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981.
Electronic structures and spectroscopic properties of the binuclear head-to-tail [Au(2)(PH(2)CH(2)SH)(2)](2+) (1) complex were investigated by ab initio calculations. The solvent effect of the complex in the acetonitrile solution was taken into account by the weakly solvated [Au(2)(PH(2)CH(2)SH)(2)](2+).(MeCN)(2) (2) moiety in the calculations. The ground-state geometries of 1 and 2 were fully optimized by the MP2 method, while their excited-state structures were optimized by the CIS method. Aurophilic attraction apparently exists between the two Au(I) atoms in the ground state and is strongly enhanced in the excited state. A high-energy phosphorescent emission was calculated at 337 nm for 1 in the absence of the interactions with solvent molecules and/or counteranion in solid state; however the lowest-energy emission of 2 was obtained at 614 nm with the nature of (3)A(u)(s(sigma)) --> (1)A(g)(d(sigma)) (metal-centered, MC) transition. The coordination of acetonitrile to the gold atom in solution results in a dramatic red shift of emission wavelength. The investigations on the head-to-tail [Au(2)(PH(2)CH(2)SCH(3))(2)](2+) (5) and [Au(2)(PH(2)CH(2)SCH(3))(2)](2+).(MeCN)(2) (6) moieties indicate that the CH(3) substituent on the S atom causes blue shifts of emission wavelength for 5 and 6 with respect to 1 and 2. By comparison between Au(I) thioether 1 and head-to-tail Au(I) thiolate [Au(2)(PH(2)CH(2)S)(2)] (7), it is concluded that the S-->Au dative bonding results in evidently different transition characteristics from the S-Au covalent bonding in the Au(I) thioether/thiolate complexes. 相似文献
982.
六氰合铁酸铜钴在蜡浸石墨电极表面的电化学沉积 总被引:3,自引:0,他引:3
首次报道了电化学沉积的混合金属六氰合铁酸盐修饰电极作为电流型传感器的研究。针对六氰合铁酸盐修饰电极在中性和碱性条件下的不稳定性,采用混合金属电沉积的方法,成功地提高了电极的稳定性,所得到的修饰电极在 pH 4~10之间均表现出良好的稳定性。该电极的响应时间(t95%)为 0.5s,并对Fe3+/Fe2+电对表现出良好的电催化作用。催化氧化峰电流与Fe2+的浓度在1.0×10-4~6.5×10-2mol/L范围内呈很好的线性关系,检测下限为 1.4×10-6mol/L。 相似文献
983.
Zhang L Mattern RH Malaney TI Pierschbacher MD Goodman M 《Journal of the American Chemical Society》2002,124(12):2862-2863
We report the results of (15)N-edited 2D transferred NOE experiments of the partially (15)N-labeled alpha(5)beta(1) antagonist c[Mpa(15)N-Arg-(15)N-Gly-(15)N-Asp-(15)N-Asp-(15)N-Val-Cys]-NH(2) (Mpa denotes mercaptopropionic acid) in the presence of the native alpha(5)beta(1) receptor. The alpha(5)beta(1) integrin receptor is believed to be involved in tumor metastasis and the rational design of alpha(5)beta(1) integrin antagonist is therefore of considerable interest. Our experiments provide insight into the alpha(5)beta(1) receptor-bound conformation of the antagonist c[MpaRGDDVC]-NH2 and will be important for the design of novel antagonists. 相似文献
984.
Single nucleotide polymorphisms (SNPs) are currently being mapped and databased at a remarkable pace, providing a viable means for understanding disease susceptibility, differential drug response and human evolution. Consequently, there is an increasing demand for SNP genotyping technologies that are simple, rapid, cost effective and readily amenable to automation for high-throughput analyses. In this study, we improved the Survivor Assay, a SNP detection method based on electrospray ionization mass spectrometry (ESI-MS), with several developments. One improvement is the development of a one-well assay, requiring no off-line purification of the polymerase chain reaction product, achieved by simple addition of reagent solution into a single well. Another is the on-line separation of magnesium and dideoxynucleotides using an in-house made monolithic metal chelating column, eliminating any off-line sample preparation prior to mass spectrometric analysis. Here the Survivor Assay is extended from a proof-of-principle concept to a validated method by genotyping six SNPs from five different regions of human genomic DNA in 55 individual samples with 100% accuracy. This improved Survivor Assay eliminates the tedious and time-consuming steps of sample preparation, minimizes sample handing and offers a high-throughput analysis of SNPs by ESI-MS. The current combined preparation and analysis time is 2 min per sample. The simplicity of this method has potential for full automation and parallel chromatography and, thus, reduced analysis time. In addition, we have adapted the Survivor Assay for quantitative SNP analysis in pooled DNA samples. The capabilities and sensitivity of this approach were evaluated. We demonstrate that an allele occurring at a frequency of 2% can consistently be quantitated. 相似文献
985.
在SmI_2-HMPA-THF-t-BuOH体系中,硫代碳酸酯的酰硫键发生还原断裂反应,得到相应的二硫醚产物。 相似文献
986.
A novel method of synthesizing protein chiral stationary phase (protein-CSP) is proposed with 2,4,6-trichloro-1,3,5-triazine as the activator. The bovine serum albumin (BSA) based chiral columns (150 x 4.6 mm I.D.) were prepared successfully within 8 h. With tryptophan as the probe solute, it was observed that the BSA immobilized by this method had a better ability to distinguish enantiomers than that activated by glutaric dialdehyde. This may be due to the well-maintained BSA conformation and the larger amount of BSA immobilized on the silica gel. The BSA-CSP prepared by this method was relatively stable under experimental conditions, and the resolution of 13 chiral compounds was achieved. The coupling reaction in this method is mild, reliable and reproducible; it is also suitable for the immobilization of various biopolymers in the preparation of bioreactor, biosensor and affinity chromatography columns. 相似文献
987.
988.
Shaobin Miao Zhan Yu Qian-Feng Zhang Yinglin Song Alexander Rothenberger Wa-Hung Leung 《Journal of Cluster Science》2006,17(3):495-507
Two isostructural crown-like heteroselenometallic cluster compounds, [Et4N]4[(μ5-WSe4)(CuX)5(μ-X)2] (X = Cl 1, Br 2), were prepared from the reactions of [Et4N]2[WSe4] with CuX and [Et4N]X· xH2O in the presence of 2-picoline and characterized by single-crystal diffraction analysis. The [(μ5-WSe4)(Cu-X)5(μ-X)2]4− anions in the cluster compounds consists of five CuX fragments coordinated to the five edges of the tetrahedral [WSe4]2− moiety along with two bridging halides connected to each of the two pairs of the symmetric copper atoms, exhibiting a novel
crown-like core structure. The nonlinear optical absorption and refraction of cluster compound 2 were determined to be α2 = 6.15 × 10−10 m/W and n
2 = 4.18 × 10−11 esu, respectively. 相似文献
989.
Xinbo Zhang Danzi Sun Wenya Yin Yujun Chai Minshou Zhao 《Journal of Solid State Electrochemistry》2006,10(4):236-242
This paper presents results concerning structure and electrochemical characteristics of the La0.67Mg0.33 (Ni0.8Co0.1Mn0.1)
x
(x=2.5–5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously
with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5–3.5 is LaMg2Ni9 phase with a PuNi3-type rhombohedral structure, but the main phase of the alloys with x=4.0–5.0 is LaNi5phase with a CaCu5-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg2Ni9phase and the LaNi5 phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g
(x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I
0) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability
of the alloy electrodes. 相似文献
990.