A sensitivity equation for quantitative analysis with multivariate curve resolution-alternating least-squares: Theoretical and experimental approach

Abstract

A new equation is derived for estimating thesensitivity when the multivariate curve resolution-alternating leastsquares (MCR-ALS) method is applied to second-order multivariatecalibration data. The validity of the expression issubstantiated by extensive Monte Carlo noise addition simulations.The multivariate selectivity can be derived from the new sensitivityexpression. Other important figures of merit, such as limit ofdetection, limit of quantitation, and concentration uncertainty ofMCR-ALS quantitative estimations can be easily estimated fromthe proposed sensitivity expression and the instrumental noise. An experimental example involving the determination of ananalyte in the presence of uncalibrated interfering agents is described in detail, involving second-order time-decaying sensitizedlanthanide luminescence excitation spectra. The estimated figures of merit are reasonably correlated with the analytical features ofthe analyzed experimental system.