用SEC柱和胶束流动相分离小分子的模型

 使用体积排阻色谱 (SEC)柱和胶束流动相成功地分离了一些小分子化合物 ,给出了分离模型。这种分离方式是基于胶束和水相在色谱过程中的不同迁移以及溶质在胶束和水相间的不同分配而实现的 ,其分离的机制与胶束电动色谱 (micellar electrokinetic chromatography,MEKC)十分相似。理论处理的结果表明 ,溶质的保留体积与胶束浓度有关 ;通过溶质的保留体积可得到溶质在胶束和水相间的分配系数。还采用了两种不同的 SEC柱分离了一些脂肪醇 ,验证了这一理论模型 ,测定了它们的分配系数 ,结果表明两种柱测得的小分子醇在胶束和水相中的分配系数具有较好的一致。     

线性程序升温气相色谱基本方程的新应用——Ⅰ.同柱不同载气时如何获得相似的色谱图

1960年,H.W.Habgood和W.E.Harris提出了线性程序升温气相色谱基本方程: integral from n=T_0 to T_r ((1/V_r)dT=r/F) (1)建立了溶质保留温度(T_r)与初始柱温(T_0)、溶质恒温保留体积(V_R)、升温速率(r)、载气流速(F)之间的联系,从而阐明了操作条件对T_r的影响方式,可用于预测不同程度下的T_r值。     

毛细管电中中性溶质在氰基柱上分离机理的研究

 对中性溶质在氰基柱上的毛细管电色谱（CEC）分离特征进行了研究 ,讨论了流动相中有机调节剂种类及其体积分数、缓冲液种类等对溶质迁移速率的影响。通过对样品在氰基柱上的分离行为与其在反相ODS柱和正相SI柱上的分离行为的比较 ,说明中性溶质在氰基柱上的分离机理既具有部分反相特征又具有部分正相特征。受两种机理的影响 ,在不同的操作条件下极性不同的中性溶质在氰基柱上的迁移速率差别很大 ,较一般的正相和反相电中更易出现出峰顺序变化的现象 ,也说明这种分离模式更易于进行分离选择性调节。     

六六六异构物的色谱分离与选择性分子间引力

在气液色谱法中,关于如何选择固定相,提高柱的分离能力已有人总结了一些普遍规律。但对于异构物的分析来说,现有的几个规律有时不够全面。本文通过六六六各异构体的分离来探讨分子结构对分离的影响。一、理论探讨气液色谱中物质的保留体积V_R值取决于固定相分子与溶质分子间的作用力。这种作用力主要有范德华力、氢键及电子转移络合作用。色谱工作者过去一般根据这些力来分析、讨论物质的出峰时     

芳氧苯氧丙酸类除草剂在两种手性柱上的对映体分离

在自制的涂敷型纤维素三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)手性柱和P irkle型(S,S)-W helk-O 1手性柱上对禾草灵,吡氟禾草灵,喹禾灵,噁唑禾草灵4种芳氧苯氧丙酸类除草剂进行了对映体分离。分别考察了在流动相正己烷中,极性醇类添加剂种类、和浓度以及溶质的结构因素对手性分离的影响,探讨了溶质在两种手性柱上的手性识别的机理。结果显示:噁唑禾草灵在(S,S)-W helk-O 1上获得了较好的分离,其它时3种溶质均在CDMPC上获得了较好的分离,各溶质都达到基线分离。两种手性柱的手性识别机理不同,溶质和固定相的结构是手性识别的关键。     

关于分子结构与气相色谱保留值规律的研究

分子结构与其保留值规律是色谱热力学研究的主要内容。鉴于此,不少色谱工作者为探求分子结构与色谱保留值之间的关系作了不懈努力。James和Martin首先注意到在气-液色谱中脂肪酸类物质保留体积的对数与溶质分子中的碳原子数存在着近似的线性关系,因而可以据此推测同系物的保留体积。Ray、Littlewood等人随后指出对于烷烃醇、酯以及甲基酮类化合物在多种固定相上也有类似的关系存在,故Ray建议采用保留体积的对数对分子的键长作图,并以此来鉴别未知物。因     

电中性溶质在反相毛细管电色谱柱上峰展宽的研究

根据溶质在色谱柱中迁移的基本特征及柱分离过程弛豫理论的一般输运方程,在平衡色谱和不单独考虑逆向流的简化情况下,得到了能够说明多种因素对半峰宽影响的流出曲线的二阶中心矩表达式。通过反相毛细管电色谱实验,讨论了电压、柱长及保留因子等因素与峰展宽之间的关系,也探讨了溶质在色谱柱内峰展宽的规律。结果表明:半峰宽随柱长的增加和保留因子的增大而线性增加,随电压的增加而呈非线性减小。     

