Modelling chromatographic behaviour as a function of pH and solvent composition in RPLC

Summary In this work we establish the basic layout of IONICS, an expert system for optimizing the separation of ionogenic solutes in Reversed-Phase Liquid Chromatography, using the pH and the organic-modifier concentration of the mobile phase as parameters. We also present REMO, a front-end system that automates the retention modelling stage, based on a 9-parameter model. This system uses a scale transformation to suppress several numerical problems previously observed and features a strategy for automatic calculation of an initial approximation to the model optimum. The successful application of this system to a set of seven drugs is described. The final models are accurate and have smaller numerical problems. We also describe the use of a genetic algorithm instead of classical non-linear least-squares for fitting the model to the experimental data. Results indicate that genetic algorithms are a valuable, complementary tool for retention modelling.     

pH值对Co/SiO2催化剂还原性的影响

 通过用NH4NO3溶液处理商业硅胶，制备了不同pH值的硅胶载体和一系列Co／SiO2催化剂，并考察了催化剂的还原性能．结果表明，载体pH值的降低，使Co／SiO2催化剂在工业还原条件（673K）下的还原度从30．9％提高到72．4％．用TPR和EXAFS技术研究了Co／SiO2催化剂的还原过程．结果表明，催化剂较高的还原度是由于减弱了还原过程中生成的CoO与载体硅胶之间的相互作用，从而促进了CoO的进一步还原．用FT－IR技术研究了不同pH值硅胶表面硅醇基的存在状态，发现酸性较强的载体上易于发生表面硅醇基间的缩合作用．根据实验结果提出了Co／SiO2催化剂的还原机理．     

Spectrophotometric determination of the acid dissociation constants for cacodylic acid and p-Nitrophenol at elevated temperatures

Using 2.5-dinitrophenol as an optical indicator, the pK_a of cacodylic acid were spectrophotometrically determined at elevated temperatures under saturation vapor pressures. The result is pK_a = -26.41 + 1296/T + 4.973 InT whereT is in Kelvin. In a similar way, the pK_a ofp-nitrophenol were obtained up to 200‡C giving pK_a = -24.82 + 2135/T + 4.353 InT From these results, several thermodynamic functions of cacodylic acid andp- nitrophenol were calculated.     

Factors affecting glycerol production byPichia farinosa under alkaline conditions

Glycerol is an important and valuable chemical that can be produced from renewable resources by fermentation. The desirable features of a successful process are high values of substrate conversions and high yields and concentrations of glycerol in the product broth, coupled with rapid fermentation cycles. Of the various osmophilic and nonosmophilic yeasts tested for their ability to produce glycerol in the presence and absence of steering agents (sodium sulfite or sodium carbonate), an osmophilic yeastPichia farinosa (ATCC 20210) was found to give attractive yields. Important variables influencing glycerol production by this strain under alkaline conditions using sodium carbonate have been investigated. A rapid fermentation (less than 120 h), coupled with high glycerol yields (45%), has been obtained.     

Certified reference materials to support a European thematic strategy for soil protection: the EUROSOILS (IRMM-443) experience

The recent proposal of thematic strategy for soil protection by the European Commission outlines that knowledge of problems associated with soil has increased considerably based on surveys, monitoring systems and data networks. Although this information is very useful, its value for the policy-making process is limited due to a lack of comparability. From this unsatisfying situation the need arises to develop an EU-wide monitoring system accompanied by suitable matrix reference materials. Experiences gained from the development and certification of IRMM-443 (The EUROSOILS) show how to approach the complex problem of providing suitable (i.e. representative) soil CRMs for the arising analytical needs to support existing and upcoming EU legislation.This paper presents briefly the quantitative findings of a certification exercise (adsorption coefficients for atrazine, lindane and 2,4-D, as well as pH in suspension). A comparison of these results with those of an intercomparison exercise organised in 1989 by the German UBA on very similar soils shows the significant improvement in the determination of soil adsorption coefficients that was induced by the EUROSOIL project. Indicative values of total and organic carbon content and nitrogen according to ISO Standards are also presented.Furthermore, the idea of reference soils and derived reference materials (for analytical purposes) as well as reference matrices (substrates for ecotoxicological testing) is highlighted and set into the context of horizontal standardisation of methods.     

Use of a poly(4,4′-diaminobiphenyl) chemically modified electrode as a pH sensor

A chemically modified electrode (CME) for use as a potentiometric pH sensor was constructed by electropolymerizing a poly(4,4′-diaminobiphenyl) coating on a platinum electrode. The resulting CME gave a linear response to pH in the range 1–12 with a slope of ?56 mV pH^?1. The CME functioned well in titration experiments and in pH measurements. No significant interference of a coexisting redox couple with the pH measurements was observed. The mechanism of the pH response of the CME is considered.     

Preparation and characterization of AgSt/AgC1 composite grains

AgSt/AgC1 composite gains were prepared by adding chloride ions to a mixed solvent in which silver stearate （AgSt） grains were dispersed under the condition of controlled pH value and characterized by SEM, XRD, UV and DSC. The results showed that AgSt/AgC1 composite grains were composed of plateqike AgSt grains with small face-centered cubic AgC1 particles formed on the surface of AgSt. UV spectra displayed a red shift of absorption for AgSt/AgC1 relative to pure AgSt or AgC1. DSC showed a new thermal phase transition of AgSt/AgC1 grains.     

Sol-gel法制备W/WO3 H+选择性电极的研究

利用Sol—gel法制备了W／WO3 pH电极，研究了电极的H^ 响应范围、响应灵敏度、响应时间与滞后效应；讨论了热处理温度与H^ 响应行为的关系及干扰离子和溶液温度对H^ 响应的影响；提出了氧化膜内H^ 迁移嵌入方式和响应机理。     

以聚阳离子三甲基烯丙基氯化铵与丙烯酰胺共聚物为基础的高分子复合物的合成和表征

以不同阳离子度及分子量的三甲基烯丙基氯化铵及丙烯酰胺共聚物［Ｐ（ＴＭ ｃｏ ＡＡｍ）］为基础与不同分子量的聚丙烯酸（ＰＡＡ）作用生成相应高分子复合物，进行了结构表征，探讨了ｐＨ值、组份聚合物分子量、阳离子度等对生成复合物的影响，阐述了其形成机制及ｐＨ敏感特性．     

The Effect of Crown Ethers on the Oxidation of Triethylamine by Ferricyanide Ion in Aqueous Solutions at Different pH Values

The effect of benzo-15-crown-5,15-crown-5 and 12-crown-4 on the oxidation of triethylamine by aqueous ferricyanide ion has been studied at pH 4, 7 and 11. The crown ethers retard the normal oxidation process at all pH values, the effect depending on the crown ether concentration. The three crown ethers show the same retardation effect at pH 4 and 7, while at pH 11 the retardation decreases in the order B15C5 > 12C4 > 15C5.