The present research is focused on the development of a cryogenically modulated (CM) comprehensive two-dimensional gas chromatography-high resolution time-of-flight mass spectrometry (GC × GC-HR ToFMS) method for the in-depth profiling of the unsaponifiable fraction of vegetable oils. Specifically, twelve vegetable oils (9 extra-virgin olive, soybean, peanut, and hazelnut oils) were subjected to analysis, with particular attention devoted to the higher molecular weight constituents (sterols, vitamin E, triterpenic alcohols). Peak assignment was carried out by using commercial unit-mass MS databases, accurate mass data, literature and on-line freely-available mass spectral information, as well as an in-lab-constructed HR ToFMS lipid database. The main objective of the work was to develop a method to define a well-characterized extra-virgin olive oil fingerprint, to be potentially exploited for vegetable oil differentiation. An additional objective of the investigation was to evaluate the performance of the HR ToFMS system (operated at a mass resolution of 25,000 FWHM) under the challenging analytical conditions of a CM GC × GC-based experiment. The HR ToFMS accurate-mass lipid database was (previously) constructed by acquiring, for the main part, the mass spectra of vegetable oil constituents, well-separated from both the matrix and column bleed background.

本研究的重点是用于深度剖析不皂化物级分的低温调制（CM）综合二维气相色谱-高分辨率飞行时间质谱（GC×GC-HR ToFMS）方法的开发植物油。具体而言，对十二种植物油（9种特级初榨橄榄油，大豆，花生和榛子油）进行了分析，尤其关注较高分子量的成分（甾醇，维生素E，三萜醇）。通过使用商业单位质量MS数据库，准确的质量数据，文献和在线免费提供的质谱信息以及实验室内构建的HR ToFMS脂质数据库进行峰分配。这项工作的主要目的是开发一种方法，以定义特征明确的特级初榨橄榄油指纹，可用于植物油的鉴别。研究的另一个目标是在CM GC×基于GC的实验具有挑战性的分析条件下评估HR ToFMS系统（以25,000 FWHM的质量分辨率运行）的性能。HR ToFMS精确质量脂质数据库（以前）是通过获取主要部分植物油成分的质谱图而建立的，该质谱图与基质和色谱柱流失背景均已很好地分离。000 FWHM）在具有挑战性的CM GC×基于GC的实验的分析条件下进行。HR ToFMS精确质量脂质数据库（以前）是通过获取主要部分植物油成分的质谱图而建立的，该质谱图与基质和色谱柱流失背景均已很好地分离。000 FWHM）在具有挑战性的CM GC×基于GC的实验的分析条件下进行。HR ToFMS精确质量脂质数据库（以前）是通过获取主要部分植物油成分的质谱图而建立的，该质谱图与基质和色谱柱流失背景均已很好地分离。