Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral, Ciudad Universitaria, Santa Fe, S3000ZAA, Argentina; Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Godoy Cruz 2290 CABA, C1425FQB, Argentina; Departamento de Química Inorgánica, Analítica y Química Física, INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Intendente Güiraldes 2160, Ciudad Universitaria, Pabellón 2, C1428EGA, Buenos Aires, Argentina.
Department of Analytical Chemistry, University of Extremadura, Badajoz, 06006, Spain; Research Institute on Water, Climate Change and Sustainability (IACYS), Badajoz, 06006, Spain.
Anal Chim Acta. 2019 Nov 20;1083:41-57. doi: 10.1016/j.aca.2019.06.059. Epub 2019 Jul 2.
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.
讨论了三阶/四向和四阶/五向校准方法在理论和实验程序方面的最新进展。本报告重点介绍了激发-发射（荧光和磷光）矩阵的生成，使用不同的变量作为第三数据模式（色谱中的时间保留、pH 梯度、荧光/磷光寿命、动力学或其他化学处理）。充分利用二阶优势，即使数据复杂，也有可能开发出有吸引力的分析应用。在对高阶数据进行适当分解后，从系统中提取关于研究系统的重要化学信息以及单个贡献成分的丰度，使得进行复杂样品定量分析的分析研究人员能够实现这一目标。为了说明概念，介绍和讨论了迄今为止报告的实验工作。在整个工作中，展示了通过对三阶和四阶数据进行建模所获得的分析优势，试图为化学计量学界正在进行的关于三阶优势的存在和真正性质的争论做出贡献。
