Contribution to second-order calibration based on multivariate curve resolution with and without previous chromatographic synchronization

Abstract

Rotational ambiguity in the bilinear solutions provided by multivariate curve resolution - alternating least-squares (MCR-ALS) leads to an additional source of uncertainty in the estimation of analyte concentrations by second-order multivariate calibration. The phenomenon is particularly important when measuring matrix instrumental data derived from liquid chromatography with spectral detection, where elution time profiles usually vary from sample to sample both in position and shape. This makes the data non-trilinear, precluding the use of unique trilinear decomposition models. The present report compares some analytical results achieved by: (1) the usual MCR-ALS analysis of augmented matrices built from raw matrix data and (2) a previously reported procedure based on synchronizing the MCR-ALS elution time profiles using correlation optimized warping (COW), reconstructing the augmented matrix with the spectra and the aligned chromatograms, and then applying MCR-ALS again with the trilinearity constraint, leading to unique solutions, which is possible because the warping process restores the trilinearity of the data. We show that alternative (2) does not solve the rotational ambiguity issues and artificially modifies the original data, without significant improvements in analytical performance. In the simulated systems, the best average errors for alternative (1) were about 2%, whereas for alternative (2) they were in the range 4–11%. For the experimental system, the corresponding errors were 2–3% and 3–4% respectively, i.e. with no significant improvement in going to alternative (2). All efforts should be directed to reduce the degree of rotational ambiguity by applying a full battery of chemically reasonable constraints.