Tolley H Dennis, Tolley Samuel E, Wang Anzi, Lee Milton L
Department of Statistics, Brigham Young University, Provo, UT 84602, USA.
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602, USA.
J Chromatogr A. 2014 Dec 29;1374:189-198. doi: 10.1016/j.chroma.2014.10.090. Epub 2014 Nov 10.
This paper examines the separation effects of a moving thermal gradient on a chromatographic column in gas chromatography. This movement of the gradient has a focusing effect on the analyte bands, limiting band broadening in the column. Here we examine the relationship between the slope of this gradient, the velocity of the gradient and the resulting band width. Additionally we examine how transport of analytes along the column at their analyte specific constant temperatures, determined by the gradient slope and velocity, affects resolution. This examination is based primarily on a theoretical model of partitioning and transport of analyte under low concentration conditions. Preliminary predictions indicate that analytes reach near constant temperatures, relative positions and resolutions in less than 100cm of column transport. Use of longer columns produces very little improvement in resolution for any fixed slope. Properties of the thermal gradient determine a fixed solute band width for each analyte. These widths are nearly reached within the first 40-70cm, after which little broadening or narrowing of the bands occur. The focusing effect of the thermal gradient corrects for broad injections, reduces effects of irregular stationary phase coatings and can be used with short columns for fast analysis. Thermal gradient gas chromatographic instrumentation was constructed and used to illustrate some characteristics predicted from the theoretical results.
本文研究了气相色谱中移动热梯度对色谱柱的分离效果。梯度的这种移动对分析物谱带具有聚焦作用,限制了色谱柱中的谱带展宽。在此,我们研究了该梯度的斜率、梯度速度与所得谱带宽度之间的关系。此外,我们还研究了分析物在由梯度斜率和速度决定的其特定分析物恒定温度下沿色谱柱的传输如何影响分离度。这项研究主要基于低浓度条件下分析物分配和传输的理论模型。初步预测表明,在柱传输小于100厘米的情况下,分析物就能达到接近恒定的温度、相对位置和分离度。对于任何固定斜率,使用更长的色谱柱对分离度的提升非常小。热梯度的特性决定了每种分析物的固定溶质谱带宽度。这些宽度在最初的40 - 70厘米内几乎就能达到,此后谱带几乎不再展宽或变窄。热梯度的聚焦作用可校正宽进样,降低不规则固定相涂层的影响,并且可用于短柱进行快速分析。构建了热梯度气相色谱仪器,并用于说明从理论结果预测的一些特性。