Four- and five-way excitation-emission luminescence-based data acquisition and modeling for analytical applications....

The latest advances in both theory and experimental procedures on third-order/four-way and fourth-order/five-way calibration methods are discussed. This report is focused on excitation-emission (fluorescence and phosphorescence) matrices generation, employing different variables as the third data mode (time retention in chromatography, pH gradient, fluorescence/phosphorescence lifetime, kinetics, or other chemical treatments). Fully capitalizing on the second-order advantage, it has been possible to develop appealing analytical applications in spite of the complexity of the data. Extraction of the significant chemical information about the system under study as well as the individual abundance of the contributing constituents after proper higher-order data decomposition has allowed to analytical researchers performing quantitative analysis of complex samples. The experimental works reported up to the present are introduced and discussed in order to illustrate concepts. Throughout this work, the analytical benefits achieved by modeling third- and fourth-order data are exposed, attempting to contribute to the ongoing debate in the chemometric community regarding the existence and the true nature of the third-order advantage.