Enhancement of the static SIMS secondary ion yields of lipid moieties by ultrathin gold coating of aged oil paint surfaces

Static secondary ion mass spectrometry (SIMS) is a powerful technique for identification and localization of pigments and binding media present in traditional paintings. Coating the surface of a cross‐section with a 20 Å thick gold layer improves the yields of secondary ions from the fatty acids and diacids. A chalk tablet containing 1% stearic acid, which was partially covered during gold deposition, is used as a test system to investigate the increase of the organic secondary ion yields upon gold deposition in SIMS imaging. A comparative study of a native and gold‐coated aged surface of a lead white‐containing linseed oil paint demonstrates the enhancement of the organic ion yields on a sample relevant for painting studies. The yields of oil paint‐derived negative ions increase by a factor of 3 whereas the yields of positive ions increase by a factor of 2–4. The different types of charged functional groups determine the degree of improvement in yield. Gold coating improves the ionization process of the fatty acids and does not influence their fragmentation. The dissociation of the lead white by the primary ion beam is reduced due to the gold coating. Copyright © 2004 John Wiley & Sons, Ltd.     

芳香酸的电子结构与缓蚀性能关系的研究

用极化曲线法测试了6个芳香酸化合物对20^#碳钢在HCl溶液中的缓蚀性能，用MNDO方法得到这些分子的前线轨道能量和电荷分布等，经拟合，N原子的净电荷与缓蚀性能间有好的相关性。     

TBP萃取一元有机酸的研究

考察了不同稀释剂中ＴＢＰ对甲酸、乙酸、丙酸、丁酸、氯乙酸、二氯乙酸、三氯乙酸等一元有机酸的萃取．探讨了被萃取物结构与萃取性能的关系及稀释剂性质和温度对萃取的影响．用红外光谱对萃取机理进行了研究．正辛烷中不同有机酸的萃取顺序为，①三氯乙酸＞二氯乙酸＞氯乙酸＞乙酸，萃取平衡常数随有机酸的取代基诱导常数σ＊的增大而增大，两者间遵从Ｔａｆｔ线性关系，诱导效应是影响萃取的主要因素．②丁酸＞丙酸＞乙酸＞甲酸，随诱导效应减弱和空间效应增大，萃取能力增强，表明空腔效应起主要作用．     

对二茂铁基苯甲酸的合成和表征

以对－氨基苯甲酸为原料与亚硝酸钠和盐酸在低温下反应，制备出对－氨基苯甲酸的重氮盐， 再让其与二茂铁（摩尔比 1∶ 1）在低温和相转移催化剂的存在下反应，再由水蒸气蒸馏分离，合成出对－二茂铁基苯甲酸。通过多步实验确定出最佳合成条件，并用元素分析、红外光谱、质谱对产物进行表征。     

Sensitive and Selective Determination of Phenylhydrazine in the Presence of Hydrazine at a Ferrocene Monocarboxylic Acid Modified Carbon Nanotube Paste Electrode

In the present paper, the use of a carbon paste electrode modified by ferrocene monocarboxylic acid (FMC) and carbon nanotubes prepared by a simple and rapid method was described. The modified electrode showed an excellent character for electrocatalytic oxidization of phenylhydrazine (PHZ) and hydrazine (HZ) with a 300 mV separation of both peaks. Differential pulse voltammetric peak currents of PHZ and HZ increased linearly with their concentrations at the range of 0.8 µM to 700 µM and 16 µM to 800 µM and the detection limits (3σ) were determined to be 0.42 µM and 14 µM, respectively.     

Complexation of natural and methylated β-cyclodextrins with long-chain Carboxylic acids in aqueous solutions. Calorimetric studies at 298 K

