title: Partial least-squares with residual bilinearization for the spectrofluorimetric determination of pesticides. A solution of the problems of inner-filter effects and matrix interferents.
abstract: This paper demonstrates for the first time the power of a chemometric second-order algorithm for predicting, in a simple way and using spectrofluorimetric data, the concentration of analytes in the presence of both the inner-filter effect and unsuspected species. The simultaneous determination of the systemic fungicides carbendazim and thiabendazole was achieved and employed for the discussion of the scopes of the applied second-order chemometric tools: parallel factor analysis (PARAFAC) and partial least-squares with residual bilinearization (PLS/RBL). The chemometric study was performed using fluorescence excitation-emission matrices obtained after the extraction of the analytes over a C18-membrane surface. The ability of PLS/RBL to recognize and overcome the significant changes produced by thiabendazole in both the excitation and emission spectra of carbendazim is demonstrated. The high performance of the selected PLS/RBL method was established with the determination of both pesticides in artificial and real samples.
authors.affiliation: Departamento de Química Analítica, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531 (2000) Rosario, Argentina.
authors.forename: Gisela N
authors.initials: GN
authors.lastname: Piccirilli
authors.forename: Graciela M
authors.initials: GM
authors.lastname: Escandar
mesh_terms: D000465:Algorithms; D001562:Benzimidazoles / Q000032:analysis*; D002138:Calibration; D002219:Carbamates / Q000032:analysis*; D005374:Filtration; D016018:Least-Squares Analysis; D016014:Linear Models; D010575:Pesticides / Q000032:analysis*; D013050:Spectrometry, Fluorescence / Q000379:methods; D013827:Thiabendazole / Q000032:analysis*
chemical_list: D001562:Benzimidazoles; D002219:Carbamates; D010575:Pesticides; C006698:carbendazim; D013827:Thiabendazole