Geometrical structures,electronic states,and stability of NinAl clusters

Density‐functional with generalized gradient approximation (GGA) for the exchange‐correlation potential has been used to calculate the energetically global‐minimum geometries and electronic states of Ni_nAl (n = 2–8) neutral clusters. Our calculations predict the existence of a number of previously unknown isomers. All structures may be derived from a substitution of a Ni atom at marginal positions by an Al atom in the Ni_n+1 cluster. Aluminum atom remains on the surface of the geometrical configurations. Moreover, these species prefer to adopt three‐dimensional (3D) spacial forms at the smaller number of nickel atoms compared with the pure Ni_n+1 (n ≥ 3) configuration. Atomization energies per atom for Ni_nAl (n = 2–8) have the same trend as the binding energies per atom for Ni_n (n = 3–9). The stabilization energies reveal that Ni₅Al is the relatively most stable in this series. In comparison with the magnetic moment of pure metal nickel (0.6 μ_B), the average magnetic moment of Ni atom increases in Ni Al clusters except the Ni₃Al. Moreover, except the case of Ni₅Al, Ni average magnetic moment decreases when alloyed with Al atoms than that in pure Ni clusters, which originate the effective charge transferring from Al to Ni atoms. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

A Blue Light-inducible Phosphodiesterase Activity in the Cyanobacterium Synechococcus elongatus

A blue light-inducible phosphodiesterase (PDE) activity, specific for the hydrolysis of cyclic di-GMP (c-di-GMP), has been identified in a recombinant protein from Synechococcus elongatus. Blue light (BL) activation is accomplished by a light, oxygen, voltage (LOV) domain, found in plant phototropins and bacterial BL photoreceptors. The genome of S. elongatus contains two genes coding for proteins with LOV domains fused to EAL domains (SL1 and SL2). In both cases, a GGDEF motif is placed in between the LOV and the EAL motifs. Such arrangement is frequently found with diguanylate-cyclase (DGC) functions that form c-di-GMP. Cyclic di-GMP acts as a second messenger molecule regulating biofilm formation in many microbial species. Both enzyme activities modulate the intracellular level of this second messenger, although in most proteins only one of the two enzyme functions is active. Both S. elongatus LOV-GGDEF-EAL proteins were expressed in full length or as truncated proteins. Only the SL2 protein, expressed as a LOV-GGDEF-EAL construct, showed an increase of PDE activity upon BL irradiation, demonstrating this activity for the first time in a LOV-domain protein. Addition of GTP or c-di-GMP did not affect the observed enzymatic activity. In none of the full-length or truncated proteins was a DGC activity detected.     

Characterization and thermal analysis of thiourea and bismuth trichloride complex

A complex of thiourea and bismuth trichloride has been synthesized. Its composition is Bi₃Cl₉[SC(NH₂)₂]₇. Crystallographic data are a = 7.141(2) Å, b = 8.820(3) Å, c = 16.365(5) Å, α = 99.389(4)°, β = 95.422(4)°, γ = 106.177(4)°, triclinic system. There are the mononuclear anion [BiCl₅SC(NH₂)₂]^2? and the dinuclear cation {Bi₂Cl₄[SC(NH₂)₂]₆}²⁺ with the Bi–Cl–Bi bridge bonds in the complex. The electric conductance of the absolute methanol solution contained the complex indicates that the complex is an ionic compound. Raman spectra indicate that the bismuth ion is coordinated by the sulfur atoms of the thiourea. The thermal analysis verifies the structure of complex. The TG–MASS curves show the structure rearrangement in the complex at about 118 °C. The DSC curves and calculation means that the structure rearrangement is irreversible.     

