Selenium-catalyzed oxidative carbonylation of 1,2,3-thiadiazol-5-amine with amines to 1,2,3-thiadiazol-5-ylureas

With cheap and easily available 1,2,3-thiadiazol-5-amine and amines as raw materials, cheap and reusable selenium as the catalyst, CO as the carbonylation reagent and O₂ as the oxidizing agent, the selenium-catalyzed oxidative carbonylation reaction of 1,2,3-thiadiazol-5-amine can proceed smoothly with a series of amines in one-pot manner in the presence of triethylamine, affording 1,2,3-thiadiazol-5-ylureas mostly in moderate to good yields.     

高温压电材料、器件与应用

作为重要的功能材料,压电材料已经在国民经济的多个领域里有着重要应用.随着现代工业的快速发展,特别是新能源、交通和国防工业的高速发展,功能材料的应用已经从常规使用转向极端环境下的服役.本文综述了具有高居里点的压电材料,包括钙钛矿型压电陶瓷、铋层状结构氧化物压电陶瓷、钨青铜结构压电陶瓷以及非铁电压电单晶等;介绍了其晶体结构特征和高温压电性能、最新研究进展,并列举了一系列的高温压电器件和应用,包括高温压电探测器、传感器、换能器和驱动器等.另外,本文总结了高温压电材料的热点研究问题,并展望了今后的发展方向.     

由马来酐、邻苯二甲酸酐合成(硫)脲衍生物

马来酐和邻苯二甲酸酐的含氮衍生物具有很强的生理活性,它们作为驱鼠剂,除草剂,植物生长调节剂已有报导。我们以马来酐和邻苯二甲酸酐为原料合成了16种(硫)脲衍生物并测定了它们的结构,这些化合物均未见文献报导。其合成路线如下:     

赞比西河水资源调度

研究了赞比西河水资源的调度决策问题。赞比西河上的卡里巴大坝年久失修,赞比西河管理局给出了3种方案:维修、重建或用多个大坝代替现有的卡里巴大坝。通过查阅赞比西河相关资料及沿岸的地形地貌信息,首先确定了11个大坝的地理位置及每个大坝发电机组的装机容量,目标是满足水库附近居民及工农业的用水和用电需求;其次,根据投入产出比对管理局提出的3种方案进行了评价,以确定最优决策方案;最后,基于多坝替代系统建立了梯级水库的水资源调度模型,利用坐标轮换方法分别对平水年、丰水年和枯水年进行了水资源调度。模型的敏感性分析表明调度方案模型是稳健的,建立的调度模型符合实际,使得多坝系统水管理能力增强。     

Fabrication of metallized nanoporous films from the self-assembly of a block copolymer and homopolymer mixture

Inorganic compound HAuCl4, which can form a complex with pyridine, is introduced into a poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) block copolymer/poly(methyl methacrylate) (PMMA) homopolymer mixture. The orientation of the cylindrical microdomains formed by the P2VP block, PMMA, and HAuCl4 normal to the substrate surface can be generated via cooperative self-assembly of the mixture. Selective removal of the homopolymer can lead to porous nanostructures containing metal components in P2VP domains, which have a novel photoluminescence property.     

Probability of random events of inspection and repair and maintaining reliability of structures

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检修事件的概率分析与结构的维修可靠性

定期检修结构的可靠性分析,需要定量处理大量复杂的随机事件。综合考虑各种随机因素,较全面地分析了检修过程中影响可靠性的诸多复杂随机事件及其发生概率。系统地建立了检修结构的动态可靠性分析模型,整个模型程序化程度高,易于实施。     

随机有限元方法与结构可靠性

简要介绍和综合论述了随机结构的有限元分析及可靠性分析方法的研究及发展情况．包括随机结构的离散化、随机有限元控制方程的求解、随机有限元可靠性方法及随机结构的可靠性分析等．讨论了随机结构分析中存在的一些问题．概要论述了可能的发展方向．     

Radical homopolymerization of tetrafluoroethylene initiated by perfluorodiacyl peroxide in supercritical carbon dioxide: Reaction mechanism and initiation kinetics

Radical homopolymerizations of tetrafluoroethylene (TFE) in supercritical carbon dioxide (sc-CO₂) initiated by bis(perfluoro-2-n-propoxypropionyl) peroxide (BPPP) were conducted. Low molecular weight polytetrafluoroethylenes (PTFEs) which are widely used in diverse fields with stable end groups were successfully obtained. PTFEs were characterized by solid-state ¹⁹F NMR and FT-IR spectroscopy. From rational assignment of the characteristic signals, an overall reaction mechanism explaining the homopolymerization processes is proposed. The carboxyl radicals resulted from thermal decomposition of BPPP were completely decarboxylated to n-C₃F₇OCF(CF₃) before reacting with TFE. Additionally, a small amount of n-C₃F₇OCF(CF₃) rearranged into n-C₃F₇ with decreased rearrangement fraction from 0.11 to 0.04 when the reaction temperature was lowered from 35 to 5 °C. Initiation rate constants (k_d) were slightly increased with elevated pressure. The initiation activation energy derived from k_d is 90.3 kJ mol^?1, which is much lower than those of the other systems where nonfluorinated diacyl peroxides are used. Such mechanism and kinetics insights into the homopolymerizations of TFE in sc-CO₂ will be instructive for the syntheses of fluoropolymers with desired properties in future.     

Development and validation of an LC-MS-MS method for determination of methyl kulonate in rat plasma

A sensitive, rapid and specific LC‐MS‐MS method was established and validated for determination of methyl kulonate, a major bioactive constituent isolated from Meliae Cortex, in rat plasma. Plasma samples were treated by precipitating protein with methanol and were chromatographed using a Capcell Pak C₁₈ column (100 × 4.6 mm, 5 µm) with the mobile phase comprising a mixture of methanol, 10 m m ammonium formate and formic acid (95:5:0.1, v/v/v). Detection and quantification were performed by mass spectrometry in the multiple reaction monitoring mode with positive atmospheric ionization at m/z 467 → 311 for methyl kulonate, and m/z 469 → 451 for dubione B (internal standard), respectively. A good linear response was observed over the concentration range 1.00–500 ng/mL with the lower limit of quantification 1.00 ng/mL in rat plasma. The method also afforded satisfactory results base on sensitivity, specificity, precision, accuracy, recovery, freeze–thaw and long‐time stability. The validated method was successfully applied to determine the pharmacokinetic properties of methyl kulonate in rats after oral administration at dose of 100 mg/kg. This pharmacokinetic study of methyl kulonate is reported here for the first time. Copyright © 2011 John Wiley & Sons, Ltd.