Effects of partial/asymmetrical filling of micelles and chiral selectors on capillary electrophoresis enantiomeric separation: generation of a gradient

The effect of several experimental parameters on enantiomeric separations in micellar capillary electrophoresis (MCE) was studied. A model separation system was tested. It was composed of an acidic phosphate buffer with sodium dodecyl sulfate (SDS) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD) as the chiral selector. A substituted angelicin was used as a chiral analyte. Changes in the concentration of SDS micelles/SDS monomers in the presence of HP-beta-CD and their impact on the enantioselective separation were investigated. Variation of the composition of electrolytes in the individual compartments of the separation system (inlet vial, capillary, and outlet vial) affected both the migration times and the resolution of the enantiomers. Current vs. time dependencies also were monitored during the separations. A mathematical model of electromigration in micellar systems with chiral selector present was proposed and a computer simulation was used to explain the observed phenomena and to confirm the generation of a CD/SDS-micelle concentration gradient under certain experimental conditions. This is the reported first attempt of a computer simulation of the complex, dynamic chiral environment of the CD-SDS-MCE system.     

Eigenmobilities in background electrolytes for capillary zone electrophoresis: III. Linear theory of electromigration

A mathematical model of capillary zone electrophoresis (CZE) based on the conception of eigenmobilities, which are the eigenvalues of a matrix M tied to the linearized governing equations is presented. The model considers CZE systems, where constituents, either analytes or components of the background electrolyte (BGE), are weak electrolytes--acids, bases, or ampholytes. There is no restriction on the number of components nor on the valence of the constituents nor on pH of the BGE. An electrophoretic system with N constituents has N eigenmobilities. In most BGEs one or two eigenmobilities are very close to zero so their corresponding eigenzones move very slowly. However, there are BGEs where no eigenmobility is close to zero. The mathematical model further provides: the transfer ratio, the molar conductivity detection response, and the relative velocity slope. This allows the assessment of the indirect detection, conductivity detection and peak broadening (distortion) due to electromigration dispersion. Also, we present a spectral decomposition of the matrix M to matrices allowing the assessment of the amplitudes of system eigenpeaks (system peaks). Our model predicted the existence of BGEs having no stationary injection zone (or water zone, gap, peak, dip). A common practice of using the injection zone as a marker of the electroosmotic flow must fail in such electrolytes.     

Physico-chemical Characterization of Mo-Hβ Zeolite Catalysts

A series of Mo-impregnated Hβ samples, with MoO3 loading in Hβ zeolite in the mass fraction range of 0. 5%-6.0%, were studied by means of XRD and IR in order to characterize their structures. Mo/Hβ sampies‘ crystallinity almost linearly decreases with increasing the amount of MoO3 loaded, The IR spectra and XRD patterns suggest that the progressive destabilization of the Hβ zeolite structure is caused by increasing Mo loading in (MoO3 Hβ zeolite). During the calcination, Al2(MoO4)3 formed from the dealumination of Hβ zeolite, causes the substantially partial breakdown of the zeolite framework when the Mo loading in MoO3 Hβ is relatively high.     

Nanofibers of Semiconductor Oxides as Sensitive Materials for Detection of Gaseous Products Formed in Low-Temperature Pyrolysis of Polyvinyl Chloride

Nanofibers of semiconducting oxides SnO₂, ZnO, WO₃, produced by the electrospinning method, were tested as sensitive materials for detection of products formed in pyrolysis of polyvinyl chloride in conditions simulating the smoldering of electrically insulating materials upon occurrence of a short-circuit failure in electrical circuits. The method of thermal analysis with mass-spectroscopic determination of gaseous products demonstrated that, in pyrolysis of polyvinyl chloride in the temperature range 200–400°C corresponding to the invisible-smoke stage, the main component of the gas mixture being formed is HCl. It was shown that the materials synthesized can be used to develop gas sensors for early fire warning.     

