流动注射-电化学氧化法测定水体化学需氧量

采用硼掺杂金刚石(Boron-doped diamond,BDD)薄膜电极为工作电极,利用流动注射分析方法测定水体化学需氧量(COD),根据水样中有机物组分在工作电极表面氧化消耗的电量(Qoxidation)测定样品的COD值。考察了一些基本参数包括载液、工作电位、流速对检测信号的影响并选定了最佳检测条件。在最佳检测条件下,本法检测COD的线性范围为2.5~120 mg/L,检出限为1 mg/L。用该法测定化工厂和食品厂废水的COD值,相对标准偏差和回收率分别在2.4%~4.8%和96%~106%之间,且检测结果与国家标准方法(CODcr法)有良好的一致性。     

An Experimental Design for Simultaneous Determination of Carbendazim and Fenamiphos by Electrochemical Method

This study is aimed to develop an electroanalytical methodology using a boron‐doped diamond electrode (BDD) associated with experimental design in order to determine simultaneously and selectively carbendazin (CBZ) and fenamiphos (FNP) pesticides. In previous studies oxidation peaks were observed at 1.10 V (CBZ) and 1.20 V (FNP), respectively, with characteristics of irreversible processes controlled by diffusion of species (in pH 2.0 (CBZ) and pH 3.5 (FNP)) using a BR buffer 0.1 mol L^?1 as support electrolyte. The differences between the potentials for both pesticides, (about 100 mV) indicate the possibility of selective determination of FNP and CBZ. However, employing an equimolar mixture of analytes, the peaks overlap to form a single oxidation peak. Thus, we used a 3⁴ full factorial design with four parameters to be analyzed in three levels, in order to obtain the optimized parameters for the separation of the peaks. The best separation conditions were pH 5.0, square wave frequency of 300 s^?1, pulse amplitude of 10 mV and scan increment of 2 mV. These parameters were used to obtain the calibration curves of CBZ and FNP. For CBZ the analytical curve was obtained in the concentration range of 4.95×10^?6 to 6.90×10^?5 mol L^?1 with good sensitivity and linearity (0.175 A/mol L^?1 and 0.999, respectively). The limits of detection (LOD) and quantification (LOQ) were 1.6×10^?6 mol L^?1 and 5.5×10^?6 mol L^?1, respectively. For FNP the linear concentration interval was 4.95×10^?6 to 3.67×10^?5 mol L^?1, with a sensitivity of 0,207 A/mol L^?1 and linearity of 0.996. The LOD and LOQ were 4.1×10^?6 mol L^?1 and 13.7×10^?6 mol L^?1, respectively. Using these experimental conditions it was possible to separate the oxidation peaks of CBZ (E_p=1.08 V) and FNP (E_p=1.23 V). The electroanlytical method was applied in lemon juice samples. The recovery values were 110.0 % and 92.5 % for CBZ and FNP, respectively. The results showed that the developed method is suitable for application in foodstuff samples.     

The New Application of Boron Doped Diamond Electrode Modified with Nafion and Lead Films for Simultaneous Voltammetric Determination of Dopamine and Paracetamol

A new voltammetric procedure for the simultaneous determination of dopamine (DA) and paracetamol (PA) using boron doped diamond electrode modified with Nafion and lead films (PbF/Nafion/BDDE) was investigated. The use of this electrode resolved the overlapped voltammetric waves of DA and PA into well‐defined peaks with peak to peak separation of about 320 mV. Under the optimized experimental conditions in differential pulse voltammetric technique, DA and PA gave a linear response over the ranges 2.0×10^?7–1.0×10^?4 mol L^?1*(R²=0.9996) and 5.0×10^?7–1.0×10^?3 mol L^?1 (R²=0.9979), respectively. The detection limits were found to be 5.4×10^?8 mol L^?1 for DA and 1.4×10^?7 mol L^?1 for PA. They are lower, comparable or in some cases a little bit higher than those obtained using other electrochemical sensors. However, the proposed procedure of the sensor preparation is much simpler than procedures described in the literature with a lower detection limit. The proposed procedure was successfully applied to the determination of PA in some commercial pharmaceuticals as well as to the simultaneous determination of DA and PA in human urine, whole blood and serum samples directly without any separation steps.     

