二元铜团簇催化水煤气变换反应机理的理论研究

水煤气变换反应是一个重要的反应体系, 它可以去除H₂中少量的CO而被应用在质子膜燃料电池中. 然而关于水煤气变换的反应机理还存在一定的争议, 为阐明其反应机理, 本文采用密度泛函理论PBE方法, 金属元素采用Lanl2dz基组, 非金属元素采用6-311++G(d,p)基组, 对系列二元铜团簇Cu₆TM (TM=Co, Rh, Ir, Ni, Pd, Pt, Ag, Au)催化水煤气变换反应机理进行了研究. 结果表明: CO分子比H₂O分子更容易吸附到团簇上. 水煤气变换反应包括三种反应机理: 羧基反应机理, 氧化还原反应机理, 甲酸反应机理, 相对应的基元反应分别为CO^*+O^*→CO₂(g), CO^*+OH^*→COOH^*→CO₂(g)+H^*, 和CO^*+H^*+O^*→CHO^*+O^*→HCOO^**→CO₂(g)+H^*. 甲酸根是实验中最可能检测到的中间物, 这是由于生成甲酸根有较低的能垒以及甲酸根解离有较高的解离能. Co, Rh, Ni, Pd掺杂在Cu₇团簇中对水煤气转化反应的催化效果明显比纯Cu₇团簇催化效果好. 采用CO的初始消耗率以及最终CO₂的产率进一步研究了在Cu₆TM (TM=Co, Rh, Ni, Pd)表面甲酸根是反应过程中的旁观者还是一种重要的中间物. 计算结果还表明, 对于Cu₆TM (TM=Ni, Pd), 由于CO较低的反应能垒, 水煤气变换反应主要按照氧化还原反应机理进行反应, 而对于Cu₆TM (TM=Co, Rh), 水煤气变换反应三种反应机理均可进行反应. 本文的结果有助于理解水煤气变换反应和设计更好的催化剂.     

分散固相萃取气相色谱-负化学离子源质谱法测定大豆和玉米中20种农药的残留量

建立了一种大豆和玉米中20种农药残留量的分散固相萃取气相色谱-负化学离子源质谱分析方法。样品经乙腈提取并浓缩后加入N-丙基乙二胺（PSA）、石墨化碳黑和C18 3种填料进行分散固相萃取净化,气相色谱-负化学离子源质谱分时段选择离子监测技术测定与确证,外标法定量。所有农药在20～400 μg/L范围内线性均良好;方法的定量限(LOQ)均不高于2 μg/kg;在5,10和20 μg/kg 3个添加水平下所有农药的平均回收率均处于70%～130%之间,相对标准偏差(RSD)低于17%;运用该方法检测大豆和玉米样品时没有干扰现象。     

An acceleration method for integral equations by using interpolation post-processing

Two post-processing techniques are widely used in the literature in the context of convergence acceleration. One of them is an interpolation technique, used for partial differential equations and integral differential equations, and the other is an iteration technique used for integral equations. These two techniques, interpolation and iteration, are quite different, and the former is simpler. Can we use the interpolation technique for integral equations instead of using the second iteration technique? This report gives a positive answer.

     

Preparation and third-order nonlinear optical properties of self-organized complex oxide Ce: BaTiO3 quantum dots

Pulsed laser ablation epitaxial Strancky-Krastanow growth of self-organized complex oxide Ce:BaTiO₃ quantum dots on MgO(lOO) substrates is demonstrated. Atomic force microscopy and X-ray diffraction are used to observe the structure and the growth process of the self-organized complex oxide quantum dots. The average dimension, height, and the density of self-organized complex oxide Ce:BaTiO₃ quantum dots are given. The nonlinear refractive indexes of the wetting layer and the selforganized ordered quantum dots are determined by the single beam Z-scan method. The mechanisms of the nonlinear effect enhancement for these low-dimensional structure are discussed.     

Numerical Simulation for Convection-Diffusion Problem with Periodic Micro-Structure

In this article, the convection dominated convection-diffusion problems with the periodic micro-structure are discussed. A two-scale finite element scheme based on the homogenization technique for this kind of problems is provided. The error estimates between the exact solution and the approximation solution, of the homogenized equation or the two-scale finite element scheme are analyzed. It is shown that the scheme provided in this article is convergent for any fixed diffusion coefficient 5, and it may be convergent independent of δ under some conditions. The numerical results demonstrating the theoretical results are presented in this article.     

