title: Modeling nonbilinear total synchronous fluorescence data matrices with a novel adapted partial least squares method.
abstract: A new residual modeling algorithm for nonbilinear data is presented, namely unfolded partial least squares with interference modeling of non bilinear data by multivariate curve resolution by alternating least squares (U-PLS/IMNB/MCR-ALS). Nonbilinearity represents a challenging data structure problem to achieve analyte quantitation from second-order data in the presence of uncalibrated components. Total synchronous fluorescence spectroscopy (TSFS) generates matrices which constitute a typical example of this kind of data. Although the nonbilinear profile of the interferent can be achieved by modeling TSFS data with unfolded partial least squares with residual bilinearization (U-PLS/RBL), an extremely large number of RBL factors has to be considered. Simulated data show that the new model can conveniently handle the studied analytical problem with better performance than PARAFAC, U-PLS/RBL and MCR-ALS, the latter modeling the unfolded data. Besides, one example involving TSFS real matrices illustrates the ability of the new method to handle experimental data, which consists in the determination of ciprofloxacin in the presence of norfloxacin as interferent in water samples.
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, Santa Fe S3000ZAA, Argentina.
authors.forename: Agustina V
authors.initials: AV
authors.lastname: Schenone
authors.affiliation: Laboratório de Automação e Instrumentação em Química Analítica e Quimiometria (LAQA) Universidade Federal da Paraíba, CCEN, Departamento de Química, Caixa Postal 5093, CEP 58051-970, João Pessoa, PB, Brazil.
authors.forename: Adriano
authors.initials: A
authors.lastname: de Araújo Gomes
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, Santa Fe S3000ZAA, Argentina.
authors.forename: María J
authors.initials: MJ
authors.lastname: Culzoni
authors.affiliation: Department of Chemistry, University of Central Florida, Orlando, FL 32816, USA.
authors.forename: Andrés D
authors.initials: AD
authors.lastname: Campiglia
authors.affiliation: Laboratório de Automação e Instrumentação em Química Analítica e Quimiometria (LAQA) Universidade Federal da Paraíba, CCEN, Departamento de Química, Caixa Postal 5093, CEP 58051-970, João Pessoa, PB, Brazil.
authors.forename: Mário Cesar Ugulino
authors.initials: MC
authors.lastname: de Araújo
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, Santa Fe S3000ZAA, Argentina. Electronic address: hgoico@fbcb.unl.edu.ar.
authors.forename: Héctor C
authors.initials: HC
authors.lastname: Goicoechea
keywords: Ciprofloxacin; Residual modeling; Second-order advantage; Synchronous fluorescence