Simultaneous determination of uric acid and ascorbic acid at the film of chitosan incorporating cetylpyridine bromide modified glassy carbon electrode

A glassy carbon electrode (GCE) modified with the film composed of chitosan incorporating cetylpyridine bromide is constructed and used to determine uric acid (UA) and ascorbic acid (AA) by differential pulse voltammetry (DPV). This modified electrode shows efficient electrocatalytic activity and fairly selective separation for oxidation of AA and UA in mixture solution. UA is catalyzed by this modified electrode in phosphate buffer solution (pH 4.0) with a decrease of 80 mV, while AA is catalyzed with a decrease of 200 mV in overpotential compared to GCE, and the peak separation of oxidation between AA and UA is 260 mV, which is large enough to allow the determination of one in presence of the other. Under the optimum conditions, the anodic peak currents (I _pa) of DPV are proportional to the concentration of UA in the range of 2.0 × 10⁻⁶ to 6.0 × 10⁻⁴ M, with the detection limit of 5.0 × 10⁻⁷ M at a signal-to-noise ratio of 3 (S/N = 3) and to that of AA in the range of 4.0 × 10⁻⁶ to 1.0 × 10⁻³ M, with the detection limit of 8.0 × 10⁻⁷ M (S/N = 3).     

分子模拟用于尤文肉瘤EWS-FLI1蛋白HLA-A2.1限制性CTL表位的筛选

为获得尤文肉瘤EWS-FLI1融合蛋白有效的HLA-A2.1限制性CTL表位, 综合运用BIMAS, SYFPEITHI, Predep和IEDB方案对EWS-FLI1进行CTL表位的预测, 得出8个CTL表位9肽序列; 应用多项式方案、量化基序方案对8个表位9肽进一步进行筛选, 获得其中4个9肽序列, 并进一步运用分子模拟方法初步模拟了4个表位肽与HLA-A2.1分子间的相互结合作用; 应用标准Fmoc方案合成CTL表位肽, RP-HPLC与MS分别鉴定合成肽的纯度与分子量; 通过亲和力实验验证了表位肽QIQLWQFLL_{(EWS-FLI1 304)}与HLA-A2.1有较强的结合力, 从而为表位肽的后继免疫学特性研究提供了基础. 本研究提供了一个合理高效的表位筛选方法.     

Low-temperature Heat Capacities and Thermodynamic Properties of the Solid State Complexes(C2H10N2)MCl4(s)(M=Cu and Cd)

The tetrachlorocuprate(II) ethylenediammonium and tetrachlorocadmate(II) ethylenediammonium were synthesized. Chemical analysis, elemental analysis, and X‐ray crystallography were applied to characterize the compositions and crystal structures of the two complexes. The lattice potential energies and the radiuses of the anions of two complexes were calculated to be U_POT[(C₂H₁₀N₂)CuCl₄]=1810.19 kJ·mol^?1, U_POT[(C₂H₁₀N₂)CdCl₄]=1784.39 kJ·mol^?1, r[(CuCl₄)^2?]=0.308 nm, and r[(CdCl₄)^2?]=0.321 nm from the data of the crystal structure, respectively. Low‐temperature heat capacities of the two complexes were measured by a precision automatic adiabatic calorimeter with the small sample over the temperature range from 78 to 400 K, respectively. Two polynomial equations of heat capacities against the temperatures were fitted by least square method: C_p,_m[(C₂H₁₀N₂)CuCl₄, s] =213.553+118.578X?5.816X²+4.392X³+0.276X⁴ and C_p,_m[(C₂H₁₀N₂)CdCl₄, s] =190.927+98.501X?7.931X²+0.657X³+3.834X⁴, in which X= (T?239)/161. Based on the fitted polynomial equations, the smoothed heat capacities and thermodynamic functions of the two complexes relative to the standard reference temperature 298.15 K were calculated at intervals of 5 K.     

