title: Modeling four and three-way fast high-performance liquid chromatography with ﬂuorescence detection data for quantitation of fluoroquinolones in water samples.
abstract: 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).
authors.affiliation: Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000, Santa Fe, Argentina.
authors.forename: Mirta Raquel
authors.initials: MR
authors.lastname: Alcaráz
authors.affiliation: Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000, Santa Fe, Argentina.
authors.forename: Gabriel G
authors.initials: GG
authors.lastname: Siano
authors.affiliation: Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000, Santa Fe, Argentina.
authors.forename: María Julia
authors.initials: MJ
authors.lastname: Culzoni
authors.affiliation: Department of Analytical Chemistry, Faculty of Sciences, University of Extremadura, 06006, Badajoz, Spain.
authors.forename: Arsenio
authors.initials: A
authors.lastname: Muñoz de la Peña
authors.affiliation: Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000, Santa Fe, Argentina. Electronic address: hgoico@fbcb.unl.edu.ar.
authors.forename: Héctor C
authors.initials: HC
authors.lastname: Goicoechea
mesh_terms: D000465:Algorithms; D002851:Chromatography, High Pressure Liquid; D005453:Fluorescence; D024841:Fluoroquinolones / Q000032:analysis*; D016018:Least-Squares Analysis; D008962:Models, Theoretical; D015999:Multivariate Analysis; D013050:Spectrometry, Fluorescence; D014867:Water / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis*; D014881:Water Supply / Q000032:analysis
chemical_list: D024841:Fluoroquinolones; D014874:Water Pollutants, Chemical; D014867:Water
keywords: Fluoroquinolones; Liquid chromatography; Third-order data; Water samples