The formation of complexes between β-cyclodextrin or methyl-β-cyclodextrin and monocarboxylic acids from C₅ to C₁₂ has been studied calorimetrically at 298 K in aqueous buffer phosphate, pH 11.3. When a complex forms, calorimetry enables the calculation of both the enthalpy and the association constant, from which the Gibbs free energy and the entropy of the process can be obtained. The forces involved in the association process are then discussed in the light of the signs and values of the thermodynamic parameters obtained. For β-cyclodextrin, 1:1 inclusion complexes form, characterized by an irregular variation in the values of enthalpies, entropies and association constants at increasing alkyl chain length. A model is proposed to explain this unusual behaviour for acids longer than ten carbon atoms. The association involving methyl-β-cyclodextrin shows, instead, a regular variation of the thermodynamic parameters up to the C₁₂ term. An elongation of the cavity effect is discussed: the cavity behaves as it were deeper than that of the natural cyclodextrins. Association is characterized prevailingly by hydrophobic interactions; for the longer terms, the high and almost invariant entropic contribution determines the large association constants, notwithstanding the positive, unfavorable enthalpic contribution. This is an indication that the relaxation of water molecules from the hydrophobic hydration shells of the external methyl groups is the contribution that mainly determines the association process.     

Relative efficiencies of substituted aromatic monocarboxylic acids as eluents in ion chromatographic separation of inorganic and organic anions

The eluent strengths of para, ortho and meta substituted hydroxy-, nitro-, amino- and sulfobenzoic acids in single column ion chromatographic separations of inorganic and organic anions have been evaluated and compared with benzoic acid.o-Sulfobenzoic acid turns out to be a stronger and efficient eluent compared to others for the separation and determination of monovalent (Cl^–, NO ₂ ^– , Br^–, NO ₃ ^– ) and divalent (SO ₄ ^2– , SeO ₄ ^2– , S₂O ₃ ^2– , S₂O ₆ ^2– ) inorganic anions. In addition it also functions as an appropriate mobile phase for the detection and quantification of some substituted benzoate ions in an aqueous medium.     

Geochemical studies of low molecular weight organic acids in the atmosphere: sources,formation pathways,and gas/particle partitioning

Low molecular weight monocarboxylic acids (LMW monoacids, C₁–C₁₀) are the most abundant gaseous organic compound class in the atmosphere. Formic or acetic acid is the dominant volatile organic compound (VOC) in Earth’s atmosphere. They can largely contribute to rainwater acidity, especially in the tropical forest, and react with alkaline metals, ammonia, and amines, contributing to new particle formation and secondary organic aerosol production. Gaseous and particulate LMW monoacids were abundantly reported in China. They can be directly emitted from fossil fuel combustion and biomass burring; however, the secondary formation is more important than primary emissions via the photochemical oxidation of anthropogenic and biogenic VOCs. In this paper, we review the distributions of LMW monoacids from urban, mountain, and marine sites as well as from rainwater and alpine snow samples and discuss their sources and formation mechanisms in the atmosphere. We also discuss their importance as cloud condensation nuclei (CCN) and provide future perspectives of LMW monoacids study in the warming world.     

The effect of different monocarboxylic acids on the gelation behaviour of Cu ethoxide

Cu ethoxide becomes soluble in methoxyethanol when formic, acetic, or acrylic acid is added. For the complete dissolution, the minimum molar ratio of an acid to Cu ethoxide is two for formic acid (HOFA), and one for acetic (HOAC) or acrylic (HOAA) acid. The solutions of Cu ethoxide with any amounts of formic acid are incapable of forming gels. Those with acetic or acrylic acid/Cu ratio of 1 are able to convert to gels. For the range of the water concentration from 1.5 to 10 M, the gelation time is strongly dependent on [H₂O] for the solution with HOAC/Cu ratio of 1, while it is almost independent for the solution with HOAA. It is suggested that the differences in the behaviour of soluble Cu species derived from the three acids are attributed to different coordination forms and the bonding strength between ligands and copper ions.     

Correlations for the solubility of normal alkanoic acids ando-toluic acid in binary solvent mixtures

Reasonable estimates of ternary solid-liquid equilibrium can be obtained by application of the Wilson and UNIFAC models. The solubilities of octadecanoic, eicosanoic, docosanoic, and o-toluic acids in binary solvents consisting of a common component (cyclohexane) and a varying second component (heptane, ethanol, methanol, 2-propanol, and 1-butanol) have been measured by a dynamic method from 290 to 340 K. The systems containing cyclohexane-alcohols mixed solvents were found to exhibit a synergistic effect of solubility. The best prediction was obtained for the Wilson equation utilizing temperature dependent _ij parameters. For solubilities in nonpolar solvents, the standard deviations for predicted solubilities are comparable to the experimental errors.Presentation to First International Symposium on Solubility Phenomena, University of Western Ontario, London, Ontario, August 21–23, 1984.