Dipartimento di Scienza e Tecnologia del Farmaco, Università degli Studi di Torino, Via P. Giuria 9, 10125, Torino, Italy.
Anal Bioanal Chem. 2018 Jul;410(19):4657-4668. doi: 10.1007/s00216-018-0922-0. Epub 2018 Feb 13.
Fragrances and products deriving from essential oils are often formulated or diluted in aqueous media, usually ethanol/water. Gas chromatography (GC) is the technique of choice to analyze volatiles. However, when using columns coated with conventional stationary phases, its application to aqueous samples often requires time-consuming and/or discriminative sample preparation techniques to extract the target analytes from the aqueous medium, so as to avoid its direct injection. In GC with conventional columns, water produces peak asymmetry, poor sensitivity and efficiency, strong adsorption, stationary phase degradation, and, last but not least, it is not easy to detect reliably when present in high amounts. In 2012, Armstrong's group introduced new fully water-compatible ionic-liquid (IL)-based GC capillary columns based on phosphonium and imidazolium derivative cations combined with trifluoromethanesulphonate. These columns were recently made available commercially by Supelco, under the trade name Watercol™. These derivatives maintain IL's unique selectivity and chromatographic properties, and enable water to be used as injection solvent, thus avoiding the sample preparation procedures required by conventional columns. This study reports and critically discusses the results of commercially available water-compatible IL columns for direct analysis of aqueous samples in the fragrance and essential oil fields by GC with thermal conductivity (TCD) and/or flame ionization detectors (FID). The results showed that water-compatible IL-based stationary phases can successfully be adopted for qualitative and quantitative analysis of fragrances and essential oils directly diluted in aqueous solvents. On the other hand, the study also shows that their inertness needs to be further increased and (possibly) the range of operative temperature extended when water is the main solvent of the sample.
香水和精油产品通常在水介质中配制或稀释,通常是乙醇/水。气相色谱(GC)是分析挥发性物质的首选技术。然而,当使用涂有常规固定相的柱子时,其应用于水相样品通常需要耗时且/或具有鉴别性的样品制备技术,以从水介质中提取目标分析物,从而避免直接进样。在使用常规柱子的 GC 中,水会产生峰不对称、灵敏度和效率差、强吸附、固定相降解等问题,最后但并非最不重要的是,当大量存在时,很难可靠地检测到。2012 年,Armstrong 小组引入了新型完全水兼容的基于离子液体(IL)的 GC 毛细管柱,这些柱子基于膦和咪唑衍生阳离子与三氟甲磺酸根结合。这些柱子最近由 Supelco 以 Watercol™的商品名商业化供应。这些衍生物保持了 IL 的独特选择性和色谱性能,并能够将水用作进样溶剂,从而避免了常规柱子所需的样品制备程序。本研究报告并批判性地讨论了市售的水兼容 IL 柱在 GC 中用于直接分析香水和精油领域的水相样品的结果,使用的检测器为热导(TCD)和/或火焰离子化(FID)。结果表明,水兼容的 IL 固定相可以成功地用于直接稀释在水溶剂中的香水和精油的定性和定量分析。另一方面,该研究还表明,当水是样品的主要溶剂时,需要进一步提高其惰性,并可能扩大操作温度范围。