Novel Method for Preparing NH4NiPO4·6H2O: Hydrogen Bonding Coacervate Selective Self-assembly

The single phase NH₄NiPO₄·6H₂O was synthesized by solid‐state reaction at room temperature using NiSO₄·6H₂O and (NH₄)₃PO₄·3H₂O as raw materials. The NH₄NiPO₄·6H₂O and its calcined products were characterized using X‐ray powder diffraction (XRD), thermogravimetry and differential thermal analyses (TG/DTA), Fourier transform IR (FT‐IR), ultraviolet‐visible (UV‐vis) absorption spectroscopy, and scanning electron microscopy (SEM). The results showed that the product dried at 80°C for 3 h was orthorhombic NH₄NiPO₄·6H₂O [space group Pmm2(25)], and surfactant polyethylene glycol (PEG)‐400 can direct growth of crystal NH₄NiPO₄·6H₂O. The thermal process of NH₄NiPO₄·6H₂O experienced three steps, which involve the dehydration of the five crystal water molecules at first, and then deamination, dehydration of the one crystal water, intramolecular dehydration of the protonated phosphate groups together, at last crystallization of Ni₂P₂O₇. The product of thermal decomposition at 150°C for 2 h, orthorhombic NH₄NiPO₄·H₂O, is layered compound with an interlayer distance of 0.8370 nm.     

Enhancement of Lovastatin Production by Supplementing Polyketide Antibiotics to the Submerged Culture of <Emphasis Type="Italic">Aspergillus terreus</Emphasis>

Feedback inhibition existed in lovastatin biosynthesis from Aspergillus terreus. Exogenous lovastatin and other different polyketide antibiotics biosynthesized by polyketide synthase were supplemented to the cultures of A. terreus to investigate their influences on lovastatin production. Supplementing exogenous lovastatin of 100 mg l⁻¹ at the early stage of fermentation and the fast stage of its biosynthesis resulted in decreases of 76.4% and 20% in final lovastatin production, respectively. However, the fungal cell growth was not affected; the growing cycle was only prolonged in the submerged cultivation. Separate supplementation of the five kinds of polyketide antibiotics such as tylosin, erythromycin, tetracycline, daunorobin, and rifamycin to the cultures resulted in increases of about 20~25% in the final lovastatin production. Especially, supplementing tylosin of 50 mg l⁻¹ at the beginning of lovastatin biosynthesis led to the final lovastatin production of 952.7 ± 24.3 mg l⁻¹, which was improved by 42% and 22% compared with that produced in the control and the original culture, respectively. These results are helpful to understand the regulations on lovastatin biosynthesis and improve the final desired metabolite contents in many antibiotics production.     

Hydrothermal synthesis of (Fe,N) co-doped TiO<Subscript>2</Subscript> powders and their photocatalytic properties under visible light irradiation

(Fe, N) co-doped titanium dioxide powders have been prepared by a quick, low-temperature hydrothermal method using TiOSO₄, CO(NH₂)₂, Fe(NO₃)₃, and CN₃H₅ · HCl as starting materials. The synthesized powders were characterized by XRD, TEM, BET, XPS, and UV–Vis spectroscopy. Experimental results show that the as-synthesized TiO₂ powders are present as the anatase phase and that the N and Fe ions have been doped into the TiO₂ lattice. The specific surface area of the powders is 167.8 m²/g by the BET method and the mean grain size is about 11 nm, calculated by Scherrer’s formula. UV–Vis absorption spectra show that the edge of the photon absorption has been red-shifted up to 605 nm. The doped titanium dioxide powders had excellent photocatalytic activity during the process of photo-degradation of formaldehyde and some TVOC gases under visible light irradiation.     

制备方法对Ce0.5Zr0.5O2固溶体微观晶相结构及还原性能影响的研究

采用不同合成方法制备了4种组成为Ce0.5Zr0.5O2的铈锆固溶体.通过XRD,BET,H2-TPR,HREM以及SEAD等表征手段,研究了微观晶相结构对铈锆固溶体还原性能的影响规律,以及对固溶体储放氧能力的影响.分析结果表明,在同一组成下,不同制备方法得到截然不同的晶相组成,4种固溶体包含4种不同的晶相组合.通过对微观晶相结构的定量分析,发现立方相的形成对促进固溶体的还原性能起到重要作用.其中,反相微乳法制得的铈锆固溶体能够形成完整的立方相结构,在H2-TPR还原过程中耗氢量最大,表明其具有优良的可还原性及储放氧能力,适合作为TWC,POX等催化剂载体.