New Transition Metal Oxo‐Thiostannate: Synthesis,Characterization, and Investigation of its Photocatalytic Properties

The new transition metal oxo‐thiostannate {[Ni(cyclen)]₆[Sn₆S₁₂O₂(OH)₆]} · 2(ClO₄) · 19H₂O ( 1 ) was prepared under hydrothermal conditions using Na₄SnS₄ · 14H₂O and [Ni(cyclen)](ClO₄)₂ as reactants. In the crystal structure the rare [Sn₆S₁₂O₂(OH)₆]^10– anion is observed, which is composed of SnS₂O(OH)₃ and SnS₄O₂ octahedra, and SnS₄ tetrahedra sharing edges and corners. The anion is expanded by six Ni²⁺ centered complexes via Ni–S and Ni–OH bonds. The photocatalytic properties for the visible light driven hydrogen evolution reaction shows that 26.6 mmol · g^–1 H₂ were evolved after 3 h.     

Hydrothermal syntheses, structures, and properties of [Cu3Cl2CN(pyrazine)] and copper(I) halide pyrazine polymers

Crystals of copper halide and pseudohalide compounds with pyrazine are synthesized under hydrothermal conditions. The title compound, [Cu3Cl2CNPz] (1) (Pz = pyrazine), is a new copper compound exhibiting an unusual -(Cu3Cl2)- polymeric stair structural motif and three-coordinate cyanide. Compound 1 crystallizes in the monoclinic space group P2(1)/m, with a = 3.6530(7) A, b = 17.160(3) A, c = 6.9800(14) A, beta = 90.58(3) degrees, and Z = 2. In addition, the series of complexes [Cu2X2Pz] for X = Cl (2), Br (3), and I (4) are also crystallized under hydrothermal conditions. The inorganic polymer [Cu2Br2Pz] (3) belongs to the triclinic space group P1, with a = 6.9671(14) A, b = 7.849(2) A, c = 8.099(2) A, alpha = 71.69(3) degrees, beta = 70.71(3) degrees, gamma = 85.43(3) degrees, and Z = 2. The structure of 3, is similar to the recently reported structure for [Cu2Cl2Pz] (2) (Kawata, S.; Kitagawa, S.; Kumagai, H.; Iwabuchi, S.; Katada, M. Inorg. Chim. Acta 1998, 267, 143). The third member of the series, [Cu2I2Pz], is found to be isostructural on the basis of X-ray powder diffraction results. The lattice parameters are refined from indexed reflections to a = 7.115(10) A, b = 8.321(19) A, c = 8.378(17) A, alpha = 71.1(3) degrees, beta = 67.3(1) degrees, and gamma = 83.0(2) degrees. Electronic spectra show that compounds 1-4 have optical band gaps in the range 2.2-2.4 eV. The infrared and Raman spectra as well as the thermal properties of all compounds are presented.     

Establishment of “one-piece” large-gel 2-DE for high-resolution analysis of small amounts of sample using difference gel electrophoresis saturation labelling

Large-gel two-dimensional gel electrophoresis (2-DE) is the method of choice for high-resolution proteome analysis of complex protein mixtures. Until now, however, the advantages of large 2-DE in combination with multiplexed fluorescence dye protein labelling has been complicated by the separate handling and analysis of the second-dimension gels. Therefore, we adapted the large 2-DE procedure allowing us to run “one-piece” large 2-DE gels (40 cm × 30 cm) in the second dimension for high resolution proteome analysis. Here, we show that in combination with fluorescence dye protein saturation labelling “one-piece” large 2-DE enables analysis of small amounts of sample (3 μg protein) for high-resolution proteome analysis.     

Directed Dehydration of Na4Sn2S6 ⋅ 5H2O Generates the New Compound Na4Sn2S6: Crystal Structure and Selected Properties

The new thiostannate Na₄Sn₂S₆ was prepared by directed crystal water removal from the hydrate Na₄Sn₂S₆ ⋅ 5H₂O at moderate temperatures. While the structure of the hydrate comprises isolated [Sn₂S₆]⁴⁻ anions, that of the anhydrate contains linear chains composed of corner-sharing SnS₄ tetrahedra, a structural motif not known in thiostannate chemistry. This structural rearrangement requires bond-breakage in the [Sn₂S₆]⁴⁻ anion, movements of the fragments of the opened [Sn₂S₆]⁴⁻ anion and Sn−S−Sn bond formation. Simultaneously, the coordination environment of the Na⁺ cations is significantly altered and the in situ formed NaS₅ polyhedra are joined by corner- and edge-sharing to form a six-membered ring. Time-dependent in situ X-ray powder diffraction evidences very fast rehydration into Na₄Sn₂S₆ ⋅ 5H₂O during storage in air atmosphere, but recovery of the initial crystallinity requires several days. Impedance spectroscopy demonstrates a mediocre room-temperature Na⁺ ion conductivity of 0.31 μS cm⁻¹ and an activation energy for ionic transport of E_a=0.75 eV.     

