Application of a sparseness constraint in multivariate curve resolution - Alternating least squares

Abstract

The use of sparseness in chemometrics is a concept that has increased in popularity. The advantage is, above all, a better interpretability of the results obtained. In this work, sparseness is implemented as a constraint in multivariate curve resolution - alternating least squares (MCR-ALS), which aims at reproducing raw (mixed) data by a bilinear model of chemically meaningful profiles. In many cases, the mixed raw data analyzed are not sparse by nature, but their decomposition profiles can be, as it is the case in some instrumental responses, such as mass spectra, or in concentration profiles linked to scattered distribution maps of powdered samples in hyperspectral images. To induce sparseness in the constrained profiles, one-dimensional and/or two-dimensional numerical arrays can be fitted using a basis of Gaussian functions with a penalty on the coefficients. In this work, a least squares regression framework with L0-norm penalty is applied. This L0-norm penalty constrains the number of non-null coefficients in the fit of the array constrained without having an a priori on the number and their positions. It has been shown that the sparseness constraint induces the suppression of values linked to uninformative channels and noise in MS spectra and improves the location of scattered compounds in distribution maps, resulting in a better interpretability of the constrained profiles. An additional benefit of the sparseness constraint is a lower ambiguity in the bilinear model, since the major presence of null coefficients in the constrained profiles also helps to limit the solutions for the profiles in the counterpart matrix of the MCR bilinear model. © 2017 Elsevier B.V.