title: A new modeling strategy for third-order fast high-performance liquid chromatographic data with fluorescence detection. Quantitation of fluoroquinolones in water samples.
abstract: 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.
authors.affiliation: Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral-CONICET, Ciudad Universitaria, 3000, Santa Fe, Argentina.
authors.forename: Mirta R
authors.initials: MR
authors.lastname: Alcaráz
authors.forename: Santiago A
authors.initials: SA
authors.lastname: Bortolato
authors.forename: Héctor C
authors.initials: HC
authors.lastname: Goicoechea
authors.forename: Alejandro C
authors.initials: AC
authors.lastname: Olivieri
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D024841:Fluoroquinolones / Q000032:analysis*; D013050:Spectrometry, Fluorescence / Q000379:methods*; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D024841:Fluoroquinolones; D014874:Water Pollutants, Chemical