新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

Photolysis of gamma-(alpha-carboxy-2-nitrobenzyl)-L-glutamic acid investigated in the mcrosecond time scale by time-resolved FTIR

The photolytic release of substrates from caged substrates has proven to be an excellent method to generate concentration jumps for kinetic measurements in the microsecond time scale. In this report we use time-resolved FTIR in the step-scan mode to probe the photolysis mechanism of one such caged compound, namely gamma-(alpha-carboxy-2-nitrobenzyl)glutamate, and to obtain a direct measure of the rate of photorelease of the substrate glutamate. The time-resolved difference FTIR spectra exhibit specific signals that can be assigned to the reactant caged glutamate, photolytically released product glutamate, as well as to the aci-nitro intermediate, the key intermediate of the photolysis reaction. Therefore these signals allow the characterization of the kinetics of formation and decay of the intermediate and products. This is the first such report that provides a direct determination of the rate of formation of the photolysis product from a caged compound in the microsecond time scale. Furthermore, the results presented provide a good basis for further time-resolved FTIR studies of molecular reaction mechanisms, such as ligand protein interactions, in the microsecond time scale through the photolytic release of substrates from caged compounds.     

Cu（I）/Diamine-catalyzed Aryl-alkyne Coupling Reactions

Arylalkynes are important building blocks for the synthesis of natural products,pharmaceuticals,and artificial molecular devices1.They are often synthesized via the Pd-catalyzed Sonogashira coupling reactions between aryl halides and terminal alkynes2,3.Unfortunately,it remains difficult to apply the Sonogashira reaction to industrial scale and/or pharmaceutical synthesis,due to the high cost of Pd and the difficulty in removing the toxic Pd residues from the reaction products.Thus it is wor…     

前驱体水解对纳米铂形状控制合成的影响

以聚丙烯酸钠(NaPA: M_w ≈ 2100)为保护剂，对比研究了H_2还原K_2PtCl_4 和K_2PtCl_6水溶液制备纳米铂晶粒的形状选择性，揭示了前驱体的水解对纳米铂 晶粒的形状控制合成具有显著影响。文献中通常采用的合成立方形状纳米铂的 K_2PtCl_4前驱体在水溶液中不稳定，避光静置一周会析出黑色沉淀。这种不稳定 性导致了以K_2PtCl_4为Pt前驱体的合成结果难以重复。相比而言，避光静墨的 K_2PtCl_6水溶液很稳定，以它为前驱体合成的纳米铂通常为削角八面体。 K_2PtCl_6水溶液暴露于室内光线中会出现[PtCl_6]~(-2)的光致水解。当[PtCl_6] ~(2-)的紫外特征吸收峰(260nm)由于光致水解完全消失后，以聚丙烯酸钠为保护剂 ，通过H_2还原可以有选择性地(约80%)合成由{100}晶面包裹的立方体形状的纳米 铂。     

二水草酸锌脱水的热分解动力学研究

提出一种多升温速率-等温法确定机理函数g(α)的新方法;并用迭代的等转化率法求出较为可靠的活化能Ea;在Ea和g(α)的基础上计算出指前因子A.用该法对二水草酸锌（ZnC2O4•2H2O）脱水反应的热分解动力学三因子进行了求算,得出Ea为87.22 kJ•mol－1, A为4.2120×108～7.2328×108 s－1;以及随机成核和随后生长型机理函数Am（Avrami-Erofeer）,其积分形式g(α)=[－ln(1－α)] 1/m和微分形式f(α)=m(1－α)•[－ln(1－α)](1－1/m),调节因子m=1.85～2.00.     

潜在表示学习框架下的低冗余多视图聚类算法

基于潜在空间学习的多视图聚类研究得到了较大发展,但其通常忽略了原始数据中冗余信息的存在可能会带来不理想的聚类结果。为解决这个问题,提出一种潜在表示学习框架下的低冗余多视图聚类算法。基于k-means的方法,直接从各视图数据学习其低维表示,由于该低维表示的各个特征相互正交,学习到的低维表示通常含有较少的冗余信息。基于潜在空间的假设,各视图的低维表示可由同一个潜在表示投影得到。将两者结合,就能得到一个具有低冗余信息的统一的潜在表示。设计了一个优化算法来求解目标问题,在多个公开数据集上的实验表明了该算法的有效性。     

泵引起的液压系统振动分析

通过液压系统产生振动和噪音的振源及振动量传递的分析,开发了测定泵的振源特性的新方法,－２压力／２系统”法,介绍了用阻抗求解管内压力脉动的方法及通用仿真程序包,实验表明,仿真结果与实测结果一致。     

Inclusion complexes of alcohols with α-cyclodextrin

Calorimetric studies of the inclusion complexes of straight and branched alcohols and of diols with alpha-cyclodextrin (-CD) have been carried out in water solvent. The data suggest that straight and branched chain alcohols enter the cavity of -CD alkyl end first. The hydroxyl group hydrogen bonds to the outer oxygen ring of the cyclodextrin. For branched chain alcohols the longer alkyl part of the molecule penetrates the -CD cavity up to the hydroxyl group. Diols form two hydrogen bonds to the outer oxygen ring of the cyclodextrin with some penetration into its interior.     

An exponent bound on skew Hadamard abelian difference sets

A difference setD in a groupG is called a skew Hadamard difference set (or an antisymmetric difference set) if and only ifG is the disjoint union ofD, D(^–1), and {1}, whereD(^–1)={d^–1|dD}. In this note, we obtain an exponent bound for non-elementary abelian groupG which admits a skew Hadamard difference set. This improves the bound obtained previously by Johnsen, Camion and Mann.     

智能网联车辆节能自适应巡航控制研究

现有车辆自适应巡航控制多专注于单一的轨迹跟踪目标,而决定控制技术实际应用效益的关键是系统的节能性能.为了能够同时保证跟踪误差收敛性与燃油经济性,研究了一种车辆节能自适应巡航控制器设计方法：首先以轨迹跟踪为目标,设计了具有时变反馈增益的状态反馈控制律;其次,以反馈增益为优化变量,以整个预测时域内各采样时刻自身车辆单位位移燃油消耗量的累加为代价函数,基于经济模型预测控制方法设计了节能控制算法,并通过构建共同Lyapunov函数,给出了保证跟踪误差以指数速度收敛的反馈增益选取范围;最后,通过数值仿真验证了控制器设计的有效性,定量展示了本文所提出的方法在降低燃油消耗量方面的有效性.