速差动力学分析及其应用进展

速差动力学分析是不经分离同时或连续测定混合物中性质密切相关的多组份的重要方法。本文综述了该法在１９８９－１９９２年间国内外新进展，尤着重其在有机，生物混合物中多组份分析的应用及新的计算方法，化学计量学的引入。引用最新文献６７篇。     

Study of donepezil binding to serum albumin by capillary electrophoresis and circular dichroism

The interaction between human serum albumin (HSA) and the acetylcholinesterase inhibitor donepezil, has been studied by means of capillary electrophoresis frontal analysis (CE/FA) and circular dichroism. CE/FA enabled rapid and direct estimation of the quantity of free donepezil present at equilibrium with a physiological level of serum albumin (600 mol L^–1). Application of Scatchard analysis enabled estimation of the binding parameters of HSA towards donepezil, such as association constant and number of binding sites on one protein molecule. Furthermore, due to enantioseparation ability shown by HSA on donepezil in CE mode, displacement experiments were carried out using ketoprofen and warfarin as coadditives to the HSA based running buffer. The addition of these compounds reduced the enantioresolution of donepezil by HSA only when used at high concentration. These data were confirmed and corroborated by circular dichroism (CD) experiments. Using CD, bilirubin was also applied as a ligand specific to site III of HSA. The observed behaviour suggested that donepezil could be considered a ligand with independent binding to sites I and II; although site III is not the highest affinity site, indirect interaction (i.e. cooperative binding) can be assumed.     

Polarographic Behaviour and Determination of Kinetic Parameters of Lead-Pamoate Complex in Dimethyl Sulfoxide

The polarography of lead ion in dimethyl sulfoxide (DMSO) was investigated in the DMSO concentration range 0–80 vol.%. The complex species identified were Pb₂(DMSO)⁴⁺₃, Pb(DMSO)²⁺₃ and Pb(DMSO)²⁺₆ in [DMSO]<10 vol.%, 10< [DMSO]<43 vol.% and [DMSO]>43 vol.%, respectively. In the presence of pamoic acid, the reduction of lead ion in DMSO was two-electron reversible diffusion-controlled at pH≤6.0, but it became irreversible at pH>6.0. The complex species identified was Pb(D_m)₂(P_m)₃(OH)^6? at pH>6.0. The rate constants of electro-reduction and electro-oxidation, activation energies were determined. The hydrolysis constants of lead ion in dimethyl sulfoxide concentration 40–70 vol.% at pH 4.5–6.0 were found to be of the order of 10^?6. The stability constants of the Pb(DMSO)²⁺₃ and Pb(DMSO)²⁺₀ were also determined to be of the orders of 10¹ and 10⁵, respectively.     

Kinetic analysis of thermogravimetric data

Four many curves methods, viz. calculation techniques based on Eqs (30), (31), (34) and (36), respectively, for deriving kinetic parameters from several TG curves recorded with different heating rates are tested on two sets of theoretical TG curves. The maximum reaction rate temperature and conversion, as well as the approximate formulae used for their calculation are discussed. Some aspects of the kinetic compensation effect are analysed. The final conclusion is that the use of the many curves methods is not reasonable.     

Photophysical studies of some dyes in aqueous solution of triton X-100

The spectral (both absorption and fluorescence) and photoelectrochemical studies of a few selective dyes, namely, anionic erythrosin B, neutral riboflavin and cationic safranin O have been carried out in aqueous solution of triton X-100, a neutral surfactant. The results show that the ionic dyes, erythrosin B and safranin O form 1:1 electron donor-acceptor (EDA) or charge-transfer (CT) complexes with triton X-100 both in the ground and excited states, whereas neutral dye riboflavin in its excited state forms 1:1 complex with triton X-100. In these complexes, the dyes act as electron acceptors whereas triton X-100 acts as an electron donor. The fluorescence spectra of erythrosin B and safranin O in presence of triton X-100 show enhancement of fluorescence intensity with red and blue shifts respectively while riboflavin shows normal quenching of fluorescence. A good correlation has been found among photovoltage generation of the systems consisting of these dyes and triton X-100, spectral shift due to complex formation and thermodynamic properties of these complexes.     

ADSORPTION OF 2,4-D ON MODIFIED HYPERCROSSLINKED POLYSTYRENE （NDA-99） AND XAD-4 RESIN

The adsorption behavior of pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution has been investigated using a hypercrosslinked polystyrene adsorbent (NDA-99) modified by dimethylamine group as well as a nonionic macroporous adsorbent (XAD-4). The Langmuir and Freundlich isotherm models were employed to fit the experimental data to describe adsorption mechanism. It shows that NDA-99 resin exhibits an adsorption affinity for 2,4-D higher than XAD-4 resin owing to its exceptional micropore structure and the amine group of the hypercrosslinked matrix.Further studies indicate that the hydrogen bonding interaction and the stronger π-π conjugation play a significant role in the course of the adsorption of 2,4-D on NDA-99 resin, which is in agreement with the IR spectroscopic results and the △E values of HOMO (the highest occupied molecular orbit) of adsorbent and LUMO (the lowest unoccupied molecular orbit) of adsorbate calculated from the MINDO/3 model.     

动力学电位法测定硼

本文根据硼酸，苯乙醇酸，孔雀绿形成三元离子缔合型配合物的反应，用孔雀绿离子选择性电极监测反应速率，在最佳实验条件下，用固定时间法，电位变化与硼量在０．２－５．０μｇ／ｍＬ范围呈线性关系，用於测定标准钢样和玻璃标样中的硼，结果与标准值十分接近。     

The relaxation field for the general case of electrolyte mixtures

The relaxation field for solutions of mixed electrolytes of any type is calculated. the calculation is based on the well-known treatment due to Fuoss-Onsager with the same distance parameter for all the ions in solution. A general conductance-continuity equation has been established and an improved iterative method of calculation, using Laplace transforms, is proposed. The relaxation-field results are derived to the second iteration in the perturbation method of integration.     

Molecular octopus: octa functionalized calix[4]resorcinarene-hydroxamic acid [C4RAHA] for selective extraction, separation and preconcentration of U(VI)

A solvent extraction separation of uranium, in the presence of thorium, cerium and lanthanides with a new calix[4]resorcinarene bearing eight hydroxamic acid groups (C4RAHA) is described. Quantitative extraction of uranium is possible in ethyl acetate solution of C4RAHA at pH 8.0. The lambda(max) and molar absorptivity (varepsilon) for uranium is 356nm and 8352Lmol(-1)cm(-1). The Binding ratio of uranium with C4RAHA as evaluated by Job's method is 4:1. The system obeys Beer's law over the range 0.075-6.0mugml(-1) of uranium with Sandell sensitivity 0.0284mugcm(-2). A preconcentration factor of 142 was achieved by directly aspirating the extract for GF-AAS measurements. The two-phase stability constant evaluated at 25 degrees C for uranium is 15.91. The complexation is characterized by favorable enthalpy and entropy changes. A liquid membrane transport study of uranium was carried out from source to the receiving phase under controlled conditions and a mechanism of transport is proposed. Uranium has been determined in standard and environmental samples.