Ar—Kr溶液扩散系数的分子动力学模拟及其与温度的关系

用分子动力学模拟方法研究确定Ａｒ－Ｋｒ溶液的自扩散系数Ｄ１、Ｄ２和互扩散系数Ｄ１２以及它们随温度变化的规律。结果表明，分别用Ｇｒｅｅｎ－Ｋｕｂｏ法和Ｅｉｎｓｔｅｉｎ法得到的扩散系数在数值上一致；该溶液的３种扩散系数均满足Ｄ＝Ｄ０ｅ＾Ｅ／ＲＴ关系。     

2-巯基乙醇自组装膜电极对多巴胺电催化氧化及其分析应用

在裸金电极上制备了 2 巯基乙醇自组装膜电极 (ME AuSAMs) ,研究了多巴胺 (DA)在ME AuSAMs上的电化学行为 ,发现该膜电极对DA的氧化具有良好的电催化作用 ,氧化过电位降低了 3 94mV ,测得DA的扩散系数D为 9.1 4 5× 1 0 - 7cm2 s,初步探讨了电催化机理。采用水平衰减全反射 傅里叶变换红外光谱 (ATR FTIR)技术对ME AuSAMs进行了表征 ;方波伏安法 (squarewavevoltammetry ,SWV)测定DA ,其氧化峰电流与DA浓度在 2 .0 0× 1 0 - 6 ～ 1 .0 0× 1 0 - 4 mol L范围内呈线性关系 ;相关系数为 0 .9998,检出限为 4 .0 0× 1 0 - 7mol L。该电极用于DA药物针剂的测定 ,结果满意     

Short Te …︁ Te bonding contacts in a new layered ternary telluride: Synthesis and crystal structure of 2D Nb3GexTe6 (x ≃ 0.9)

The new layered ternary compound Nb₃Ge_xTe₆ (x ? 0.90) was prepared by direct combination of the elements taken in the stoichiometric proportions 3 : 1 : 6, heated at 1 000 °C for 10 days in silica tubes and quenched to room temperature. The phase crystallizes in the orthorhombic symmetry, space group Pnma (#62), with the following single crystal refined parameters: a = 643.18(5) pm, b = 1391.98(11)pm and c = 1 154.07(5) pm, with Z = 4. The structure was refined to an R of 3.4% (R_w = 4.6%), with 1969 independent reflexions and 49 parameters. The structure is based on the close stacking of trigonal prismatic (TP) slabs in the AA/BB mode. The slabs can be seen as built up from face sharing biprisms, which are filled either by one or by two niobium cations situated in the middle of the trigonal prisms. The germanium is located in the middle of the common face of two prisms, leading to a rather unusual anionic square coordination. The refinements showed that this latter cation does not fill completely its square site. No cation was found in the van der Waals gap between the slabs. The mean d_{Ge? Te} distance (276.5 pm) is in agreement with Ge^II cations, while some Te …? Te distances (from 333.84 to 361.65pm) are too short for anions in a simple contact. These bonding distances, already mentionned in some MTe₂ compounds, are to be ascribed to charge transfer in the structure, with a partial oxidation state for the tellurium anions. Short Nb? Nb and Nb? Ge distances (292.0 and 281.3 pm, respectively) imply intercationic bonding within the slabs.     

最小一乘稳健多元分析校正

本文论述最小一乘求解的多元分析校正算法，探讨了最小一乘较常规最小二乘法及其他隐健算法的优点。用计算机数值模拟及实际多组分光谱体系对方法进行了检验，展示了最小一乘法在分析化学计量学中实际应用的可行性。     

Determination of BHT in the presence of surfactants using a cellulose acetate coated electrode and square wave voltammetry

A direct voltammetric method for the rapid determination of butylated hydroxytoluene has been developed. The procedure utilizes a hydrolyzed cellulose acetate film in intimate contact with a glassy carbon electrode and square wave voltammetry. The coated electrode prevents passivation due to adsorption of polymeric oxidation products by way of a size exclusion principle. BHT solutions containing lipid-like surfactants can be analyzed without the need for frequent resurfacing of the electrode.     

