Dealing with overlapped and unaligned chromatographic peaks by second-order multivariate calibration for complex sample analysis: Fast and green quantification of eight selected preservatives in facial masks.

The quantification of preservatives in cosmetics has attracted great attentions for their controversial and widespread use. HPLC is a prevailing method for preservatives determination among various analytical methods. However, it takes long time to fully separate these compounds because of the complexity of cosmetic matrices. In this study, a fast and green HPLC-DAD strategy assisted with second-order multivariate calibration methods based on alternating trilinear decomposition (ATLD) and multivariate curve resolution-alternating least squares (MCR-ALS) was developed for the simultaneous determination of eight selected preservatives in complex facial mask samples. This appealing strategy proved to be a useful tool for eliminating unknown interferences in complex matrices without complete separation, which benefited from the "second-order advantages" and thus made the determination of the eight analytes in facial mask samples shorten to 8.2 min under a fast elution program. In particular, for the first time, we focused on the applicability of ATLD method for modeling of HPLC-DAD data with severe signal overlapping and slight time shifts. The spiked recovery values were in the range of 71.4-124.6%, and the RMSEP and REP values ranged from 0.07 to 2.4 μg mL and 1.3-14.5%, respectively, indicating that the ATLD method could provide satisfactory prediction. The resolved spectral profiles and concentration values were compared with those obtained by the MCR-ALS method, an excellent tool for modeling of data deviating from trilinearity. Both qualitative and quantitative results from the two methods were consistent with each other, which evidenced the competence of ATLD method in handling HPLC-DAD data with severe signal overlapping and slight time shifts.