Abstract Comprehensive multidimensional chromatographic techniques, such as GC×GC coupled to FID or MS and LC×LC coupled to UV or MS, have gained popularity in recent years. From the analytical perspective, these techniques allow obtaining higher peak capacities and resolution power, as well as adding selectivity from the second orthogonal dimension. From the chemometric point of view, these multidimensional techniques generate highly complex datasets, which present several challenges for their analysis. On the one hand, the selection of the appropriate chemometric data analysis tool requires the understanding of the underlying data structure and its multilinear behavior. On the other hand, peak resolution in complex samples is still a challenge, because of their possible overlapping in one or two chromatographic dimensions despite the increased resolution power. In this work, a comprehensive two-dimensional liquid chromatography method hyphenated simultaneously to PDA and MS detectors was employed for the analysis of a mixture of 31 pharmaceutical compounds. Chemometric evaluation of the obtained two-dimensional chromatograms focuses on two different goals. First, the assessment of the multilinear behavior of the high-dimensional data for each of the two detection modes (LC×LC-UV and LC×LC-MS) and, also, for the multiset data obtained by fusion of the data coming from both detectors. In addition, the chemometric resolution of peaks of overlapping compounds was evaluated using the multivariate curve resolution alternating least squares (MCR-ALS) method. Finally, the advantages of data fusion from UV and MS detectors were discussed, such as the increased ability for compound identification.

中文翻译：

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综合二维液相色谱中的化学计量学：数据结构及其多重线性行为的研究

摘要 综合多维色谱技术，如GC×GC 与FID 或MS 联用和LC×LC 与UV 或MS 联用，近年来得到了普及。从分析的角度来看，这些技术可以获得更高的峰容量和分辨率，并增加了第二个正交维度的选择性。从化学计量学的角度来看，这些多维技术生成高度复杂的数据集，这对其分析提出了几个挑战。一方面，选择合适的化学计量数据分析工具需要了解底层数据结构及其多重线性行为。另一方面，复杂样品中的峰分辨率仍然是一个挑战，因为尽管分辨率提高了，但它们可能在一两个色谱维度上重叠。在这项工作中，使用一种同时与 PDA 和 MS 检测器联用的综合二维液相色谱方法来分析 31 种药物化合物的混合物。获得的二维色谱图的化学计量学评估侧重于两个不同的目标。首先，评估两种检测模式（LC×LC-UV 和 LC×LC-MS）中每一种的高维数据的多线性行为，以及通过融合来自两个探测器。此外，使用多元曲线分辨率交替最小二乘法 (MCR-ALS) 方法评估重叠化合物峰的化学计量分辨率。最后，