Chemometric analysis of comprehensive LC×LC-MS data: Resolution of triacylglycerol structural isomers in corn oil

• A multivariate curve resolution based approach is proposed to resolve LC×LC-MS data.
• Bilinear and trilinear behaviour of LC×LC-MS data is discussed.
• Results obtained by MCR-ALS, MCR-ALS trilinear, PARAFAC and PARAFAC2 are compared.
• TAGs positional isomers in corn oil are resolved and identified.

Comprehensive hyphenated two-dimensional liquid chromatography mass spectrometry (LC×LC-MS) is a very powerful analytical tool achieving high throughput resolution of highly complex natural samples. However, even using this approach there is still the possibility of not resolving some of the analytes of interest. For instance, triacylglycerols (TAGs) structural isomers in oil samples are extremely difficult to separate chromatographically due to their very similar structure and chemical properties. Traditional approaches based on current vendor chromatographic software cannot distinguish these isomers from their different mass spectral features. In this work, a chemometric approach is proposed to solve this problem. First, the experimental LC×LC-MS data structure is discussed, and results achieved by different methods based on the fulfilment of the trilinear model are compared. Then, the step-by-step resolution and identification of strongly coeluted compounds from different examples of triacylglycerols (TAGs) structural isomers in corn oil samples are described. As a conclusion, the separation power of two-dimensional chromatography can be significantly improved when it is combined with the multivariate curve resolution method.

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