Kinetic investigation on carbamate formation from the reaction of carbon dioxide with amino acids in homogeneous aqueous solution

The kinetics of carbamate formation from the reaction of carbon dioxide with α‐amino acids in D₂O was first investigated by means of nuclear magnetic resonance spectroscopy. Potassium carbonate was used as the CO₂ source. For each amino acid, the maximum carbamate yield, the apparent rate constant for the carbamate formation k_app, and the rate constants for the formation k₁ and the breakdown k_?1 of the carbamate were estimated. Plots of log k₁ or log k_?1 versus pK_a of amino acids indicated that the formation rate k₁ increased with the basicity (pK_a) of amino acid, while the decomposition rate k_?1 decreased. A Br?nsted β value of 0.39 was obtained from the former plot, being in good agreement with the previously reported ones (0.26–0.43). The observed negative pK_a dependence of log k_?1 (Br?nsted α = 0.34) is reasonable, because the carbamate decomposition is acid‐catalyzed and the steady‐state concentration of H⁺ should be higher for weaker basic amines. The charge (σ) and the lone‐pair energy (E_N) at the nitrogen atom of the amino group were calculated. Although log k₁ correlated with σ and E_N, log k_?1 was unrelated with both of these parameters. Considering that the carbamate formation (k₁) is not only base‐catalyzed but should also be promoted by the nucleophilicity of the amino nitrogen, its correlation with σ and E_N in addition to pK_a is rational. The irrelevance of log k_?1 to σ and E_N is not surprising, because σ and E_N are not a direct measure of [H⁺] of the solution. Copyright © 2011 John Wiley & Sons, Ltd.     

Ag‐doped TiO2 enhanced photocatalytic oxidation of 1,2‐cyclohexanediol

The superiority of silver‐doped titania for photocatalytic oxidation (PCO) of organic compounds inspired us to investigate PCO of 1,2‐cyclohexanediol. Ag/TiO₂ was prepared, characterized (nanosize 19–24 nm) and used for oxidation of 1,2‐cyclohexanediol (1) in acetonitrile. The photolysate was analyzed using GC and GC/MS techniques. The PCO products are 2‐hydroxylcyclohexanone (2), 1,2‐cyclohexandione (3), 2‐cyclohexenone(4), cyclohexanone (5), and adipic acid (6).The formation of electron–hole pair at the surface of the catalyst followed by oxidation reactions was the suggested mechanism. Kinetic studies revealed first‐order mechanism for PCO of 1 and rate constant (k) = ?0.145 h^–1. Copyright © 2012 John Wiley & Sons, Ltd.     

Studies of structural and electrical properties on four-layers Aurivillius phase BaBi4Ti4O15

BaBi₄Ti₄O₁₅ (BBT) ceramic was synthesized using mixed oxide route and the structural and electrical properties were investigated systematically. The structural studies confirmed it to be an n=4 member of the Aurivillius oxide. A broad dielectric peak with frequency dependent dielectric maximum temperature was observed. The dielectric relaxation obeyed the Vogel–Fulcher relation wherein f₀=8.37E+14 Hz, E_a=0.13 eV, and T_f=608.18 K. The diffuseness parameter γ established the relaxor nature and it was attributed to the A-site cationic disorder. The specimen exhibited the excellent reproducibility in the measurements of displacement current, a remnant polarization of 5.4 μC/cm², and a coercive field of 4.03 MV/m. The room temperature piezoelectric coefficient d₃₃ was found to be 23 pC/N and the field-induced strain S was about 0.018% at the 8 MV/m electric field.     

