Solvatochromic solvent polarity measurements and retention in reversed-phase liquid chromatography.

Solvatochromic solvent polarity measurements and retention in reversed-phase liquid chromatography.
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反相液相色谱中的溶剂变色溶剂极性测量和保留。

DOI:
10.1021/ac00125a003
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发表时间:
1986
影响因子:
7.4
通讯作者:
Dorsey,JG
Dorsey,JG
中科院分区:
化学1区
文献类型:
--
作者:
Johnson,BP;Khaledi,MG;Dorsey,JG

文献摘要

被引文献

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测定了反相液相色谱中乙腈/水和甲醇/水二元移动的流动相的ε T(30)极性值,并与色谱保留值进行了比较。通常发现log k '对极性的曲线是比常用的log k'对有机改性剂百分比的曲线更好的保留描述符。对于这里检查的332个数据集,使用简单线性回归,绘制log ft'与有机改性剂百分比或ε T(30)极性的平均r2值分别为0.9783和0.9910。在这些log ft'与ε T(30)极性的图中,仅在25种情况下观察到与线性的显著偏离。发现斜率和y轴截距取决于溶质、溶剂系统和色谱柱。斜率和y轴截距都随溶质大小的增加而增加。溶剂化显色溶剂极性的测定可以独立地考察移动的相极性的改变对色谱保留的影响,反相液相色谱(RPLC)中保留的确切机理一直是人们争论的焦点。理想情况下,这种机制的知识将允许保留时间的先验预测,而不管所使用的柱,以及基于计算机的给定分离的优化。阐明保留机制的困难在于溶质在固定相和移动的相中可能发生许多相互作用。因此,溶质保留的研究可能涉及固定相、移动的相或两者的某种组合(实际保留测量)的物理测量。
The£ T (30) polarity values of binary acetonitrile/water and methanol/water mobile phasesused In reversed-phase liquid chromatography were measured and compared with chro-matographic retention. Plots of log ft'vs.£^ 30) polarity were generally found to be better descriptors of retention than commonly used plots of log k'vs. percent organic modifier. For the 332 data sets examined here, the average r2 values for plotting log ft'vs. percent organic modifier or£ T (30) po-larity were 0.9783 and 0.9910, respectively, using simple linear regression. In these plots of log ft'vs.£ T (30) polarity, significant deviations from linearity were observed in only 25 cases. The slope and y intercept were found to be dependent on the solute, solvent system, and column. Both slope and y intercept Increase In magnitude with Increasing solute size. Solvatochromic solvent polarity measurements allow an independent examination of the effect of changing mobile phase polarity on chromatographic retention.The exact mechanism of retention in reversed-phase liquid chromatography (RPLC) has been the subject of much con-troversy anddebate. Ideally, knowledge of this mechanism would allow a priori prediction of retentiontimes regardless of the column being used, as well as computer-based opti-mization of a given separation. The difficulty in elucidating the mechanism of retention lies in the many interactions that a solute may undergo in both the stationary and mobile phases. Thus, investigation of solute retention may involve a physical measurement of the stationary phase, the mobile phase, or some combination of the two (actual retention measurement).