Iterative solution techniques for finite element applications

An iterative solver has been recently developed to solve very large systems of linear equations. The application of such a solver in commercial finite element software is not yet accepted. The purpose of the paper is to describe the new iterative solver and report on the practical application of this capability in different fields of interest.

The iterative solver uses the conjugate gradient method and employs two types of preconditioning: the traditional Jacobi and the incomplete Cholesky decomposition method. An option has been added for diagonal scaling to handle matrices whose entries greatly differ in magnitude. This paper illustrates the reduction possible in both central processor time and disk storage for problems with very large, well-conditioned matrices. Problems arising in electromagnetic analysis as well as in structural analysis have been solved with different options available in the iterative solver and compared with the standard, direct solver results. Guidelines on the use of the new solver and the status of research on even more efficient preconditioners are given.     

Ga掺杂ZnO的电子结构与电性能的研究

采用密度泛函理论广义梯度近似第一性原理计算的方法研究了n型Ga掺杂的纤锌矿结构氧化物ZnO的晶格结构、能带结构和态密度,在此基础上分析了其电性能.计算结果表明,掺杂ZnO氧化物晶格a,b轴增大,c轴略有减小;Ga掺杂ZnO氧化物两能带之间具有0.6eV的直接带隙,需要载流子(电子)跃迁的能隙宽度较未掺杂的ZnO氧化物减小;掺杂体系费米能级附近的态密度大大提高,其能带主要由Gas态、Zns态和Os态电子构成,且他们之间存在着强相互作用,其中Gas态电子对导带贡献最大.电输运性能分析结果表明,Ga掺杂ZnO氧化物导电机构由Znp-Op电子在价带与导带的跃迁转变为Gas-Znd-Os电子在价带与导带的跃迁,这也表明Gas态电子在导电过程中的重要作用;掺杂体系费米能级附近的载流子有效质量较未掺杂体系增大,且价带中的载流子有效质量较大,导带中的载流子有效质量较小.     

The mononuclear metal center of type-I dihydroorotase from aquifex aeolicus

Background

Dihydroorotase (DHO) is a zinc metalloenzyme, although the number of active site zinc ions has been controversial. E. coli DHO was initially thought to have a mononuclear metal center, but the subsequent X-ray structure clearly showed two zinc ions, α and β, at the catalytic site. Aquifex aeolicus DHO, is a dodecamer comprised of six DHO and six aspartate transcarbamoylase (ATC) subunits. The isolated DHO monomer, which lacks catalytic activity, has an intact α-site and conserved β-site ligands, but the geometry of the second metal binding site is completely disrupted. However, the putative β-site is restored when the complex with ATC is formed and DHO activity is regained. Nevertheless, the X-ray structure of the complex revealed a single zinc ion at the active site. The structure of DHO from the pathogenic organism, S. aureus showed that it also has a single active site metal ion.

Results

Zinc analysis showed that the enzyme has one zinc/DHO subunit and the addition of excess metal ion did not stimulate catalytic activity, nor alter the kinetic parameters. The metal free apoenzyme was inactive, but the full activity was restored upon the addition of one equivalent of Zn²⁺ or Co²⁺. Moreover, deletion of the β-site by replacing the His180 and His232 with alanine had no effect on catalysis in the presence or absence of excess zinc. The 2.2 Å structure of the double mutant confirmed that the β-site was eliminated but that the active site remained otherwise intact.

Conclusions

Thus, kinetically competent A. aeolicus DHO has a mononuclear metal center. In contrast, elimination of the putative second metal binding site in amidohydrolyases with a binuclear metal center, resulted in the abolition of catalytic activity. The number of active site metal ions may be a consideration in the design of inhibitors that selectively target either the mononuclear or binuclear enzymes.