Advantages of Soft versus Hard Constraints in Self-Modeling Curve Resolution Problems. Penalty Alternating Least Squares (P-ALS) Extension to Multi-Way Problems

Abstract

An extension to the penalty alternating least squares (P-ALS) method, called multi-way penalty alternating least squares (NWAY P-ALS), is presented. Optionally, hard constraints (no deviation from predefined constraints) or soft constraints (small deviations from predefined constraints) were applied through the application of a row-wise penalty least squares function. NWAY P-ALS was applied to the multi-batch near-infrared (NIR) data acquired from the base catalyzed esterification reaction of acetic anhydride in order to resolve the concentration and spectral profiles of 1-butanol with the reaction constituents. Application of the NWAY P-ALS approach resulted in the reduction of the number of active constraints at the solution point, while the batch column-wise augmentation allowed hard constraints in the spectral profiles and resolved rank deficiency problems of the measurement matrix. The results were compared with the multi-way multivariate curve resolution (MCR)-ALS results using hard and soft constraints to determine whether any advantages had been gained through using the weighted least squares function of NWAY P-ALS over the MCR-ALS resolution.