Mechanism and kinetics of thermal decomposition of precipitates of the zinc oxide-aluminium oxide system from non-isothermal tg curves

Kinetics of decomposition of the precipitates of the ZnO&2sbndAl₂O₃ system, prepared by coprecipitation and mechanical mixing of the individual precipitates, have been studied. The decomposition of zinc basic carbonate is a first order rate process with an activation energy of 34.5 kcal/mole (Coats and Redfern equation). The decomposition of aluminium hydroxide is also best described as a first order rate process with one break in the Coats and Redfern plot corresponding to activation energies of 29.4 and 8.3 kcal/mole respectively. The entire course of decomposition of coprecipitated as well as mechanically mixed samples cannot be described by any one of the many rate equations available. Consequently, the Coats and Redfern equation has been employed. The plots indicate one or two breaks and thus two to three values of activation energy are reported. From the results it is to be concluded that decomposition of these precipitates is a heterogeneous process. The first step is definitely the decomposition of zinc basic carbonate followed by decomposition of aluminium hydroxide and/or interaction of the two precipitates resulting in the formation of “precursor” to spinel. The results of our earlier investigation on the same system (especially the formation of precursors) are well supported by the results reported in this investigation. p]A new equation (a modified form of the Elovich equation) has been proposed for such heterogeneous decomposition processes. The proposed equation also appears to be the general form of the equations where diffusion is the rate controlling process.     

Facile Synthesis of Porous Ag Crystals as SERS Sensor for Detection of Five Methamphetamine Analogs

Porous noble metal nanomaterials have attracted extensive attention due to their high specific surface area and surface plasmon resonance effect. However, it is difficult to form porous structures due to the high mobility and low reduction potential of noble metal precursors. In this article, we developed a facile method for preparing porous Ag with a controllable structure at room temperature. Two kinds of Ag crystals with different porous structures were successfully prepared by using AgCl cubes as sacrificial templates. Through the galvanic replacement reaction of Zn and AgCl, Ag crystals with a sponge-like porous structure were successfully prepared. Additionally, using NaBH₄ as the reducing agent, we prepared granular porous Ag cubes by optimizing the amount of reducing agent. Both the sponge-like and granular porous Ag cubes have clean and accessible surfaces. In addition, we used the prepared two porous Ag cubes as substrate materials for SERS detection of five kinds of methamphetamine analogs. The experimental results show that the enhancement effect of granular porous Ag is better than that of sponge-like porous Ag. Furthermore, we probed the hot spot distribution of granular porous Ag by Raman mapping. By using granular porous Ag as the substrate material, we have achieved trace detection of 5 kinds of methamphetamine analogs including Ephedrine, Amphetamine, N-Methyl-1-(benzofuran-5-yl)propan-2-amine (5-MAPB), N-Methyl-1-(4-methoxyphenyl)propan-2-amine (PMMA) and N-Methyl-1-(4-fluorophenyl)propan-2-amine (4-FMA). Furthermore, to achieve qualitative differentiation of analogs with similar structures we performed density functional theoretical (DFT) calculations on the Raman spectra of the above analogs. The DFT calculations provided the vibrational frequencies, Raman activities, and normal mode assignment for each analog, enabling the qualitative differentiation of the above analogs.     

Benzamides Substituted with Quinoline-Linked 1,2,4-Oxadiazole: Synthesis,Biological Activity and Toxicity to Zebrafish Embryo

To develop new compounds with high activity, broad spectrum and low-toxicity, 17 benzamides substituted with quinoline-linked 1,2,4-oxadiazole were designed using the splicing principle of active substructures and were synthesized. The biological activities were evaluated against 10 fungi, indicating that some of the synthetic compounds showed excellent fungicidal activities. For example, at 50 mg/L, the inhibitory activity of 13p (3-Cl-4-Cl substituted, 86.1%) against Sclerotinia sclerotiorum was superior to that of quinoxyfen (77.8%), and the inhibitory activity of 13f (3-CF₃ substituted, 77.8%) was comparable to that of quinoxyfen. The fungicidal activities of 13f and 13p to Sclerotinia sclerotiorum were better than that of quinoxyfen (14.19 mg/L), with EC₅₀ of 6.67 mg/L and 5.17 mg/L, respectively. Furthermore, the acute toxicity of 13p was 19.42 mg/L, classifying it as a low-toxic compound.     

Melamine trisulfonic acid-catalyzed N-formylation of amines under solvent-free conditions

A highly convenient method for N-formylation of amines via treatment by formic acid in the presence of melamine trisulfonic acid as a catalyst has been developed. This method showed improvements over previous reports in terms of yield, reaction time and chemoselectivity.     

Non-compact generalized variational inequalities for quasi-monotone and hemi-continuous operators with applications

Some results are obtained for non-compact cases in topological vector spaces for the existence problem of solutions for some set-valued variational inequalities with quasi-monotone and lower hemi-continuous operators, and with quasi-semi-monotone and upper hemi-continuous operators. Some applications are given in non-reflexive Banach spaces for these existence problems of solutions and for perturbation problems for these set-valued variational inequalities with quasi-monotone and quasi-semi-monotone operators. This revised version was published online in June 2006 with corrections to the Cover Date.     

Yb原子高激发态的斯塔克光谱

采用ππ偏振激光，通过两步激发和光电离方法，在０－１５４Ｖ／ｃｍ电场范围内，测定了Ｙｂ原子ｎ－１８附近ｍ＝０的斯塔克光谱，首次把包含斯塔克效应的能量矩阵对角化方法推广到Ｙｂ原子，所获得的理论斯塔克图与实验结果基本符合，观察到低场中斯塔克簇随电场增加呈现线性结构以及＾１Ｐ１态与斯塔克簇在抗交叉过程中振子强度发生转移的现象，讨论了结构与量子亏损的关系。     

关于Banach空间中凸泛函的广义次梯度不等式

本文在前人^[1,2]的基础之上，以凸泛函的次梯度不等式为工具，将Jensen不等式推广到Banach空间中的凸泛函，导出了Banach空间中的Bochner积分型的广义Jensen不等式，给出其在Banach空间概率论中某些应用，从而推广了文献[3—6]的工作．     

Study of photophysical properties of capped CdS nanocrystals

Here, we have examined the role of capping agent on the optical properties of CdS nanoparticles by steady-state and time-resolved photoluminescence (PL) spectroscopy. The estimated particles sizes are 3.45, 2.5 and 2.39 nm for uncapped, capped with silica (SiO₂) and thiosalicylic acid (TSA), respectively. The absorption and emission spectra show a clear blue shift to shorter wavelengths in presence of TSA- and SiO₂-capped nanoparticles. It is found that the average decay time 〈τ〉 are 6.24, 4.54 and 2.84 ns for uncapped, capped with SiO₂ and TSA nanoparticles, respectively. Our analysis suggests that the hole or the electron is trapped on thiol molecule of TSA or hydroxyl group of SiO₂, then radiative recombination of the electron and hole is delayed, resulting in strong quenching of PL efficiency.