New Advances in Catalytic Systems for Conversion of CH_4 and CO_2

One of the main goals for developing the C1 chemical industry is the direct conversion of methane and carbon dioxide to useful products. To realize this goal, researches on new catalytic systems are being globally focused. The exploration has been evolved from traditional heterogeneous catalysis into homogeneous catalysis. Coordinate complexes, biochemical and bionics, and photo- and electrochemical catalysis have been extensively studied in recent years. Tests in laboratories have verified for the direct conversion of CH4 to CH3OH that single-pass converstion of CH4 can reach over 70% in both Hg(II) salt and Pt(II) complex systems. The main problem of these systems is the obstacles involving reaction kinetics, so they must be solved before moving to pilot tests. Other catalytic systems discussed in the present article include explorations in the early stage. Among them, features of photo and enzymatic catalyst systems, such as mild reaction conditions, better selectivity and environmentally friendliness     

Effect of temperature on the separation of long DNA fragments in polymer solution

Electrophoresis of long DNA fragments in polymer solutions is still attractive when performed in short capillaries. Then the separations can be accomplished in minutes rather than hours as is usual in various slab electrophoresis techniques. In this paper we focused on the behavior of large DNA fragments in pulsed field capillary electrophoresis under various temperature conditions. The mobility dependence of fragments of lambda-DNA single-cut mixture on various frequencies at three different temperatures showed that the antiresonance mobility minima are shifted to higher frequencies at higher temperatures. This interesting result is explained in terms of the geometration model of DNA motion.     

Accuracy and sensitivity of the determination of rate constants of interconversion in achiral and chiral environments by dynamic enantioselective electrophoresis

The method for determination of rate constants of interconversion of enantiomers in chiral and achiral environments of a dynamic enantioseparation system was investigated in order to reveal its accuracy, sensitivity and robustness. Two significantly different enantioseparation systems were selected, one with a single (well-defined) chiral selector (CS) and the second with a mixture of CSs, and the rate constants of interconversion for these two systems were compared statistically. While the rate constants of interconversion in the chiral environment were found to be significantly different, the rate constants in achiral environment were confirmed to be statistically the same. The accuracy of the method was independent of experimental conditions. Influence of a CS and temperature on the rate of interconversion were discussed within the scope of determined thermodynamic parameters and statistical evaluation. A certain temperature may exist at which two different types of CSs influence the rate of interconversion equally while the extent of their influence may largely differ at other temperatures.     

Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by Cu(Ⅱ)-imine complex

A series of new ligands L₁-L₇ were readily prepared in one step.Friedel-Crafts alkylation of indoles with nitroalkenes catalyzed by a novel Cu（Ⅱ）-L complex has been developed.The remarkable advantages of this reaction are mild reaction conditions,simple workup procedure,high yields of products and the use of ethanol as a green solvent.     

Determination of limiting ionic mobilities and dissociation constants of some local anaesthetics.

The limiting ionic mobilities and thermodynamic acid dissociation constants were calculated from isotachophoretic experiments for the local anaesthetics procaine, tetracaine, lidocaine, trimecaine, bupivacaine, cinchocaine, diperodone, diocaine, cocaine, psicaine-neu, tropacocaine, amylocaine, beta-eucaine and leucinocaine. The pH values at which the local anaesthetics with very similar limiting ionic mobilities can be isotachophoretically separated were determined from simulated mobility curves. The measuring apparatus employed a high-frequency contactless conductivity detector.     

光声光谱技术在层状物质的逐层分析研究中的应用——Ⅰ.光声相位精细谱技术

本文提出光声相位精细谱法(PAPFS)。通过对层状物初始态光声相位扫描和对由此产生的PAPFS曲线的解析,可获取各层与光学热学和空间坐标相关的有价值的信息。本文用该法对彩色相纸作了逐层分析,并将结果与电镜作了比较。与PAPFS相关的层状物光声理论将在本文第Ⅱ部分中涉及。