Advances in two-dimensional GC with glass capillary columns

A versatile two-dimensional gas chromatograph is described, consisting of 2 separate ovens, one intermediate trap, an auxiliary inlet, and the necessary hardware to effect off-line switching according to the principle of Deans. The unit has been designed for use with high resolution glass capillary columns. The performance of individual instrumental components was critically evaluated. Results showed that low dead volume glass to metal connections were required in the manifold and detector lines to minimize extra-column effects. The mass of the intermediate trap must be low to allow rapid heating. Operational parameters are discussed and examples of some applications are shown.     

Studies on the Complexes of N,N′-Bis[o-(diphenylphosphino)benzylidene]ethylenediamine with Transition Metal Ions

The thermodynamic parameters for the interaction of Cu²⁺, Ni²⁺, Co²⁺, Cd²⁺, andAg⁺ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag⁺ exhibited remarkably higher complexation selectivity.Ag⁺ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg⁺–M²⁺ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag⁺ was observed in both single and competitiveAg⁺–M²⁺ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P₂N₂) with silver,[Ag(P₂N₂)] (NO₃), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P2_1/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) ³ and Z = 4.     

蛋白质变性机理与变性时的热力学参数研究进展

生物大分子是近年来生命科学的研究热点和难点之一,而对蛋白质变性的研究有助于深刻揭示生命现象的机理.利用光谱学和热力学可以分别从微观和宏观角度对蛋白质变性进行研究,并由此得到表征蛋白质变性的热力学参数.这对深入了解蛋白质的折叠与伸展、变性机理、结构稳定性及生命体的新陈代谢等问题具有很大意义.近年来,国内外学者在此方面做了大量的工作,主要涉及蛋白质在水溶液中的变性机理、在有变性剂存在下水溶液中的变性机理及在含有其它物质水溶液中的变性机理.用来表征蛋白质变性的热力学参数有热容、变性自由能、变性焓和变性熵等.本文对这些研究进行了概述.     

Adsorption parameters of cyclobutane carboxylic acid at the interface of a mercury electrode with aqueous solutions of 0.4 M Na2SO4 + 0.1 M H2SO4

Based on the results of the regression analysis of differential capacitance curves of a mercury electrode in solutions of cyclobutane carboxylic acid (CBCA) at 25, 50, and 75°C, the adsorption parameters that enter into both the Frumkin isotherm and the model of two parallel capacitors are estimated. The free energies of adsorption found from the analysis of the temperature dependence of these parameters are incorrect due to the partial blowing out of CBCA during the deaeration of the solutions. The corresponding adsorption parameters are corrected under the assumption that the hydrophobic effect associated with the increase in the liquid-water entropy at the removal from it of CBCA molecules is the same as for n-valeric acid. The physical meaning of the squeezing-out effect is revised.     

固相微萃取参数选择及其对有机锡分析的影响

固相微萃取是一种新型的、不断发展和完善的样品前处理方法，它与其它技术联用可对多种样品基体中挥发、半挥发性有机化合物进行测定。目前，该技术在毒性金属有机化合物中的应用很少。本文分析参数选择对固相微萃取的影响的同时，还对其在有机锡化合物分析中的应用作了综述。     

Analysis of First-Order Reactions with Distributed Parameters

Simple methods of analysis of first-order kinetic processes controlled by distributions of parameters (activation energies and/or frequency factors) are presented. Both the isothermal and nonisothermal regimes are considered. The procedures make use of numerically calculated time derivatives of the concentrations of decaying species (reactants in the case of chemical reactions). They do not require any adjustable initial or boundary values of parameters (like concentration at the infinite time) being thus more accurate and reliable than earlier methods in which kinetic parameters were determined from the concentration, and not from its time derivative. The methods were successfully employed in analysis of the thermally driven cis–trans isomerization of a photochromic crown ether containing the azobenzene moiety incorporated in the crown.     

Probing the surface polarity of native celluloses using genuine solvatochromic dyes

The surface polarity of native celluloses has been investigated by the following solvatochromic dyes: dicyano-bis (1,10)-phenanthroline iron (II) Fe(phen)2 (CN)2 (1), bis(4-N,N-dimethylamino)-benzophenone (2), and cou-marine 153 (3). Linear Solvation Energy (LSE) relationships and the UV/Vis data have been used to characterize the surface polarity of different native cellulose batches in terms of the empirical Kamlet–Taft polarity parameters (hydrogen bond acidity), (hydrogen bond basicity), and * (dipolarity/polarizability). , , *and calculated Reichardt's E T (30) values are reported for various native and regenerated cellulose samples with different degrees of crystallinity. The degree of crystallinity of the cellulose samples has been determined by X-ray. The microcrystalline environment of cellulose can be exactly parameterized in terms of the , and *values. It shows a fairly strong acidity and a low dipolarity/polarizability. For the amorphous sections smaller and larger * values are observed. The correspondence of the empirical polarity parameters determined has been discussed in relation to results from pyrene fluorescence and zetapotential measurements.     

New stationary phase polarity parameters considering the electric intermolecular interactions in gas chromatographic column

Summary The possibility of evaluation of the parameters representing the dispersive solute-solvent interactions is presented. B_N and B_s values can be used to describe the liquid phase polarity and to predict the retention indices of alcohols when the model polyxyethylene glycol dialkyl ethers and their sulphur analogs are used as stationary phases. The possibility of the first ionization potentials estimation is also presented.     

硅钨杂多酸与牛血红蛋白相互作用的研究

多金属氧酸盐作为抗艾滋病病毒、抗流感病毒和抗肿瘤的药物,引起了人们对多金属氧酸与蛋白质之间相互作用的极大关注。蛋白质空间结构的任何变化引起的构象变化都意味着蛋白质分子的活性改变,因此,蛋白质与内源性化合物及许多药物分子之间相互作用的研究一直受到人们关注[1￣3]。血红蛋白是动物及人体内执行输氧任务的蛋白质,是生命机体进行各种生理活动的主要承担者。血红蛋白分子中每条α链和β链含有的色氨酸(Trp)残基分别为α-14Trp、β-15Trp、β-37Trp。Alpert[4]等认为位于疏水腔内的β-37Trp是血红蛋白内源荧光的主要来源,同时β…