萃取—火焰原子吸收法测定骨骼中的微量元素Cu,Zn,Cd和Fe

本文研究了以邻菲罗啉为金属螯合剂，高氯酸钠为配体，在一定酸度下用１，２－二氯乙烷萃取－火焰原子吸收法测定动物骨骼中微量Ｃｕ，Ｚｎ，Ｃｄ和Ｆｅ的条件，并确定了测定方法，方法简单，准确，可靠，元素的检测限分别为：Ｃｕ：０．０３８μｇ／ｍｌ，Ｚｎ：０．００４２μｇ／ｍｌ，Ｃｄ：０．００１９μｇ／ｍｌ，Ｆｅ：０．０２μｇ／ｍｌ，回收率在９２．８％～１０５％之间。     

ZnCdTe-ZnTe多量子阱的电场效应

本文报导了电场作用下ZnCdTe-ZnTe多量子阱的激子发光特性.用激子局域化的观点解释了激子发光峰随电场增强而增强的现象.在Zn0.8Cd0.2Te-ZnTe多量子阱中观察到了电场作用下自由激子发光谱峰较大的红移和较快的发光淬灭     

激光干涉法测压电陶瓷的压电常数d31

介绍迈克尔逊干涉仪原理在测微小位移中的应用。确定一种锆钛酸铅镧压电陶瓷的压电常数ｄ３１，得到了一种测ｄ３１的可行可靠的新方法。     

激发双参数变形奇偶相干态的压缩特性

研究了激发奇qs相干态a+mqsα〉oqs和激发偶qs相干态a+mqsα〉eqs的压缩特性,数值计算了参数m,s和q对qs压缩函数的影响.结果表明:(1)当q或s偏离1较远时,态a+mqsα〉oqs和a+mqsα〉eqs都能呈现出强烈的qs压缩,而且随着r²的增大qs压缩函数出现振幅和周期都递增的振荡现象,其振幅不但随q或s的减小而急剧增大,而且也随着m的增大而急剧增大,其周期随q或s的减小而增大但与m无关,从控制光场的压缩效应来看,场模上光子数增加数m可作为第三个独立的调节参数来使用;(2)对于大多数r,qs压缩函数对s的敏感度大于对q的敏感度,即通过调节参数s来控制光场的压缩效应要比通过调节参数q更有效.     

Annealing effects on structure and laser-induced damage threshold of Ta2O5/SiO2 dielectric mirrors

The effects of annealing on structure and laser-induced damage threshold (LIDT) of Ta₂O₅/SiO₂ dielectric mirrors were investigated. Ta₂O₅/SiO₂ multilayer was prepared by ion beam sputtering (IBS), then annealed in air under the temperature from 100 to 400 °C. Microstructure of the samples was characterized by X-ray diffraction (XRD). Absorption of the multilayer was measured by surface thermal lensing (STL) technique. The laser-induced damage threshold was assessed using 1064 nm free pulsed laser at a pulse length of 220 μs.

It was found that the center wavelength shifted to long wavelength gradually as the annealing temperature increased, and kept its non-crystalline structure even after annealing. The absorbance of the reflectors decreased after annealing. A remarkable increase of the laser-induced damage threshold was found when the annealing temperature was above 250 °C.     

On the interaction between dislocations and cracks in one-dimensional hexagonal quasi-crystals

The solution of elasticity problems involving the interaction between dislocations and cracks plays a fundamental role in many practical and theoretical applications. Although elasticity problems involving dislocation or cracks in quasi-crystals have been investigated in many papers, the analysis is limited to a single defect. This paper investigates the interaction of defects in one-dimensional hexagonal quasi-crystals using the complex variable function method. The interaction force between two parallel dislocations is presented and the analytic solutions of elastic fields of interaction between a dislocation and a crack are obtained. A version of the well-known Peach－Koehler formula in one-dimensional hexagonal quasi-crystals is given.     

光学多普勒层析三维矢量测速方法研究

光学多普勒层析术(ODT)是一种高分辨、非侵入的生物医学成像手段,能同时得到组织的结构信息和组织内血管的流速信息.提出了一种新型的基于相位分辨技术的ODT三维矢量测速方法.在ODT系统样品臂的准直镜和聚焦透镜之间加入窄带相位片,形成三个不同的相位延迟,通过计算多普勒频移和不同相位延迟下的多普勒展宽,可得到毛细管内的三维矢量流场分布.对已知浓度的聚苯乙烯溶液进行了一系列不同角度和不同流速的实验,结果证明这种新型的ODT矢量测速方法可以较精确的实现三维矢量流速的测量.