Food Chemistry and Food Development, Department of Life Technologies, FI-20500, University of Turku, Turku, Finland.
Food Chemistry and Food Development, Department of Life Technologies, FI-20500, University of Turku, Turku, Finland.
Anal Chim Acta. 2022 Jun 1;1210:339887. doi: 10.1016/j.aca.2022.339887. Epub 2022 May 1.
Regioisomeric analysis of triacylglycerols (TAGs) in natural oils and fats is a highly challenging task in analytical chemistry. Here we present a software (TAG Analyzer) for automatic calculation of regioisomeric composition of TAGs based on the mass spectral data from recently reported ultra-high performance liquid chromatography electrospray ionization tandem mass spectrometry (UHPLC-ESI-MS/MS) method for analyzing TAG regioisomers. The software enables fast and accurate processing of complex product ion spectra containing structurally informative diacylglycerol [M+NH-RCOH-NH] and fatty acid ketene [RCO] fragment ions. Compared to manual processing, the developed software offers higher throughput with faster calculation as well as more accurate interpretation of chromatographically overlapping isobaric TAGs. The software determines results by constructing a synthetic spectrum to match the measured fragment ion spectrum, and by reporting the optimal concentrations of TAGs used to create the synthetic spectrum. This type of calculation is often extremely challenging for manual interpretation of the fragment ion spectra of isobaric TAGs with shared fragments, hence the need for automated data processing. The developed software was validated by analyzing a wide range of mixtures of regiopure TAG reference compounds of known composition and a commercial olive oil sample. Additionally, the method was also applied for regiospecific analysis of TAGs in human milk as an example of natural fats and oils with a highly complex TAG profile. The results indicate that the software is capable of resolving regioisomeric composition of natural TAGs even of the most complex composition. This novel calculation software combined with our existing UHPLC-ESI-MS/MS method form a highly efficient tool for regioisomeric analysis of TAGs in natural fats and oils.
天然油脂中三酰基甘油（TAG）的立体异构分析是分析化学中极具挑战性的任务。在此，我们介绍了一款软件（TAG Analyzer），用于根据最近报道的超高液相色谱电喷雾串联质谱（UHPLC-ESI-MS/MS）分析 TAG 立体异构体的质谱数据，自动计算 TAG 的立体异构组成。该软件能够快速准确地处理含有结构信息的二酰基甘油[M+NH-RCOH-NH]和脂肪酸烯酮[RCO]碎片离子的复杂产物离子谱。与手动处理相比，开发的软件提供了更高的通量，更快的计算速度以及对色谱重叠等立体异构体的更准确解释。该软件通过构建一个合成谱来匹配测量的碎片离子谱，并报告创建合成谱所用的 TAG 的最佳浓度，从而确定结果。对于手动解释具有共享片段的等重 TAG 的碎片离子谱，这种类型的计算通常极具挑战性，因此需要进行自动数据处理。通过分析一系列已知组成的纯 TAG 参考化合物的混合物和商业橄榄油样品对开发的软件进行了验证。此外，还将该方法应用于人乳中 TAG 的区域特异性分析，人乳是具有高度复杂 TAG 谱的天然油脂的一个例子。结果表明，该软件甚至能够解析最复杂组成的天然 TAG 的立体异构组成。这种新的计算软件与我们现有的 UHPLC-ESI-MS/MS 方法相结合，形成了分析天然油脂中 TAG 立体异构体的高效工具。
