2-三氰基乙烯基蒽及其旋转异构体的量子化学研究

用量子化学从头算方法 ,在RHF/STO - 3G水平上 ,对 2_三氰基乙烯基蒽 (2_TCVA)分子进行了理论计算 ,优化得到了它的平衡几何构型 ,并计算了它的谐振动频率 .结果表明 :2_TCVA存在两种旋转异构体 :2_TCVA(1)和 2_TCVA(2 ) ,2_TCVA(2 )的总能量比 2_TCVA(1)的略高 .在PM3/CIS水平上计算了它们的电子光谱 ,得到了由基态到各激发态的垂直跃迁能和相应的振子强度 .研究表明 :2_TCVA(1)和 2_TCVA(2 )的强度最大的吸收波长分别为 2 4 9.72nm和 2 89.4 1nm ,2_TCVA(2 )的强度最大的吸收波长比 2_TCVA(1)的要长 .计算结果与实验结果符合得较好     

Nonenzymatic Glucose Detection with Good Selectivity Against Ascorbic Acid on a Highly Porous Gold Electrode Subjected to Amalgamation Treatment

A nonenzymatic glucose sensor with good selectivity for the ascorbic acid oxidation is presented. After the gold polycrystalline electrode was subjected to amalgamation treatment, two advantageous effects were observed. One is the enhancement of the surface roughness and the other is an increase in the catalytic current in the glucose oxidation. Besides the known first effect, the latter provided another advantageous effect in a fabrication of nonenzymatic glucose sensor. Using a gold electrode subjected to amalgamation treatment for 60 s, two calibration curves for glucose oxidation at two different potentials of ?0.1 V and 0.25 V were obtained and compared. At the potential of ?0.1 V, at which no ascorbic acid was oxidized and no interference effect was observed, a current sensitivity of 16 μA cm^?2 mM^?1 from zero to 10 mM glucose concentration range was obtained. At the other potential of 0.25 V, at which ascorbic acid was easily oxidized, a satisfactory calibration curve with negligible ascorbic acid interference was also obtained together with a more enhanced current sensitivity of 32 μA cm^?2 mM^?1.     

Preparation of ω-tetrahydropyran-2-ylsulfanylalkylmagnesium chlorides: Useful reagents for the synthesis of 1-(ω-mercaptoalkyl)-1,2-dihydrobuckminsterfullerenes (C60)

ω-Tetrahydropyran-2-ylsulfanylalkylmagnesium chlorides are prepared as Grignard reagents containing protected mercaptoalkyl chains, which are useful for the direct introduction of ω-mercaptoalkyl chains to electrophiles. In order to prove the usefulness of these reagents, they were reacted with buckminsterfullerene (C₆₀) to give 1-(ω-mercaptoalkyl)-1,2-dihydrobuck minsterfullerenes after the deprotection of THP group with TFA.     

Recent Advances in Rare‐Earth Polypnictides

The polypnictide complexes of rare earth cations have drawn the attention of the scientific community for their uncommon bonding modes and potential applications. Herein, we present a systematic and comprehensive summary on recent advances in the field of rare earth polypnictides, focusing on their synthesis, structures, and reactivities. The structural stabilizing effects imposed by the electropositive rare earth cations as well as the reducing capability of rare earth precursors in the synthesis of these polypnictide complexes are described in this review. We also disscuss in detail the bonding interactions and coordination modes between rare earth cations and polypnictide clusters as well as the similarities and the peculiarity of some structures.     

从头计算方法比较TiSi_2的C54相和C49相

采用平面波超软赝势描述多电子体系,利用密度泛函理论和广义梯度近似,计算出C54相和C49相TiSi2的晶格常数、体弹性模量、形成能、电子态密度(DOS)和Mulliken电荷布居等性质.通过比较这两种物质的性质,发现尽管两者形成能很相近,但C49相结构对称性差、体弹性模量小、熔点低,Ti原子d轨道的反键强、离子性弱.这些性质上的差异和C49相TiSi2在固相反应中优先形成有关.     

分数导数结合傅里叶最小二乘拟合处理含噪音的重迭信号

提出了一种含噪音重迭信号的综合处理方法 :先用傅里叶最小二乘法拟合噪音数据 ,然后对拟合后的信号求 2 .5次导数 ,在对模拟数据研究的基础上 ,讨论了求导后峰位漂移及其影响因素 ,给出了一个用于矫正峰位值的经验公式。用该方法对模拟和实际的紫外含噪音重迭信号进行处理 ,结果良好     

Hydroxylation of nigranoic acid to 6β-hydroxynigranoic acid by Caryospora carllicarpa YMF1.01026

Microbial transformation of nigranoic acid by Caryospora carllicarpa YMF1.01026 afforded the new derivative 6β-hydro-xynigranoic acid. Its structure was elucidated by spectroscopic methods.     

TiO(2) porous electrodes with hierarchical branched inner channels for charge transport in viscous electrolytes.

Titanium dioxide (TiO(2)) photoelectrodes with micro/nano hierarchical branched inner channels have been prepared by an electrohydrodynamic (EHD) technique and assembled to form dye-sensitized solar cells (DSSCs). Excellent penetration of ionic-liquid electrolytes and enhanced light harvesting in the longer wavelength region are realized within the composite-structure electrode, thus a better fill factor (ff) of 75.3 % and higher conversion efficiency (eta) of 7.1 % are obtained for viscous ionic-liquid electrolytes compared to pure nanostructured films. Hierarchical branched channels in the photoanodes can efficiently improve the transport properties of redox-active species in viscous electrolytes, which is demonstrated by electrical impedance spectroscopy (EIS). The incident monochromatic photon-to-electron conversion efficiency (IPCE) shows that enhanced light scattering in the composite film is of benefit for light harvesting and thus for solar energy conversion efficiency.