Chen Jian-Lian, Liu Chuen-Ying
Department of Occupational Safety and Health, Chung Shan Medical University, Taichung, Taiwan.
J Chromatogr A. 2007 Aug 17;1161(1-2):269-74. doi: 10.1016/j.chroma.2007.05.084. Epub 2007 Jun 2.
A copper mesogenic side-chain polymer (P-C(15)CuC(18)) was cross-linked onto the capillary wall as a stationary film for gas chromatography (GC) separation of alkyl sulfides. These organic sulfides are of interest for their large health impact because of their wide range of volatiles and high reactivities toward metals. Different GC parameters for optimal separation efficiency are discussed for use with a mesogenic polymer column along with flame photometric detection (FPD). Both the carrier gas flow-rate and column temperature were studied to determine the relationship of plate height to the chemical structure of the solutes, as well as to determine the morphology of the mesogenic polymer. Van 't Hoff plots show phase transitions of the stationary mesophase as the column temperature was varied. The results reveal that the separation mechanism might be based on ligand exchange and polarity interaction between the analytes and the stationary phase, with the vapor pressure of the analytes also being important. The former interaction dominates in the lamellar crystalline phase and the latter interaction dominates in the hexagonal columnar-discotic phase. With high reproducibility for retention time (RSD< or =0.37%) and for peak area (RSD< or =5.16%), the GC-FPD system produced linear calibration graphs (r> or =0.9918) for the determination of 13 sulfides with a detection limit below 2.5 ng.
一种铜介晶侧链聚合物（P-C(15)CuC(18)）被交联到毛细管柱壁上，作为用于气相色谱（GC）分离烷基硫化物的固定膜。这些有机硫化物因其挥发性范围广和对金属的高反应活性而对健康有重大影响，因而备受关注。本文讨论了使用介晶聚合物柱和火焰光度检测（FPD）时，为实现最佳分离效率的不同GC参数。研究了载气流速和柱温，以确定塔板高度与溶质化学结构之间的关系，以及确定介晶聚合物的形态。范特霍夫曲线表明，随着柱温变化，固定中间相发生了相变。结果表明，分离机制可能基于分析物与固定相之间的配体交换和极性相互作用，分析物的蒸气压也很重要。前一种相互作用在层状结晶相中占主导，后一种相互作用在六方柱状盘状相中占主导。该GC-FPD系统对保留时间（相对标准偏差≤0.37%）和峰面积（相对标准偏差≤5.16%）具有高重现性，在检测限低于2.5 ng的情况下，对13种硫化物的测定产生了线性校准曲线（r≥0.9918）。
