An amperometric detector with a tubular electrode deposited on the capillary for capillary liquid chromatography

A procedure is described for the preparation of a tubular electrode by chemical deposition of platinum at the end of a fused-silica capillary. The properties of the electrode were tested under liquid chromatographic conditions, demonstrating that both the static and the dynamic behaviour of the detection system satisfy the requirements of capillary chromatographic separations and compare well with a wall-jet amperometric system and with UV photometric detection. The detection system described is easy to prepare and does not require any time-consuming positioning of the electrode system as it is integrated into the separation part of the apparatus. (C) 1998 Elsevier Science B.V.

Theoretical study of the separation mechanism of ionizable compounds in capillary electrochromatography

The migration mechanism of ionizable compounds in capillary electrochromatography (CEC) is more complicated than in high performance liquid chromatography (HPLC) due to the involvement of electrophoresis and the second chemical equilibrium. The separation mechanism of ionizable compounds in CEC has been studied theoretically. The electrochromatographic capacity factors of ions (k *) in CEC and in the pressurized CEC are derived by phenomenological approach. The influence of pH, voltage, pressure on k* is discussed. in addition, the k * of weak acid and weak base are derived based on acid-base equilibrium and the influence of pH on k * is studied theoretically.

Highly sensitive determination of the methylated p16 gene in cancer patients by microchip electrophoresis

The p16 tumor suppressor gene is inactivated by promoter region hypermethylation in many types of tumor. Recent studies showed that aberrant methylation of the p16 gene is an early event in many tumors, especially in lung cancer, and may constitute a new biomarker for early detection and monitoring of prevention trials. We detected tumor-associated aberrant hypermethylation of the p16 gene in plasma and tissue DNA from 153 specimens using a modified semi-nested methylation-specific PCR (MSP) combining plastic microchip electrophoresis or slab gel electrophoresis, respectively. Specimens were from 79 lung cancer patients, 15 abdominal tumor patients, 30 positive controls and 30 negative controls. The results showed that the positive rate obtained by microchip electrophoresis was more than 26.6% higher and the same speciticity was kept when compared with slab gel electrophoresis. The microchip electrophoresis can rapidly and accurately analyze the PCR products of methylated DNA and obviously improve the positive rate of diagnosis of cancer patients when compared with gel electrophoresis. This method with the high assay sensitivity might be used for detection of methylation of p16 gene and even to facilitate early diagnosis of cancer patients. (C) 2004 Elsevier B.V. All rights reserved.

Protocol of capillary isoelectric focusing to separate extremely acidic and basic proteins

A new set-up was constructed for capillary isoelectric focusing (CIEF) involving a sampling capillary as a bypass fixed to the separation capillary. Sample solutions were subjected to a previously established pH gradient from the sample capillary. Besides performing conventional CIEF, the separation of ampholytic compounds with isoelectric points (p/s) beyond the pH gradient was carried out on this system. This method was termed as pH gradient driven electrophoresis (PGDE) and the basic mathematical expressions were derived to express the dynamic fundamentals. Proteins such as lysozyme, cytochrome C, and pepsin with p/s higher than 10 or below 3 were separated in a pH gradient provided by Pharmalyte (pH 3-10). Finally, this protocol convincingly exhibited its potential in the separation of a solution of chicken egg white.

On-line concentration of proteins in pressurized capillary electrochromatography coupled with electrospray ionization-mass spectrometry

Pressurized capillary electrochromatography (pCEC) and electrospray ionization-mass spectrometry (ESI-MS) have been hyphenated for protein analysis. Taken cytochrome c, lysozyme, and insulin as samples, the limits of detection (LODs) for absolute concentrations are 10(-11) mol (signal-to-noise ratio S/N = 3) with relative standard deviations (RSDs) of retention time and peak area, respectively, of less than 1.7% and 4.8%. In order to improve the detection sensitivity, on-line concentration by field-enhanced sample-stacking effect and chromatographic zone-sharpening effect has been developed, and parameters affecting separation and detection, such as pH and electrolyte concentration in the mobile phase, separation voltage, as well as enrichment voltage and time, have been studied systematically. Under the optimized conditions, the LODs of the three proteins could be decreased up to 100-fold. In addition, the feasibility of such techniques has been further demonstrated by the analysis of modified insulins at a concentration of 20 mu g/mL.

Hybrid organic-inorganic phenyl monolithic column for capillary electrochromatography

A novel hybrid organic-inorganic silica-based monolithic column possessing phenyl ligands for reversed-phase (RP) capillary electrochromatography (CEC) is described. The monolithic stationary phase was prepared by in situ co-condensation of tetraethoxysilane (TEOS) with phenyltriethoxysilane (PTES) via a two-step catalytic sol-gel procedure to introduce phenyl groups distributed throughout the silica matrix for chromatographic interaction. The hydrolysis and condensation reactions of precursors were chemically controlled through pH variation by adding hydrochloric acid and dodecylamine, respectively. The structural property of the monolithic column can be easily tailored through adjusting the composition of starting sol solution. The effect of PTES/TEOS ratios on the morphology of the created stationary phases was investigated. A variety of neutral and basic analytes were used to evaluate the column performance. The CEC columns exhibited typical RP chromatographic retention mechanism for neutral compounds and had improved peak shape for basic solutes.