反相液相色谱中固定相和流动相对柱相比的贡献

依据柱相比的热力学定义和反相液相色谱中溶质的计量置换保留理论(the stoichiometric dispheement heory of solute for retention，SDT-R)，对反相液相色谱中固定相和流动相性质、温度对柱相比的影响进行了研究。结果表明：固定相的种类和配基的疏水性对柱相比影响较大，而流动相中有机溶剂的种类，特别是脂肪酸作为置换剂时，对柱相比的影响更大，而柱相比受温度的影响较小。此外，通过用27种小分子溶质对柱相比的测定，其logI和Z良好的线性关系，进一步证明柱相比是一个与溶质性质无关的常数。     

HPLC法测定醋酸纤维素膜材料界面参数

以醋酸纤维素(CA-398)膜材料为填料,用HPLC法测定无机溶质(如氯化钠,硫酸镁)和多官能团的有机溶质(如糖等)的保留体积V_R’,平衡分配系数K_A’。由HPLC实验数据来确定聚合物膜材料界面参数。     

溶质在两种反相色谱柱中的动力学色谱行为

研究了不同流速下4种溶质在两种不同反相色谱柱上的色谱图及它们的动力学色谱性质,进一步验证了溶质相对保留值(RRT)与流动相流速之间存在良好的双对数线性关系,并对溶质在流速改变时洗脱顺序发生改变的现象从动力学因素上进行了合理的解释;同时还发现色谱填料的孔径及拓扑学构型不同将导致溶质在其上具有不同的动力学色谱参数及动力学色谱行为。     

电填充毛细管色谱柱性能的评价

报道了一种毛细管色谱柱的电填充技术,并进行了柱性能的评价研究。实验表明新的填充方法确保了色谱柱的柱效和重现性。     

Continuous‐Bed Columns Containing Sol‐Gel Bonded Packing Materials for Capillary Electrochromatography

Sol‐gel bonded packing materials in continuous‐bed columns have been prepared for capillary electrochromatography (CEC). Three packing materials were investigated: small‐pore Spherisorb ODS1 (3 μm, 80 Å) with octadecyl as stationary phase, small‐pore mixed‐mode Spherisorb ODS/SCX (3 μm, 80 Å) with octadecyl and propyl sulfonic acid as stationary phases, and large‐pore Nucleosil ODS (7 μm, 1 400 Å) with octadecyl as stationary phase. The characteristics of these columns were compared in terms of electroosmotic flow, efficiency, inertness, and retention factors. In contrast to columns containing sol‐gel bonded ODS, columns containing sol‐gel bonded mixed‐mode ODS/SCX generated nearly pH independent electroosmotic flow (EOF) over pH 2–9. Columns containing sol‐gel bonded large‐pore ODS produced nearly three times lower reduced plate height than those containing small‐pore ODS. Efficiencies of 220,000 plates per meter and 175,000 plates per meter were obtained from columns containing sol‐gel bonded 7 μm, 1 400 Å ODS and columns containing sol‐gel bonded 3 μm, 80 Å ODS, respectively, which are among the highest reported efficiencies for continuous‐bed columns. In CEC, over one million plates per meter and pH independent EOF are expected from continuous‐bed columns containing sol‐gel bonded 1.5 μm particles with large pores and mixed‐mode stationary phases.     

High Performance Size Exclusion Chromatography Using Porous Glass Packing Materials

Abstract

Porous glass packing materials of average particle diameter 5 μm have been packed into a 7.2 mm i.d. x 25 cm column by viscousslurry packing parocedure. Average pore diameters of porous glasses were 170 Â, 500 Â, 1000 A, and 2000 A. The numbers of theoretical plates were between 7000 and 8000 per a column for porous glasses of pore diameters of 170, 500, and 1000 A, and 5000 for that of 2000 A. The retention volumes of narrow molecular weight-distribution polystyrene standards have been determined using tetrahydrofuran as mobile phase for the construction of calibration curves. Separations of polystyrene over molecular weight ranges of 1000 and 4,000,000 have been obtained by combining all four porous glass columns in series. Molecular weight averages of NBS 706 polystyrene have been measured and compared with the values determined with polystyrene gel columns. Both results were equivalent to the manufacturer's data. Porous glasses thus appear to be a useful packing materials for HPSEC.     

