双烯合成反应与气相色谱法联合测定油品中共轭二烯烃含量的研究 Ⅱ.短毛细管柱气相色谱法

在填充柱气相色谱法的基础上，使用１２ｍ×０．２２ｍｍｉ．ｄ．的ＳＥ－３０短毛细管柱（ＷＣＯＴ），分析了乙烯生产副产物——未加氢裂解汽油（５５℃～２２０℃馏分）中共轭二烯烃的含量，分析一次需２２ｍｉｎ，内标物正十六烷得到了很好的分离。     

The analysis of lubricating oil additives by supercritical fluid chromatography with packed and open tubular capillary columns

Lubricating oil additives have been analyzed by supercritical fluid chromatography on open tubular and packed capillary columns. Carbon dioxide and modified carbon dioxide were used as mobile phases and detection was accomplished by flame ionization and micro UV. Rapid and efficient analysis of the lubricating oil additives was demonstrated.     

Dependence of the relative retention of organic compounds on the nature and pressure of the carrier gas and on the thickness of the PEG-20M film in the capillary column

The effects of the carrier gas nature and pressure on the relative retention values of organic compounds were studied using a series of capillary columns differing in the film thickness of the polar stationary phase (PEG-20M). Relative retention depends linearly on the carrier gas pressure. This dependence becomes more pronounced in the following order of carrier gases: helium < nitrogen < carbon dioxide. The limiting relative retention at a carrier gas pressure approaching zero rather than relative retention values measured experimentally (relative retention time, Kovats retention index,etc.) is an invariant characteristic of a compound subjected to chromatography. For the carrier gases studied, the limiting retention values almost does not depend on the nature of the carrier gas used. The limiting indicating the complex absorption-adsorption nature of these parameters. Dissolution of a carrier gas in the stationary liquid phase has an effect on the relative retention. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2177–2186, December, 1997.     

Determination of Nonsteroidal Anti‐inflammatory Drugs in Serum by Microchip Capillary Electrophoresis with Electrochemical Detection

A simple and rapid method has been developed for the analysis of four nonsteroidal anti‐inflammatory drugs (NSAIDs) in serum using microchip capillary electrophoresis with pulsed amperometric detection. The selected NSAIDs (salicylic acid, acetaminophen, diflunisal, and diclofenac) are among the most commonly used drugs to treat fever, inflammation, and pain. Used above the therapeutic levels, these drugs can cause a wide variety of adverse effects and their fast analysis could have a significant impact in treatment and recovery of the patients. Several conditions, including separation potential, pH, and concentration of the electrolyte solution were studied to optimize the separation and detection. In this study, salicylic acid, acetaminophen, diflunisal, and diclofenac were separated in less than 2 minutes using a 5 mM borate buffer at pH 11.5 and a separation potential of +1200 V. Linear relationships were obtained between the concentration and peak current in the 0.5–15.3 μg/mL range and detection limits around 0.26 μg/mL. After 30 consecutive injections, the stability of both the response and migration time of the analytes showed relative related deviations of less than 4.6% and 1.0%, respectively. The potential of this method was verified by spiking a bovine serum sample with the four NSAIDs and analyzing the recovery ratio.     

Search of ligands for the amyloidogenic protein beta2-microglobulin by capillary electrophoresis and other techniques

Beta2-microglobulin (beta2-m) is a small amyloidogenic protein normally present on the surface of most nucleated cells and responsible for dialysis-related amyloidosis, which represents a severe complication of long-term hemodialysis. A therapeutic approach for this amyloidosis could be based on the stabilization of beta2-m through the binding to a small molecule, and consequent inhibition of protein misfolding and amyloid fibril formation. A few compounds have been described to weakly bind beta2-m, including the drug suramin. The lack of a binding site for nonpolypeptidic ligands on the beta2-m structure makes it difficult for both the identification of functional groups responsible for the binding and the search of hits to be optimized. The characterization of the binding properties of suramin for beta2-m by using three different techniques (surface plasmon resonance, affinity CE (ACE), ultrafiltration) is here described and the results obtained are compared. The common features of the chemical structures of the compounds known to bind the protein led us to select 200 sulfonated/suramin-like molecules from a wider chemical library on the basis of similarity rules, so as to possibly single out some interesting hits and to gain more information on the functional groups involved in the binding. The development of screening methods to test the compounds by using ultrafiltration and ACE is described.     

