胶束介质在动力学分析中的应用

评述了胶束介质在动力学分析测定中的作用和应用状况，讨论了胶束催化的动力学特征，胶束对反应物理化学性质的修饰及其在动力学多组份测定和酶催化动力学分析中的应用。     

Chemistry of polyfunctional molecules-123. Reactions of BiBr3, SbI3 and AsI3 with LiN(PPh2)2; X-ray structure of a cyclophosphazene salt containing arsenic(I)

BiBr₃ or SbI₃ react at 20°C with LiN(PPh₂)₂ (1) to give elementary Bi or Sb and the P---P coupled phosphazene ligand Ph₂P---N=PPh₂---PPh₂=N---PPh₂ (2). The reaction of AsI₃ with 1 at room temperature formed yellow needles of the eight-membered heterocycle (3), whereas AsI₃ interacted at 80°C with 1 in the molar ratio of 1:3 to give elementary arsenic and 2. Treatment of AsI₃ and 1 at 20°C in a 1:2 stoichiometry yielded the seven-membered, cyclic arsenium(I) salt

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I·4THF (5·4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis.     

二维卷积在动力学分析中的应用

本文用计算机模拟和二维卷积研究了稀土与间乙酰基偶氮氯膦的显色反应，选择不同的模型参数可描述这类反应的细节，二维卷积则增强对叠合二维谱的分辨。     

Determination of dissolved manganese in natural waters by differential pulse cathodic stripping voltammetry

A procedure based on differential pulse cathodic stripping voltammetry on the graphite electrode is described for the determination of dissolved manganese in natural waters buffered at pH about 6.5 with acetate solution. In order to avoid interference of iron(II) the addition of fluoride is used. The limit of detection is 3 g/l for a deposition time of 6 min. Acidification and UV-irradiation are recommended for samples containing dissolved organic matter. Results of manganese determination in table mineral waters are reported and the possibility of manganese speciation is discussed.     

Interaction of aminoazoles with Meldrum’s acid and dialkyl ketones or cyclohexanone

Interaction of 3-amino-5-methylpyrazole, 3-amino-5-methylthio-, and 3,5-diamino-1,2,4-triazole with Meldrum’s acid, acetone, ethyl methyl ketone, and cyclohexanone leads to alkyl-substituted pyrazolo[3,4-b]pyridin-6-ones and 1,2,4-triazolo[1,5-a]pyrimidin-7-ones respectively. The structure of 5,5-dimethyl-2-methylthio-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidin-7-one was demonstrated by an X-ray structural investigation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 595–601, April, 2007.     

多维气相色谱法提高丙烯腈色谱分析速度的方法

采用多维气相色谱法,既可提高丙烯醛、丙酮、乙腈、丙烯腈相邻两组分的分离度,又可提高分析速度。按GDX-502与402的体积比为85∶15比例混装长4.5m、内径3mm的色谱柱;氢气作为载气,流速为65mL/min;柱箱初温140℃保持15min,以15℃/min的速率升至180℃保持12min。丙烯腈样品中7种组分即可全部出峰,总分析时间为30min,比原国标推荐的方法缩短了近50min。     

Study of gas-liquid partitioning of alkane solutes in several organic solvents by using principal component analysis and linear solvation energy relationships

Principal component analysis (PCA) was used to extract the number of factors which can describe the 737 gas-liquid partition coefficients of five linear, four branched, and two cyclic alkanes in 67 common solvents. Based on the reconstruction of partition coefficient data matrix, we concluded that the experimental dataset could readily be reduced to two relevant factors. Using only these two factors, there were no errors larger than 3%, 7 cases had errors larger than 2%, and in 34 cases, errors were between 1 and 2%. n-Hexane and ethylcyclohexane were chosen as the test factors, and all other partition coefficients were expressed in terms of these two test factors. Prediction of the logarithmic partition coefficient of these alkanes in seven chemically different solvents, which were originally excluded from the data matrix, was excellent: the root mean square error was 0.064, only in 11 cases the errors were larger than 1%, and only 3 had errors larger than 4%.Linear solvation energy relationships (LSERs) using both theoretical and empirical solvent parameters were used to explain the molecular interactions responsible for partition. Several combinations of parameters were tried but the standard deviations were not less than 0.31. This could be attributed to the model itself, imprecisions in the data matrix or in some of the LSER parameters. Solvent cohesive parameters and surface tension in combination with polarity-polarizability or dispersion parameters perform the best.Finally, the two principal component factors were rotated onto the most relevant physicochemical parameters that control the gas-liquid partitioning phenomena.     

The application of the OTA of kerogen to the evaluation of the rockmass heating

Oxyreactive thermal analysis (OTA) carried out in the conditions of full access of oxygen to each reacting particle of the sample investigated is a suitable method for the determination of important properties of the organic matter dispersed in the rocks. Its results may be easily evaluated to the form of values to be used in a clear diversification and classification system of organic matter/kerogen, as well as to the evaluation of its transformation process in a rockmass. The OTA also enables the distinguishing of the transformation stages and the investigation of the results of the gaseous products liberation from organic matter and kerogen. The OTA method may be applied as a complementary one for the Rock Eval analysis and be used for the organic geochemical and bituminological studies for geological bitumen prospecting.This revised version was published online in November 2005 with corrections to the Cover Date.     

Hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone)s: swelling behavior and water states

Hemocompatibility is an essential aspect of blood contacting polymers. Knowledge of the relationship between polymer structure and hemocompatibility is important in designing such polymers. In this work, the effect of swelling behavior and states of water on the hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP) films was studied. Platelet adhesion and plasma recalcification time tests were used to evaluate the hemocompatibility of the films. Considering the importance of surface properties on the hemocompatibility of polymers, static water contact angles were measured by both sessile drop and captive bubble methods. It was found that, on the film surface of PANCNVP with a higher NVP content, adhered platelets were remarkably suppressed and the recalcification time was longer. The total water content adsorbed on the PANCNVP film was determined through swelling experiments performed at temperatures of interest. Differential scanning calorimetry and thermogravimetric analysis were used to probe the states of water in the films. Based on the results from these experiments, it was hypothesized that the better hemocompatibility of PANCNVP films with higher NVP contents was due to their higher free water content, because water molecule exchange at the polymer/liquid interface, facilitated by a high free water content, is unfavorable for the formation of surface bound water, which causes poor hemocompatibility. [diagram in text].     

Electrochemical response of ascorbic acid at conducting and electrogenerated polymer modified electrodes for electroanalytical applications: a review

The present short review deals with electroanalytical aspects of electrochemical response of ascorbic acid (Vitamin C) at conducting and electrogenerated polymer modified electrodes. Two main topics are considered: (i) electrocatalytic oxidation of ascorbate at conducting polymer modified electrodes, leading to electroanalytical techniques for ascorbate assay, and (ii) retardation of ascorbate penetration through a layer of electrogenerated polymers, leading to permselective coatings and their diverse uses, especially for biosensing devices.