铁基超细粒子催化剂结构与还原行为的Mssbauer谱研究

铁基超细粒子催化剂具有优良的F-T反应性能。本工作利用原位Mssbauer谱辅以XRD技术研究了含有钾助剂的F-T合成铁基超细粒子催化剂的结构与还原行为,考察了催化剂组成和第二金属组分(Mn,Zn,Mg)的影响。“纯”铁超细粒子催化剂在氢气中很容易经Fe_3O_4还原为零价铁。第二金属组分的引入,一方面阻碍了催化剂的还原,另一方面稳定了Fe~(2+)的存在而使其成为还原的主要中间相,这有利于反应条件下形成类尖晶石结构的活性相。对于Fe-Mn催化剂,上述效应随锰含量的增加而更趋显著。铁基超细粒子催化剂在氢气中的还原能力依“纯”Fe>Fe-Zn>Fe-Mn>Fe-Mg的顺序递减,这在一定程度上反映了铁与第二金属组分之间相互作用的强弱。     

聚苯乙烯—钛酸钡复合材料介电性能的研究

以聚苯乙烯与化学沉淀法钛酸钡陶瓷为基本组成，采用溶液共混，溶液聚合，表面处理后溶液聚合三种方法进行复合，发现后两种复合的钛酸钡颗粒表面发生界面变化，形成活性界面，使得溶液聚合法和表面处理后溶液聚合所得到的材料具有较低的介电损耗，在高频下能保持较高的介电系数。     

Mechanism of Copper(I)‐Catalyzed Allylic Alkylation of Phosphorothioate Esters: Influence of the Leaving Group on α Regioselectivity

The mechanism of Cu^I‐catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)₂; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)₂Cu]^? prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α‐ or γ‐selective product. If OPiv, SPiv, Cl, or SPO(OiPr)₂ groups are present, the optimal route for the formation of both α‐ and γ‐substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α‐ and γ‐substituted products are 2.75 kcal mol^?1 with SPO(OiPr)₂, 2.44 kcal mol^?1 with SPiv, 2.33 kcal mol^?1 with OPiv, and 1.98 kcal mol^?1 with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)₂>SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)₂, SPiv, OPiv, and Cl groups on the Cu group.     

Modification of Cr/SiO2 for the dehydrogenation of propane to propylene in carbon dioxide

Summary Dehydrogenation of propane to propylene in carbon dioxide was investigated over promoted Cr/SiO2. The results showed that the catalysts were effective for the reaction and CO2 in the feed promoted the catalytic activity. XRD, TPR and microcalorimetric adsorption techniques were used to study the structure and surface acidity of the catalysts. It was found that the surface acidity decreased with the increase of K in the Cr/SiO2 and led to the increase of selectivity toward propylene. A propane conversion of 31% with 91% selectivity to propylene over the 5%Cr-0.4%K/SiO2 catalyst was observed at 923 K with CO2 /C3H8 molar ratio of 3.6.     

基体辅助激光解吸电离飞行时间质谱用于寡糖的分析

将基体辅助激光解吸电离飞行时间质谱这种新兴的质谱方法用于植物中寡糖的分析。比较了不同的样品制备方法和检测方法对分析结果的影响,给出各寡糖样品的分子量分布,单体和端基基团的分子量。     

Surface Functionalization of PEO Nanofibers Using a TiO2 Suspension as Sheath Fluid in a Modified Coaxial Electrospinning Process

Convenient and integration fabrication process is a key issue for the application of functional nanofibers. A surface functionalization method was developed based on coaxial electrospinning to produce ultraviolet(UV) protection nanofibers. The titanium dioxide(TiO₂) nanoparticles suspension was delivered through the shell channel of the coaxial spinneret, by which the aggregation of TiO₂ nanoparticles was overcome and the distribution uniformity on the surface of polyethylene oxide(PEO) nanofiber was obtained. With the content of TiO₂ increasing from 0 to 3%(mass fraction), the average diameter of nanofibers increased from (380±30) nm to (480±100) nm. The surface functionalization can be realized during the electrospinning process to gain PEO/TiO₂ composite nanofibers directly. The uniform distribution of TiO₂ nanoparticles on the surface of nanofibers enhanced the UV absorption and resistance performance. The maximum UV protection factor(UPF) value of composite nanofibers reaches 2751. This work presented a novel surface-functionalized way for the preparation of composite nanofiber, which has great application potential in the field of micro/nano system integration fabrication.     

Synergistic effects on iodine release in potassium iodide solution by combination of ultrasound and visible light irradiations

Iodine release in potassium iodide solution has been investigated under the irradiations of ultrasound and visible light respectively and simultaneously. We have observed that the amount of iodine liberated under the combined irradiation of ultrasound and visible light is larger than the sum of that under the respective irradiations of ultrasound and visible light, indicating a synergistic effect of ultrasound and visible light irradiations. Based on the investigation of the reaction kinetics of iodine liberated, we have ascribed the synergistic effect to the perfect stirring of the photochemical reactor induced by the applying simultaneous ultrasound. The ideal stirring can result in the homogenization of the primary light effect in the whole reaction medium, which induces the acceleration of the photochemical reaction. On behavior of our knowledge, there are few reports on the investigations of utilizing the combination of ultrasonic energy and light energy to accelerate the reaction yield and rate as well as the kinetics of the reaction.     

Design,synthesis and evaluation of a novel fluorescent probe to accurately detect H2S in lysosomes

A novel H₂S-responsive fluorescent probe Rh-Lyso-H₂S has been designed and synthesized. The Rh-Lyso-H₂S shows high sensitivity and selectivity toward H₂S, with a limit of detection of 3.36?×?10^?7?M. The reason is that Rh-Lyso-H₂S changed from a stable non-conjugated closed-ring lactone conformation with weak fluorescence to a conjugated open-ring conformation with strong fluorescence in the presence of H₂S. The Rh-Lyso-H₂S has a good lysosome-targeting capacity and is used to detect lysosomal H₂S in living cells, which is driven via the protonation of its basic morpholine moiety by acidic lysosomes. Rh-Lyso-H₂S is triggered by H₂S via removing the thiophenecarboxylate group, and the corresponding activated mechanism of Rh-Lyso-H₂S toward H₂S is proposed.     

串联双环光微谐振器的滤波特性

详细研究了串联双环光微谐振器的光带通滤波特性，给出了其通带带宽的公式，分析了出／入环光耦合系数和环间光耦合系数对通带特性的影响，计算并特别强调了滤波通带的结构特点，也分析了微环中存在的光损耗对串联双环光微谐振器的滤波特性的影响。     

认可机制下实验室人员培训工作的组织与开展

针对部分实验室在人员培训工作中存在的培训模式不清、培训机制不健全、培训质量较低的问题,系统地分析了计量实验室人员培训所涉及的主要类别、内容及要求等。对培训工作的流程逐个进行详尽地描述,分内部培训和外部培训两个方面对培训中应注意的问题进行重点说明,为广大计量实验室管理人员开展人员培训工作提供借鉴。