Modeling four and three-way fast high-performance liquid chromatography with fluorescence detection data for quantitation of fluoroquinolones in water samples

ALCARAZ, MIRTA RAQUEL; SIANO, GABRIEL; CULZONI, MARÍA JULIA; MUÑOZ DE LA PEÑA, ARSENIO; GOICOECHEA, HÉCTOR

ANALYTICA CHIMICA ACTA

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2014 vol. 809 p. 37 - 46

0003-2670

This paper presents a study regarding the acquisition and analytical utilization of four and three-way data, acquired by following the excitation?emission fluorescence matrices at different elution times, in a fast liquid chromatographic HPLC procedure. This kind of data were implemented for first time for quantitative purposes, and applied to the determination of two fluoroquinolones in tap water samples, as a model to show the potentiality of the proposed strategy of four-way data generation. The data were modeled with three well-known algorithms: PARAFAC, U-PLS/RTL and MCR-ALS, the latter conveniently adapted to model third-order data. The second-order advantage was exploited when analyzing samples containing uncalibrated interferences. PARAFAC and MCR-ALS were the algorithms that better exploited the second-order advantage when no peak time shifts occurred among samples. On the other hand, when the quadrilinearity was lost due to the occurrence of temporal shifts, MCR-ALS furnished the better results. Relative error of prediction (REP%) obtained were 9.9% for ofloxacin and 14.0% for ciprofloxacin. In addition, a significant enhancement in the analytical figures of merit was observed when going from second- to third-order data (reduction of ca. 70% in LODs).