反相毛细管电色谱中溶质保留值与溶剂化结构参数间的定量关系  

Relationship Between Retention and Solvatochromic Parameters of Solutes in Reversed Phase Capillary Electrochromatography

作　　者：张丽华[1] 邹汉法[1] 施维[1] 倪坚毅[1] 张玉奎[1] 

机构地区：[1]中国科学院大连化学物理研究所国家色谱研究分析中心

出　　处：《色谱》1998年第3期203-207,共5页Chinese Journal of Chromatography

基　　金：中科院院长基金;辽宁省青年人才基金

摘　　要：利用线性溶剂化能关系（ＬＳＥＲ）方法，研究了反相毛细管电色谱（ＲＰ－ＣＥＣ）中溶质保留值与溶剂化结构参数间的定量关系。发现决定溶质在ＲＰ－ＣＥＣ中保留行为的主要因素为溶质的体积及溶质作为氢键受体的碱性大小；建立了溶质在ＲＰ－ＣＥＣ中的ｌｏｇｋ′以及保留方程ｌｏｇｋ′＝ｌｏｇｋ′ｗ－Ｓφ中ｌｏｇｋ′ｗ，Ｓ与溶质的溶剂化结构参数间的定量关系；此外，还建立了不同流动相体系间溶质的ｌｏｇｋ′ｗ和Ｓ值的换算方程。Through Linear Solvation Energy Relationships(LSER) method, the main factors that contributed to the retention of solutes in reversed phase capillary electrochromatography(RP CEC) were found to be the solute size and the ability of solute to accept hydrogen bond The former made a positive contribution and the latter made a negative one These were similar to those in RP HPLC. Quantitative relationships between  log k ′, log k ′ w and S in retention equation  log k ′= log k ′ w -Sφ and the solvatochromic parameters of solute were studied respectively in four binary mobile phase systems. The changing trends of coefficients in LSER equation with organic modifier concentration were different from each other. With the larger portion of organic modifier in the mobile phase, s and b increased; m decreased; while a increased with methanol and acetonitrile as organic modifiers and decreased with isopropanol and tetrahydrofuran as organic modifiers. By using these LSER equations, the retention of solute at different organic modifier concentrations could be predicted with good accuracy . In addition, the values of  log k ′ w and S of solute with different organic modifiers could be calculated from each other, so capacity factors of solute in different mobile phases could be further predicted from each other.

关 键 词：毛细管电色谱 CEC 反相 保留值 溶剂化 溶质 

分 类 号：O657.8[理学—分析化学]