Nonlinear Four-Way Kinetic-Excitation−Emission Fluorescence Data Processed by a Variant of Parallel Factor Analysis and by a Neural Network Model Achieving the Second-Order Advantage: Malonaldehyde Determination in Olive Oil Samples

• Published in: Analytical chemistry (Washington) Vol. 80; no. 19; pp. 7248 - 7256
• Main Authors: García-Reiriz, Alejandro, Damiani, Patricia C, Olivieri, Alejandro C, Cañada-Cañada, Florentina, Muñoz de la Peña, Arsenio
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.10.2008
• Subjects: Algorithms; Analytical chemistry; Chemical reactions; Chemistry; Data Interpretation, Statistical; Discriminant analysis; Exact sciences and technology; Fluorescence; Food Analysis - methods; Kinetics; Malondialdehyde - analysis; Malondialdehyde - chemistry; Methylamines - analysis; Methylamines - chemistry; Neural networks; Neural Networks (Computer); Nonlinear Dynamics; Olive Oil; Plant Oils - analysis; Plant Oils - chemistry; Reaction kinetics; Spectrometric and optical methods; Spectrometry, Fluorescence - methods; Second order; Chemical analysis; Factor analysis; Reaction product; Interference; Foodstuff; Olive oil; Neural network; Fluorescence spectrometry; Methylamine; Fluorescent compound; Chemometrics; Principal component analysis
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac8007829

Four-way data were obtained by recording the kinetic evolution of excitation−emission fluorescence matrices for the product of the Hantzsch reaction between the analyte malonaldehyde and methylamine. The reaction product, 1,4-disubstituted-1,4-dihydropyridine-3,5-dicarbaldehyde, is a highly fluorescent compound. The nonlinear nature of the kinetic fluorescence data has been demonstrated, and therefore the four-way data were processed with parallel factor analysis combined with a nonlinear pseudounivariate regression, based on a quadratic polynomial fit, and also with a recently introduced neural network methodology, based on the combination of unfolded principal component analysis, residual trilinearization, and radial basis functions. The applied chemometric strategies are not only able to adequately model the nonlinear data but also to successfully determine malonaldehyde in olive oil samples. This is possible since the experimentally recorded four-way data, modeled with the above-mentioned advanced chemometric approaches, permit the achievement of the second-order advantage. This allows us to predict the analyte concentration in a complex background, in spite of the nonlinear behavior and in the presence of uncalibrated interferences. The present work is a new example of the use of higher-order data for the resolution of a complex nonlinear system, successfully employed in the context of food chemical analysis.