Organically modified sols as pseudostationary phases for microchip electrophoresis

We demonstrate that the selectivity of microchip electrophoresis separations is greatly improved by the presence of organically modified silica (Ormosil) sols in the run buffer. A negatively-charged N-(trimethoxysilylpropyl)ethylenediamine triacetic-acid (TETT)-based sol is used for improving the selectivity between nitroaromatic explosives and a methyltrimethoxysilane (MTMOS)-based sol is employed for enhancing the microchip separation of environmental pollutants, aminophenols. These sols are added to the run buffer and act as pseudostationary phases. Their presence in the run buffer changes the apparent mobility of studied solutes, and leads to a higher resolution. The observed mobilities changes reflect the interactions between the Ormosil sols and the solutes. Relevant experimental variables have been characterized and optimized. The diverse chemistry of Ormosil sols should be extremely useful for tailoring the selectivity of a wide range of electrophoresis microchip separations.     

Contactless conductivity detection of synthetic polymers in non-aqueous size-exclusion electrokinetic chromatography

A capacitively coupled contactless conductivity detection (CCD) system has been applied for the detection of neutral synthetic polymers in capillary size-exclusion electrokinetic chromatography (SEEC). Polystyrene standards, that were used as a model compounds, were separated on a capillary column packed with porous 10 microm silica particles with an electrokinetically driven mobile phase, and detected by CCD and UV detection simultaneously. Mass-calibration curves for polystyrene were constructed. Satisfactory results were obtained for the linearity, the run-to-run repeatability (<0.2% for the relative retention and <4% for the peak area) and the robustness of the detector. One of the major issues in this preliminary study was to investigate the origin of the peaks observed for the polystyrene standards. The effect of the molar mass of the polystyrenes on the sensitivity was small. Therefore, the signals obtained could not be explained as the result of an increased viscosity and a decreased solution conductivity of the solute zone. An alternative hypothesis is suggested, and recommendations for further research are given.     

Low-temperature bath/coupled-capillary/sweeping-micellar electrokinetic capillary chromatography for the separation of naphthalene-2,3-dicarboxaldehyde-derivatized dopamine and norepinephrine

The use of a low-temperature (0 degrees C) bath-assisted coupled capillary for the separation of naphthalene-2,3-dicarboxaldehyde (NDA)-derivatized dopamine and norepinephrine using the sweeping-micellar electrokinetic capillary chromatography (MEKC) mode is described. In this technique, a capillary consisting of two portions with different inside diameters is used. Therefore, the field strength inside the capillary is different. Hence, the electrophoretic migration velocities of the analytes and the electro-osmotic flow (EOF) also are different. Furthermore, when a portion of the capillary (wide portion, used for sweeping) is immersed in a low-temperature bath, the viscosity of the buffer and the retention factor of the analytes inside are increased. Thus, not only are the interactions between the SDS micelles and the analytes increased, but the SDS-analytes also move more slowly. As a result, a more complete separation can be achieved, even when the sample injection volume is large, up to approximately 2 microL. In general, when the volume of an injected sample is larger, the effects of sweeping and separation would become insufficient, especially when the retention values (k) of the analytes are quite different. However, this limitation can be improved when the low-temperature bath/coupled capillary/sweeping-MEKC mode is used.     

天祝煤MRF工艺热解焦油的组成分析

本文对天祝煤ＭＲＦ（ＭｕｔｉｓｔａｇｅＲｏｔａｒｙＦｕｒｎａｃｅ）热解焦油进行了常规及元素分析，了解其基本特性；用毛细管色谱分别对焦油各馏分进行了分析，共定性定量了１０３种化合物，酚类化合物以低级酚（苯酚、甲酚）为主，中性化合物为多烷基芳烃衍生物、脂肪族链状烷烃和烯烃。上述分析结果为从焦油中提取酚类化工原料或将其加工成各种燃料油的可行性提供了依据。     

混合模式硅胶基质毛细管电色谱整体柱的制备及其电色谱性能研究

采用温和条件下的溶胶-凝胶技术，成功制备了阴离子交换-反相混合模式硅胶基质毛细管电色谱整体柱。通过调整反应液中不同前体的比例，优化了整体柱的制备条件。通过扫瞄电镜，对柱床进行了表征和分析。实验发现，所制备的整体柱电渗流的方向和大小可随流动相pH值的改变而改变，在酸性和中性条件下，具有从阴极流向阳极的电渗流；当流动相pH值升至约7．5时，电渗流方向发生了反转（由阳极流向阴极）。在优化的实验条件下，用所制备的整体柱对所考察的酸性（中性）化合物实现了快速分离，并获得了高达160，000N／m的柱效。