Department of Chemistry, Virginia Commonwealth University, 1001 W. Main St. Richmond, VA, 23284-2006, USA.
Department of Chemistry, Virginia Commonwealth University, 1001 W. Main St. Richmond, VA, 23284-2006, USA.
J Chromatogr A. 2018 Aug 24;1564:128-136. doi: 10.1016/j.chroma.2018.06.007. Epub 2018 Jun 15.
A previously developed liquid chromatographic simulator (see parts I and II) [1-3] is extended to allow for simulations of stationary phase gradients with isocratic and gradient mobile phases. Gradient stationary phases have recently been proposed as means of engineering unique chromatographic selectivities. In the present work, the simulator provides retention times and peak widths that agree with closed form theory for a linear gradient in retention factor and provides accurate retention time predictions for experimentally implemented continuous and discontinuous gradients. Calculation of discontinuous gradients implemented using the commercially available POPLC system have shown good agreement with experiment, with the largest deviation of the simulated retention time from experiment of 4.5%. In addition, simulations of a novel continuous amine gradient column show good agreement with experiment, and give insights into synergistic interactions on column. With the exception of solutes that show evidence of synergistic interactions, the simulated retention times are in agreement with the 95% confidence limits of the experimental values.
先前开发的液相色谱模拟程序（见第 I 部分和第 II 部分）[1-3]得到扩展，以允许使用等度和梯度流动相模拟固定相梯度。梯度固定相最近被提议作为工程独特色谱选择性的手段。在本工作中，该模拟程序提供的保留时间和峰宽与保留因子线性梯度的闭式理论一致，并为实验实施的连续和不连续梯度提供准确的保留时间预测。使用市售的 POPLC 系统实施不连续梯度的计算与实验吻合良好，模拟保留时间与实验值的最大偏差为 4.5%。此外，新型连续胺梯度柱的模拟与实验吻合良好，并深入了解柱上的协同相互作用。除了显示出协同相互作用证据的溶质外，模拟保留时间与实验值的 95%置信限一致。
