title: Sensitivity equation for quantitative analysis with multivariate curve resolution-alternating least-squares: theoretical and experimental approach.
abstract: A new equation is derived for estimating the sensitivity when the multivariate curve resolution-alternating least-squares (MCR-ALS) method is applied to second-order multivariate calibration data. The validity of the expression is substantiated by extensive Monte Carlo noise addition simulations. The multivariate selectivity can be derived from the new sensitivity expression. Other important figures of merit, such as limit of detection, limit of quantitation, and concentration uncertainty of MCR-ALS quantitative estimations can be easily estimated from the proposed sensitivity expression and the instrumental noise. An experimental example involving the determination of an analyte in the presence of uncalibrated interfering agents is described in detail, involving second-order time-decaying sensitized lanthanide luminescence excitation spectra. The estimated figures of merit are reasonably correlated with the analytical features of the analyzed experimental system.
authors.affiliation: Departamento de Química Analítica, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario and Instituto de Química Rosario (IQUIR-CONICET), Suipacha 531, Rosario (S2002LRK), Argentina.
authors.forename: María C
authors.initials: MC
authors.lastname: Bauza
authors.forename: Gabriela A
authors.initials: GA
authors.lastname: Ibañez
authors.forename: Romà
authors.initials: R
authors.lastname: Tauler
authors.forename: Alejandro C
authors.initials: AC
authors.lastname: Olivieri
mesh_terms: D000465:Algorithms; D000893:Anti-Inflammatory Agents / Q000032:analysis; D002138:Calibration; D003198:Computer Simulation; D004232:Diuretics / Q000032:analysis; D005439:Flufenamic Acid / Q000032:analysis; D005665:Furosemide / Q000032:analysis; D028581:Lanthanoid Series Elements / Q000032:analysis; D016018:Least-Squares Analysis; D057230:Limit of Detection; D008163:Luminescent Measurements / Q000379:methods*; D008956:Models, Chemical; D009010:Monte Carlo Method
chemical_list: D000893:Anti-Inflammatory Agents; D004232:Diuretics; D028581:Lanthanoid Series Elements; D005439:Flufenamic Acid; D005665:Furosemide