title: Area correlation constraint for the MCR-ALS quantification of cholesterol using EEM fluorescence data: A new approach.
abstract: This work demonstrates the use of a new additional constraint for the Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) algorithm called "area correlation constraint", introduced to build calibration models for Excitation Emission Matrix (EEM) data. We propose the application of area correlation constraint MCR-ALS for the quantification of cholesterol using a simulated data set and an experimental data system (cholesterol in a ternary mixture). This new constraint includes pseudo-univariate local regressions using the area of resolved profiles against reference values during the alternating least squares optimization, to provide directly accurate quantifications of a specific analyte in concentration units. In the two datasets investigated in this work, the new constraint retrieved correctly the analyte and interference spectral profiles and performed accurate estimations of cholesterol concentrations in test samples. This the first study using the proposed area constraint using EEM measurements. This new constraint approach emerges as a new possibility to be tested in general cases of second-order multivariate calibration data in the presence of unknown interferents or in more involved higher order calibration cases.
authors: Institute of Chemistry, Post Graduation Program in Chemistry, Biological Chemistry and Chemometrics Research Group, CEP 59072-970, Natal, RN, Brazil.
authors: Ana Carolina de Oliveira
authors: AC
authors: Neves
authors: IDAEA-CSIC, Jordi Girona 18-26, 08034 Barcelona, Spain.
authors: Romá
authors: R
authors: Tauler
authors: Institute of Chemistry, Post Graduation Program in Chemistry, Biological Chemistry and Chemometrics Research Group, CEP 59072-970, Natal, RN, Brazil. Electronic address: kassiolima@gmail.com.
authors: Kássio Michell Gomes
authors: KM
authors: de Lima
keywords: Area correlation constraint; Cholesterol; Excitation-emission matrix; MCR−ALS