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

M.R. ALCARÁZ; G.G. SIANO; M.J. CULZONI; A. MUÑOZ DE LA PEÑA; H.C. GOICOECHEA

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).