Multi-way partial least-squares coupled to residual trilinearization: a genuine multi-dimensional tool for the study of third-order data. Simultaneous analysis of procaine and its metabolite p-amino benzoic acid in equine serum

PATRICIA C. DAMIANI; ISABEL DURÁN-MERÁS; ALEJANDRO G. GARCÍA-REIRIZ; ANA JIMÉNEZ-GIRÓN; ARSENIO MUÑOZ DE LA PEÑA; ALEJANDRO C. OLIVIERI

ANALYTICAL CHEMISTRY

American Chemical Society

Año: 2007 vol. 79 p. 6949 - 6958

0003-2700

A new third-order multivariate calibration approach, based on the combination of multiway-partial leastsquares with a separate procedure called residual trilinearization (N-PLS/RTL), is presented and applied to multicomponent analysis using third-order data. The proposed chemometric algorithm is able to predict analyte concentrations in the presence of unexpected sample components, which require strict adherence to the secondorder advantage. Results for the determination of procaine and its metabolite p-aminobenzoic acid in equine serum are discussed, based on kinetic fluorescence excitationemission four-way measurements and application of the newly developed multiway methodology. Since the analytes are also the reagent and product of the hydrolysis reaction followed by fast-scanning fluorescence spectroscopy, the classical approach based on parallel factor analysis is challenged by strong linear dependencies and multilinearity losses. In comparison, N-PLS/RTL appears an appealing genuine multiway alternative that avoids the latter complications, yielding analytical results that are statistically comparable to those rendered by related unfolded algorithms, which are also able to process fourway data. Prediction was made on validation samples with a qualitative composition similar to the calibration set and also on test samples containing unexpected equine serum components.p-aminobenzoic acid in equine serum are discussed, based on kinetic fluorescence excitationemission four-way measurements and application of the newly developed multiway methodology. Since the analytes are also the reagent and product of the hydrolysis reaction followed by fast-scanning fluorescence spectroscopy, the classical approach based on parallel factor analysis is challenged by strong linear dependencies and multilinearity losses. In comparison, N-PLS/RTL appears an appealing genuine multiway alternative that avoids the latter complications, yielding analytical results that are statistically comparable to those rendered by related unfolded algorithms, which are also able to process fourway data. Prediction was made on validation samples with a qualitative composition similar to the calibration set and also on test samples containing unexpected equine serum components.