从一维程序升温气相色谱中快速测定热力学参数，用于在全二维色谱中的保留时间预测。
Rapid determination of thermodynamic parameters from one-dimensional programmed-temperature gas chromatography for use in retention time prediction in comprehensive multidimensional chromatography.
机构信息
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G2G2, Canada.
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G2G2, Canada; Department of Medicinal Chemistry, School of Pharmacy, Guilan University of Medical Sciences, Rasht, Iran.
出版信息
J Chromatogr A. 2014 Jan 17;1325:204-12. doi: 10.1016/j.chroma.2013.12.008. Epub 2013 Dec 17.
A new method for estimating the thermodynamic parameters of ΔH(T0), ΔS(T0), and ΔCP for use in thermodynamic modeling of GC×GC separations has been developed. The method is an alternative to the traditional isothermal separations required to fit a three-parameter thermodynamic model to retention data. Herein, a non-linear optimization technique is used to estimate the parameters from a series of temperature-programmed separations using the Nelder-Mead simplex algorithm. With this method, the time required to obtain estimates of thermodynamic parameters a series of analytes is significantly reduced. This new method allows for precise predictions of retention time with the average error being only 0.2s for 1D separations. Predictions for GC×GC separations were also in agreement with experimental measurements; having an average relative error of 0.37% for (1)tr and 2.1% for (2)tr.
一种新的方法用于估算ΔH(T0)、ΔS(T0)和ΔCP 的热力学参数，用于 GC×GC 分离的热力学建模。该方法替代了传统的等温分离，需要拟合三参数热力学模型到保留数据。在这里，使用非线性优化技术，使用 Nelder-Mead 单纯形算法，从一系列程序升温分离中估计参数。使用这种方法，获得一系列分析物的热力学参数估计所需的时间大大减少。这种新方法允许对保留时间进行精确预测，一维分离的平均误差仅为 0.2s。GC×GC 分离的预测也与实验测量结果一致；对于 (1)tr，平均相对误差为 0.37%，对于 (2)tr，平均相对误差为 2.1%。
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