Electrochromatographic evaluation of a silica monolith capillary column for separation of basic pharmaceuticals

A silica-based monolithic capillary column was prepared via a sol-gel process. The continuous skeleton and large through-pore structure were characterized by scanning electron microscopy (SEM). The native silica monolith has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). Column efficiencies greater than 250000 plates/m for capillary electrochromatography (CEC) separation of basic compounds were obtained. It was observed that retention of basic pharmaceuticals on the silica monolith was mainly contributed by a cation-exchange mechanism. Other retention mechanisms including reversed-phase and normal-phase mechanisms and electrophoresis of basic compounds also played a role in separation. A comparison of the differences between CEC and capillary zone electrophoresis (CZE) separation was also discussed.

两层流体热毛细对流空间实验研究=Space Experiments of Thermo Capillary Convection in Two-liquid Layers

1999年,在我国实践5号卫星上完成了两层流体空间实验,实验研究两层不相混合流体的纯Marangoni对流（温度梯度与界面垂直）与热毛细对流（温度梯度方向与流体界面平行）.前者存在发生Marangoni对流的最小临界温差值△Tc,低于该值流体系统处于静止状态;后者中只要存在沿界面的温度梯度便会产生热毛细对流.空间实验采用石蜡和氟化液两层流体新体系,实现了平整的液-液交界面,并从卫星上传回上万幅数字图像.通过多幅图像叠加处理得到了定量的流速场.数值模拟计算分析了相应工况时对流流动的速度场,两者的流场结构和速度大小基本一致,实验验证了理论模型.

Capillary Effect on Vertically Excited Surface Wave in Circular Cylindrical Vessel

In a vertically oscillating circular cylindrical container, singular perturbation theory of two-time scale expansions was developed in inviscid fluids to investigate the motion of single free surface standing wave including the effect of surface tension.

Flame Propagation of H_2-Air in a Semi-Open Obstructed Tube

针对氢／空气混合物,通过实验研究了其预混火焰在半开口管道中的火焰传播加速现象,结果表明,火焰传播状态随着氢气当量比的变化而发生改变。当氢／空气混合物被点燃后,由于障碍物的扰动,火焰在管道中不断加速传播,并最终到达一准稳态传播。在氢气当量比0.31附近时,火焰速度发生跃变。当氢气当量比足够大时,火焰传播由爆燃态转变为爆轰态。在本实验条件下,爆燃转准爆轰的临界条件是d/Lambda>=2.6（d是圆环形障碍物内径,人是爆轰格胞尺度）。障碍物阻塞比的变化对最大火焰速度和压力提升的影响不明显。

Characters of Surface Deformation and Surface Wave in Thermal Capillary Convection

In the field of fluid mechanics, free surface phenomena is one of the most important physical processes. In the present research work, the surface deformation and surface wave caused by temperature difference of sidewalls in a rectangular cavity have been investigated. The horizontal cross-section of the container is 52 mmx42 mm, and there is a silicon oil layer of height 3.5 mm in the experimental cavity. Temperature difference between the two side walls of the cavity is increased gradually, and the flow on the liquid layer will develop from stable convection to un-stable convection. An optical diagnostic system consisting of a modified Michelson interferometer and image processor has been developed for study of the surface deformation and surface wave of thermal capillary convection. The Fourier transformation method is used to interferometer fringe analysis. The quantitative results of surface deformation and surface wave have been calculated from a serial of the interference fringe patterns.The characters of surface deformation and surface wave have been obtained. They are related with temperature gradient and surface tension. Surface deformation is fluctuant with time, which shows the character of surface wave. The cycle period of the wave is 4.8 s, and the amplitudes are from 0 to 0.55 mu m. The phase of the wave near the cool side of the cavity is opposite and correlative to that near the hot side. The present experiment proves that the surface wave of thermal capillary convection exists on liquid free surface, and it is wrapped in surface deformation.

The Optical Methods on Measuring Surface Deformation and Surface Wave in The Thermal Capillary Convection

An optical diagnostic system consisting of the Michelson interferometer with the image processor has been developed for the study of the kinetics of the thermal capillary convection. The capillary convection, surface deformation, surface wave and the velocity field in a rectangular cavity with different temperature's sidewalls have been investigated by optical interference method and PIV technique. In order to calculate the surface deformation from the interference fringe, Fourier transformation is used to grating analysis. The quantitative results of the surface deformation and surface wave have been calculated from the interference fringe pattern.

A Semi-Empirical Equation of Penetration Depth on Concrete Target Impacted by Ogive-Nose Projectiles

In this paper, the penetration process of ogive-nose projectiles into the semi-infinite concrete target is investigated by the dimensional analysis method and FEM simulation. With the dimensional analysis, main non-dimensional parameters which control the penetration depth are obtained with some reasonable hypothesis. Then, a new semi-empirical equation is present based on the original work of Forrestal et al., has only two non-dimensional combined variables with definite physical meanings. To verify this equation, prediction results are compared with experiments in a wide variation region of velocity. Then, a commercial FEM code, LS-DYNA, is used to simulate the complex penetration process, that also show the novel semi-empirical equation is reasonable for determining the penetration depth in a concrete target.