A new modeling strategy for third-order fast high-performance liquid chromatographic data with fluorescence detection. Quantitation of fluoroquinolones in water samples

ALCARAZ, MIRTA RAQUEL; BORTOLATO A., SANTIAGO; GOICOECHEA, HÉCTOR C; OLIVIERI, ALEJANDRO C.

ANALYTICAL AND BIOANALYTICAL CHEMISTRY

SPRINGER HEIDELBERG

Lugar: HEIDELBERG; Año: 2015 vol. 407 p. 1999 - 2011

1618-2642

Matrix augmentation is regularly employed in extended multivariate curve resolution-alternating least-squares (MCR-ALS), as applied to analytical calibration based on second- and third-order data. However, this highly useful concept has almost no correspondence in parallel factor analysis (PARAFAC) of third-order data. In the present work, we propose a strategy to process third-order chromatographic data with matrix fluorescence detection, based on an Augmented PARAFAC model. The latter involves decomposition of a three-way data array augmented along the elution time mode with data for the calibration samples and for each of the test samples. A set of excitation?emission fluorescence matrices, measured at different chromatographic elution times for drinking water samples, containing three fluoroquinolones and uncalibrated interferences, were evaluated using this approach. Augmented PARAFAC exploits the second-order advantage, even in the presence of significant changes in chromatographic profiles from run to run. The obtained relative errors of prediction were ca. 10 % for ofloxacin, ciprofloxacin, and danofloxacin, with a significant enhancement in analytical figures of merit in comparison with previous reports. The results are compared with those furnished by MCR-ALS.