IQUIR   05412
INSTITUTO DE QUIMICA ROSARIO
Unidad Ejecutora - UE
artículos
Título:
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
Autor/es:
ALEJANDRO CESAR OLIVIERI; DURAN MERAS, ISABEL; ALEJANDRO GARCÍA-REIRIZ,; JIMENEZ GIRON, ANA; MUNOZ DE LA PENA, ARSENIO
Revista:
ANALYTICAL CHEMISTRY
Editorial:
American Chemical Society
Referencias:
Año: 2007 vol. 79 p. 6949 - 6958
ISSN:
0003-2700
Resumen:
A new third-order multivariate calibration approach, based on the combination of multiway-partial least-squares 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 second-order advantage. Results for the determination of procaine and its metabolite p-amino benzoic acid in equine serum are discussed, based on kinetic fluorescence excitation-emission four-way measurements, and application of the newly developed multi-way 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 (PARAFAC) is challenged by strong linear dependencies and multilinearity losses. In comparison, N-PLS/RTL appears an appealing genuine multi-way alternative which avoids the latter complications, yielding analytical results which are statistically comparable to those rendered by related unfolded algorithms which are also able to process four-way 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.