Syntheses,structure and characterization of a fourfold interpenetrated 3D Cd(II) organic framework constructed with a zwitterionic ligand

A 3-D cadmium(II) organic framework with a fourfold interpenetrated diamond topological structure, {[CdLBDC]·(H₂O)₂}_n (1), was synthesized through zwitterionic ligand H₃LBr₃ (1,1′,1″-(2,4,6-trimethylbenzene-1,3,5-triyl)-tris(methylene)tris(4-carboxypyridinium)tribromide), secondary ligand H₂BDC (1,4-benzenedicarboxylic acid) and Cd(NO₃)₂·4H₂O by solvothermal method. Compound 1 was characterized by elemental analyses, FT-IR spectroscopy, powder, and single-crystal X-ray diffraction and thermogravimetric analysis. The photophysical properties of 1 were investigated by solid-state diffuse reflectance spectrum. In 1, each L is linked by two separate Cd(II)-centered distorted tetrahedra, which are also linked by two L, thereby forming a head-to-tail connected 2-D layer structure and further building the 3-D framework through BDC^2?-chelating-bridging between layers.     

高温高压下石墨-Ni70Mn25Co5体系中金刚石单晶合成工艺参数对金属包膜的影响

利用扫描电子显微镜和能谱仪,研究了高温高压下金刚石单晶合成工艺参数对石墨-Ni70Mn25Co5体系中金属包膜组织形貌和成分的影响。结果发现:合成压力和合成温度都合适时,金属包膜中基本无条状石墨,而且包膜中间都存在网状物,包膜中存在着明显的碳、镍和锰的成分起伏;此时合成时间对包膜的形貌影响不明显;而合成压力为5.1GPa的包膜中存在大量条状石墨,包膜中间无网状物。分析认为,网状物为溶入了锰、钴的镍基γ固溶体,该固溶体是高温高压合成过程中促使金刚石转变的催化相。     

Shallow flow simulation on dynamically adaptive cut cell quadtree grids

A computationally efficient, high‐resolution numerical model of shallow flow hydrodynamics is described, based on dynamically adaptive quadtree grids. The numerical model solves the two‐dimensional non‐linear shallow water equations by means of an explicit second‐order MUSCL‐Hancock Godunov‐type finite volume scheme. Interface fluxes are evaluated using an HLLC approximate Riemann solver. Cartesian cut cells are used to improve the fit to curved boundaries. A ghost‐cell immersed boundary method is used to update flow information in the smallest cut cells and overcome the time step restriction that would otherwise apply. The numerical model is validated through simulations of reflection of a surge wave at a wall, a low Froude number potential flow past a circular cylinder, and the shock‐like interaction between a bore and a circular cylinder. The computational efficiency is shown to be greatly improved compared with solutions on a uniform structured grid implemented with cut cells. Copyright © 2006 John Wiley & Sons, Ltd.     

偶数维的线性化Navier—Stokes方程解之逐点估计

道德对偶数维线性化Ｎａｖｉｅｒ－Ｓｔｏｋｅｓ方程的格林函数作出估计，再用格林函数得出了其解的逐点估计。     

炸药爆轰合成超细金刚石机理的研究概况

 从实验探索、理论研究和数值模拟三方面对利用炸药分子中的碳合成超细金刚石的机理进行了系统的总结与分析，并介绍了目前这个领域的一些有待研究的问题。     

压力变化对再结晶石墨的影响

 用电子显微镜观察了不同压力下催化剂合金中花瓣状、类球状、片状再结晶石墨含量，晶粒形貌随压力变化的情况。得到如下结论：在高温高压条件下，利用过渡族金属合金作催化剂，在石墨向金刚石转化过程中，类球状再结晶石墨的存在是不可缺少的环节。     

从碳化硅和铁体系合成金刚石

 为了探明从SiC生成金刚石这一过程中触媒作用的机理，有必要调查SiC加不同金属在高压高温下的行为。在本工作中，以16重量比混合的SiC和铁粉经5.4~6.0 GPa的高压力和1 300~1 500 ℃的高温处理20 min后，样品的X射线衍射分析表明：所有实验条件下SiC都发生了分解，并分别生成了Fe₃Si和Fe₃C；温度越高，SiC分解得越彻底，在温度高于1 375 ℃的样品中，伴随Fe₃C减少，有金刚石和石墨明显析出。扫描电镜观察表明：6.0 GPa、1 500 ℃下所得的金刚石晶体具有完整的八面体晶形，平均粒度约50 μm。