Characterization of Amino-, Cyano-alkyl Bonded Silica Columns in Normal-Phase Liquid Chromatography by Using Steroids

Abstract

In order to characterize the chemically bonded phases in HPLC analysis, the retention behavior of fifteen steroids including estrogen, androgen, progestogen and corticoid were systematically examined using dioxan as the stronger component in an n-hexane-binary system. A linear relationship between the logarithm of the capacity ratio and logarithm of the molar concentration of the binary solvent was confirmed for amino- and cyano-type bonded as well as non-bonded silica gel columns. Based on the retention indices of these phases, the retentivity of the packing materials was determined as follows: the amino-type is similar to and the cyano-type is weaker (0.7 times) than bare silica gel when using dioxan as the stronger component. The specific retentivity of an amino column for polar steroids containing phenolic and alcoholic hydroxyl groups suggests a molecular interaction associated with hydrogen bonding between the polar packing surface and solute compounds. The selectivity of amino packing was found to be larger than cyano packing whose retention selectivity is similar to a bare silica gel.     

Characterization of Packing Columns For the Liquid Chromatographic Determination of Corticosteroids in Human Plasma

Abstract

Commercially available columns were characterized by examining the retentions of steroid hormones in liquid chromatography. The phase systems used were dichloromethane-ethanol for silica gel, acetonitrile-water for ODS and CN bonded columns. Solvent compositions were optimized so as to make the retention times of standard steroids less than sixty minutes. Retention data were obtained and reproducibility of the retention times was examined by repetitive injections of the standard samples. These chromatographic phase systems were applied to determine steroid hormones in human plasma following extraction by dichloromethane. CN columns showed the best reproducibility and resolution. Changes in the standing of corticosteroids in plasma under general anesthesia were investigated using CN column systems.     

日本产在线气相色谱仪柱填料的国产化

介绍了用于监测环氧丙烷生产车间原料气组成的日本产在线气相色谱仪柱填料国产化的研制工作。经大量的测试与比较,选出了４种固定相用以代替原进口柱内填充物,经模拟与现场测试,效果好。     

Packing columns for capillary electrochromatography

Considering the current interest in capillary electrochromatography (CEC), performed in packed columns, we present the different methods used to pack capillary columns for use in CEC. General considerations on column packing are given and the column fabrication process is discussed in sufficient detail to allow instruction to those who are not experienced in the field. Five different packing methods are discussed to deliver packing material into the capillary column from a practical view point: slurry pressure packing, packing with supercritical CO2, electrokinetic packing, using centripetal forces, and packing by gravity. Entrapment of particulate material by sintering and sol-gel technology is also mentioned. Although slurry pressure packing procedures are most common, higher separation efficiencies are obtained using other packing approaches. Electrokinetic packing seems to be the simplest technique to deliver the packing material into the capillary columns. Nevertheless, as with the other packing techniques, skill and experience are required to complete all the steps involved in the fabrication of packed columns for CEC.     

毛细管电色谱柱制备技术的进展

介绍了毛细管电色谱开管柱、填充柱和整体柱的各种制备技术及其优势与不足,特别是对于近期发展的毛细管电色谱整体柱的制备方法及其应用进行了系统综述。引用文献100篇。     

A drying step in the protocol to pack capillary columns by centripetal forces for capillary electrochromatography.

Capillary columns have been packed for capillary electrochromatography (CEC) using centripetal forces. The packed columns were maintained under wet conditions or they were dried with nitrogen gas prior to forming the retaining frits. Upon fabrication of the retaining frits, the dried columns were resolvated with the mobile phase. The performance of the columns was evaluated to determine the effect of the drying step during the packing procedure. The columns submitted to the drying step showed improved separation efficiencies and stronger retention characteristics than those kept under wet conditions. The drying step allows the silica-based packing material to be better accommodated inside the capillary column. Upon solvation, the packing material "swells," resulting in a greater packing density, which allows for a stronger retention and improved separation efficiencies. The drying step led to a 13% increase in retention on columns packed with isopropanol. An increase of 15-20% in theoretical plates for the most retained compounds was also observed in such columns.     

Comparison of Retention Indices of Some Explosives and Related Compounds Calculated by Different Mathematical Methods in Reversed-Phase Liquid Chromatography

In reversed phase liquid chromatography, the retention indices of some neutral and acidic explosives and related compounds (nitramines, nitroaromatics, aminoaromatics, and nitrophenols) based on the alkan-2-one, alkyl aryl ketone, and 1-nitroalkane retention index standards have been determined by the application of a new mathematical adaptation method, viz. a multiparametric least-squares regression iterative method. This method was applied to two types of columns. The first group includes six octadecyl-C₁₈ columns with different packing materials and obtained from different manufacturers, while the second group comprises one octyl-C₈ column. The retention indices have been extensively studied using either methanol-water or methanol-phosphate buffer mobile phase systems. The calculated multiparametric retention indices values were compared with those obtained by Guardino's, Grobler's, and Kovàts' methods. The influences of the concentration of the organic modifier in the mobile phase, aqueous mobile phase pH, and the column packing material on the retention indices of the explosives were also investigated. Good agreement was observed between the retention indices calculated by the use of the four mathematical methods for both neutral and acidic explosives.