A study of preferential solvation of N-alkyl pyridinium iodides in mixed solvents containing acetonitrile

The charge transfer (CT) band maximum of N-alkyl pyridinium iodide (NAPI) has been studied as a function of the composition of binary mixed dipolar aprotic solvents. The deviation from linearity of the energy maximum (E₁₂) and the mole fraction (of a component solvent) plot is explained as due to a preferential solvation by the more polar cosolvent in the binary mixture. The extent of preferential solvation has been observed to vary with the composition, the maximum being towards the less-polar end. The role of hydrogen bond donating ability of a solvent in preferential solvation is discussed.     

高分子量的枝状聚硅烷的合成与表征

根据硅氢加成反应机理设计了“顺点滴式”工艺 ,高效、低耗地合成了甲基苯乙基二氯硅烷和甲基正己基二氯硅烷 .根据Wurtz还原偶联反应原理 ,采用“预聚”和“混聚”两种工艺分别合成枝状共聚硅烷 ,发现运用“预聚”工艺可以合成分子量很高的枝状聚硅烷 .     

N-Acyltrifluoromethanesulfonamides as new chemoselective acylating agents for aliphatic and aromatic amines

This work describes advances in the study of the internal condensation of ammonium salts of N-acylsulfonamides. N-Acyltrifluoromethanesulfonamides show considerable advantages over the non fluorinated analogues by virtue of their higher reactivity and acidity. The reaction chemoselectivity has been investigated using a wide range of amines. The sensitivity of the reaction to steric and electronic effects confirms the potential application of these reagents in chemoselective acylation of polyamines.     

Dynamic Modelling of Nickel Complexation in Xylem Sap of Quercus ilex: A Voltammetric Study

Holm oak (Quercus ilex) is the dominant tree growing on serpentine soils of northeast Portugal, characterized by elevated soil concentrations of Ni and Mg, combined with low Ca concentrations. Apparently Q. ilex does not suffer from excessive concentrations of Ni in the soil. In this work we report a complexation study of nickel by the relevant ligands present in xylem sap: histidine, aspartic acid, oxalic and citric acids, at 0.10 M ionic strength and pH 5.5. Single and mixed complexes were characterized. To validate the proposed complexation model, diluted solutions of Q. ilex xylem sap were titrated with nickel. All studies were done using square‐wave voltammetry (SWV) at a hanging mercury drop electrode. Due to the dynamic nature of SWV, it is possible to obtain the conditional stability constants of the complexes formed but also to have knowledge on the kinetics of the interconversion of the species present.     

Mixed Cationic‐nonionic Surfactants and pH Adjustment Route to Synthesize High‐quality MCM‐48

Using the mixture of cetyltrimethylammonium bromide (CTAB) and p‐Octyl polyethylene glycol phenyl ether (OP‐10) as templates, siliceous MCM‐48 materials can be synthesized with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca.5%) and within a wide range of OP‐10/CTAB ratio (0.08?0.25). The materials were characterized by X‐ray powder diffraction, N₂ adsorption/desorption isotherm, TEM, TG‐DSC and ²⁹Si MAS NMR. Measurements indicated that the use of mixed surfactants allowed better condensation and higher ordering of the cubic mesostructure; at the same time, some properties of these materials were sensitive to the OP‐10/CTAB ratio. It was also found that the reduced pH of the gel which had been crystallized for a certain time gave a highly reproducible synthesis with a high silica yield (about 95%). Furthermore, the reaction mechanism of the synthesis is discussed in detail.     

Surface mixed adsorption films of 2,4,6- trimethylphenol–2,4,6-trichlorophenol at aqueous solution/air interface

 The results of experimental studies of the adsorption at the solution/air interface from an aqueous mixture: 2,4,6-trimethylphenol–2,4,6-trichlorophenol are presented. The surface properties of the above-mentioned mixture were studied by surface potential and surface tension measurements. These measurements were carried out as a function of the concentration of 2,4,6-trimethylphenol aqueous solution at a constant concentration of 2,4,6-trichlorophenol. Using the results obtained and based on the Gibbs equation, Helmholtz formula and Motomura’s method the relative surface excesses of adsorbed substances, effective dipole moments, surface molar fractions of solutes and miscibility of adsorbed films were determined. Received: 7 November 1997 Accepted: 26 February 1998     

The effects of polymer chain rigidification, zeolite pore size and pore blockage on polyethersulfone (PES)-zeolite A mixed matrix membranes

The polyethersulfone (PES)-zeolite 3A, 4A and 5A mixed matrix membranes (MMMs) were fabricated with a modified solution-casting procedure at high temperatures close to the glass transition temperatures (T_g) of polymer materials. The effects of membrane preparation methodology, zeolite loading and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. SEM results show the interface between polymer and zeolite in MMMs experiencing natural cooling is better (i.e., less defective) than that in MMMs experiencing immediate quenching. The increment of glass transition temperature (T_g) of MMMs with zeolite loading confirms the polymer chain rigidification induced by zeolite. The experimental results indicate that a higher zeolite loading results in a decrease in gas permeability and an increase in gas pair selectivity. The unmodified Maxwell model fails to correctly predict the permeability decrease induced by polymer chain rigidification near the zeolite surface and the partial pore blockage of zeolites by the polymer chains. A new modified Maxwell model is therefore proposed. It takes the combined effects of chain rigidification and partial pore blockage of zeolites into calculation. The new model shows much consistent permeability and selectivity predication with experimental data. Surprisingly, an increase in zeolite pore size from 3 to 5 Å generally not only increase gas permeability, but also gas pair selectivity. The O₂/N₂ selectivity of PES-zeolite 3A and PES-zeolite 4A membranes is very similar, while the O₂/N₂ selectivity of PES-zeolite 5A membranes is much higher. This implies the blockage may narrow a part of zeolite 5A pores to approximately 4 Å, which can discriminate the gas pair of O₂ and N₂, and narrow a part of zeolites 3A and 4A pores to smaller sizes. It is concluded that the partial pore blockage of zeolites by the polymer chains has equivalent or more influence on the separation properties of mixed matrix membranes compared with that of the polymer chain rigidification.     

Minimax principles for elliptic mixed hemivariational–variational inequalities

In this paper, minimax principles are explored for elliptic mixed hemivariational–variational inequalities. Under certain conditions, a saddle-point formulation is shown to be equivalent to a mixed hemivariational–variational inequality. While the minimax principle is of independent interest, it is employed in this paper to provide an elementary proof of the solution existence of the mixed hemivariational–variational inequality. Theoretical results are illustrated in the applications of two contact problems.     

钼钨铌磷杂多化合物的研究（Ⅰ）：杂多酸的合成和表征

提出了分步酸化一分步加料合成[PNb_2Mo_xW_(10-x)O_(40)]~(5-)(x=0,2,4,6)系列杂多酸的方法,给出了最佳配料比和生成反应的pH值,并进行了红外、紫外、极谱、电位滴定及热稳定性研究。