M-矩阵平方根的一类迭代法

矩阵平方根在数学的许多应用中起着重要的作用.本文研究M-矩阵平方根的计算问题,提出一种计算正则M-矩阵平方根的迭代方法.首先将这个问题转化为M-矩阵代数Riccati方程,进而提出一种有效的方法来求解这个特殊的MARE.理论分析表明,该方法在一定条件下是收敛的.数值实验表明该方法是可行的,且优于二项式迭代法.     

A law of the iterated logarithm for processes with independent increments

ＡＬＡＷＯＦＴＨＥＩＴＥＲＡＴＥＤＬＯＧＡＲＩＴＨＭＦＯＲＰＲＯＣＥＳＳＥＳＷＩＴＨＩＮＤＥＰＥＮＤＥＮＴＩＮＣＲＥＭＥＮＴＳＷＡＮＧＪＩＡＧＡＮＧ（汪嘉冈）（ＥａｓｔＣｈｉｎａＵｎｉｖｅｒｓｉｔｙｏｆＳｃｉｅｎｃｅ＆Ｔｅｃｈｎｏｌｏｇｙ,Ｓｈａｎｇ...     

The Employ of Multiple Voltammetric Pulses for the Study of the Adsorption of Bipyridilium Pesticides in River Sediment

The multiple square‐wave voltammetry (MSWV) allied to gold microelectrode (Au‐ME) was used to establish an electroanalytical procedure for the determination of the paraquat and diquat pesticides in river sediment samples. For both pesticides, two reduction peaks, at around ?0.70 V (peak 1) and around ?1.00 V vs. Ag/AgCl 3.00 mol L^?1 (peak 2), with profile of the totally reversible redox process, were observed. The experimental and voltammetric conditions showed that the best conditions to reduce paraquat and diquat were a pH of 6.0, a frequency of 250 s^?1, a scan increment 2 mV, a square‐wave amplitude of 50 mV and pulse number of 8 pulses of potential in each step of staircase of potential. Under such conditions, the detection limit of 0.044 μg L^?1 (0.044 ppb) and 0.360 μg L^?1 (0.360 ppb ) for peak 1 and peak 2 of paraquat and 0.159 μg L^?1 (0.159 ppb) and 0.533 μg L^?1 (0.533 ppb) for peak 1 and peak 2 of diquat, respectively, were obtained. These results are an order of magnitude of about two less than those obtained and published in the literature. Also, the electroanalytical procedure proposed was applied for the determination of adsorption isotherms of pesticides on river sediments samples collected from Mogi‐Guaçu River in Sao Paulo State, Brazil. The experimental data were fitted using the Langmuir and Freundlich isotherms models; and the results indicated low intensities of adsorption process of the pesticides in the samples employed with distribution coefficients (K_d) lower 5.0, and paraquat showed slightly higher affinity than diquat in the sediments. The increase in organic matter and organic carbon leads to an increase in the K_d values, and consequently an increase in the organic matter constant (K_OM) organic carbon constant (K_OC) values. All results demonstrated that isotherms “L” type in the Giles classification were obtained, indicating that sediments have a medium affinity for the pesticides, and no strong competition from the solvent used (in this case Na₂SO₄) for adsorption sites occurs.     

Isolated square planar metal complexes of carbon

Based on the group theory analysis and quantum chemical calculations within the framework of SW X _α method (in relativistic approximation for core electrons and non-relativistic for valence ones), the existence possibility of square planar complexes [M₄C] and [M₄C]^2? (M = Al, Ga, In, Tl, Sc, and Y) in gas phase has been shown. The extraction of Kt₂[M₄C] square planar complexes of carbon in the crystal state is possible too. A high stability of these complexes, in comparison with usual tetrahedral, is achieved due to the formation of five-and four-center bonds (bonds M-M and M-C).     

Fe_3(CO)_9(μ_3-S)_2的P(SR)Cl_2和P(SR′)_3取代物的合成和结构研究

用P(SR)Cl_2和P(SR′)_3作n-酸配体,分别与Fe_3(CO)_9(μ_3-S)_2进行取代反应,得到6种新的一取代产物Fe_3(CO)_8(μ_3-S)_2L和3种新的二取代产物Fe_3(CO)_7(μ_3-S)_2L_2,并对它们进行了IR、~1H NMR和MS表征,测定了其中一种取代物Fe_3(CO)_8(μ_3-S)_2[P(SC_6H_5)Cl_2]的分子和晶体结构。