properly folded and functionally active. Urea unfolding experiments imply that the reduction of the single disulfide bridge decreases stability of the protein. Analysis of inter-residue contact density through the PsbO molecule shows that Cys51 is located in a cluster with high contact density. Reduction of the Cys28–Cys51 bond is proposed to perturb the packing interactions in this cluster and destabilize the protein as a whole. Taken together, our results give evidence that PsbO exists in solution as a compact highly ordered structure, provided that the disulfide bridge is not reduced.
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| 3. |
- Shutova, Tatiana, 1964-, et al.
(författare)
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The photosystem II-associated Cah3 in Chlamydomonas enhances the O-2 evolution rate by proton removal
- 2008
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Ingår i: EMBO Journal. - : Wiley. - 0261-4189 .- 1460-2075. ; 27:5, s. 782-791
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Tidskriftsartikel (refereegranskat)abstract
- Water oxidation in photosystem II ( PSII) is still insufficiently understood and is assumed to involve HCO3-. A Chlamydomonas mutant lacking a carbonic anhydrase associated with the PSII donor side shows impaired O-2 evolution in the absence of HCO3-. The O-2 evolution for saturating, continuous illumination (R-O2) was slower than in the wild type, but was elevated by HCO3- and increased further by Cah3. The R-O2 limitation in the absence of Cah3/HCO3- was amplified by H2O/D2O exchange, but relieved by an amphiphilic proton carrier, suggesting a role of Cah3/HCO3- in proton translocation. Chlorophyll fluorescence indicates a Cah3/HCO3- effect at the donor side of PSII. Time-resolved delayed fluorescence and O-2-release measurements suggest specific effects on proton-release steps but not on electron transfer. We propose that Cah3 promotes proton removal from the Mn complex by locally providing HCO3-, which may function as proton carrier. Without Cah3, proton removal could become rate limiting during O-2 formation and thus, limit water oxidation under high light. Our results underlie the general importance of proton release at the donor side of PSII during water oxidation.
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| 4. |
- Zarechnaya, E Yu, et al.
(författare)
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Superhard Semiconducting Optically Transparent High Pressure Phase of Boron
- 2009
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Ingår i: PHYSICAL REVIEW LETTERS. - 0031-9007. ; 102:18, s. 185501-
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Tidskriftsartikel (refereegranskat)abstract
- An orthorhombic (space group Pnnm) boron phase was synthesized at pressures above 9 GPa and high temperature, and it was demonstrated to be stable at least up to 30 GPa. The structure, determined by single-crystal x-ray diffraction, consists of B-12 icosahedra and B-2 dumbbells. The charge density distribution obtained from experimental data and ab initio calculations suggests covalent chemical bonding in this phase. Strong covalent interatomic interactions explain the low compressibility value (bulk modulus is K-300=227 GPa) and high hardness of high-pressure boron (Vickers hardness H-V=58 GPa), after diamond the second hardest elemental material.
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