Superconvergence analysis and a posteriori error estimation of a finite element method for an optimal control problem governed by integral equations

In this paper, we discuss the numerical simulation for a class of constrained optimal control problems governed by integral equations. The Galerkin method is used for the approximation of the problem. A priori error estimates and a superconvergence analysis for the approximation scheme are presented. Based on the results of the superconvergence analysis, a recovery type a posteriori error estimator is provided, which can be used for adaptive mesh refinement. The research project is supported by the National Basic Research Program under the Grant 2005CB321701 and the National Natural Science Foundation of China under the Grant 10771211.     

Superconvergence analysis of the nonconforming quadrilateral linear-constant scheme for Stokes equations

In this paper, the superconvergence analysis of the nonconforming quadrilateral linear-constant scheme for Stokes Equations is discussed. The superclose property is proven for rectangular meshes; then global superconvergence is derived by applying a postprocessing technique. In addition, some numerical examples are presented to demonstrate our theoretical results. The research was supported by National Natural Science Foundation of China (No. 60474027).     

QuEChERS-超高效液相色谱-串联质谱法快速测定凉茶中非法添加的12种化学药物

建立了凉茶中马来酸氯苯那敏、吡罗昔康、α-细辛脑等12种非法添加的化学药物的QuEChERS结合超高效液相色谱-串联质谱(UPLC-MS/MS)的检测方法。样品经乙腈提取,应用QuEChERS技术净化,经0.22 μm微孔滤膜过滤后进行UPLC-MS/MS测定,以乙腈-0.1%(v/v)乙酸水溶液为流动相梯度洗脱,在XBridge BEH C₁₈柱(100 mm×2.1 mm, 3.5 μm)上实现12种化学药物的基线分离。该方法采用多反应监测(MRM)正离子模式扫描,标准曲线外标法定量。12种待测物在各自的质量浓度范围内线性关系良好,相关系数均大于0.997,检出限为0.1~2.1 μg/L,定量限为0.4~8.0 μg/L。在3个不同添加水平下的平均回收率为62.7%~95.2%, RSD为1.3%~10.8%。应用该方法对市面上销售的74批次凉茶进行了筛查测定,部分样品的测定结果为阳性。该方法操作简单,净化效果好,灵敏度高,适用于凉茶中12种非法添加的化学药物的快速分析。     

一种力-电协同驱动的细胞微流控培养腔理论模型

细胞培养液在微流控生物反应器中受到外界物理场（如压力梯度或者电场）作用流动而产生流体剪应力,并进一步刺激种子细胞调控其内部基因的表达,从而促进细胞的分化和生长,这个过程在自然生命组织内的微管中亦是如此。考虑到细胞培养微腔隙中液体流动行为很难实验量化测定,理论建模分析是目前可行的研究手段。因此建立了矩形截面的细胞微流控培养腔理论模型,将外部的物理驱动场（压力梯度与电场）与培养腔内液体的流速、切应力和流率联系起来,分别得到了压力梯度驱动（Pressure gradient driven,PGD）、电场驱动（Electric field driven,EFD）及力-电协同驱动（Pressure-electricity synergic driven,P-ESD）三种驱动方式下的液体流动理论模型。结果表明该理论模型与现有的实验结果基本一致,具体地:力-电协同作用下的解答为压力梯度驱动和电场驱动结果的叠加。细胞培养腔内的流体流速、剪应力及流率幅值均正比于外部物理场强幅值,但随着压力梯度驱动载荷频率的增大而减小,随着电场驱动频率的变化不明显。在压力梯度驱动作用下,细胞贴壁处的切应力随着腔高的增大而线性增大,流率则随着腔高的增大而非线性增大,而电场驱动下的结果不受腔高的影响。生理范围内的温度场变化对压力和电场驱动的结果影响不大。另外,在引起细胞响应的流体切应力水平,电场驱动能提供较大的切应力幅值而压力梯度驱动则能提供较大的流率幅值。该理论模型的建立为细胞微流控生物反应器实验系统的设计及参数优化提供理论参考,同时也为力-电刺激细胞生长、分化机理的研究的提供基础。