Exploiting second-order advantage from mathematically modeled liquid chromatography–mass spectrometry data for simultaneous determination of polyphenols in Chinese propolis

The quantification of polyphenols in propolis has attracted considerable concerns for their biological properties. Liquid chromatography–mass spectrometry (LC–MS) coupled with chemometrics multivariate calibration analytical strategy was developed for simple and rapid determination of eleven polyphenols in Chinese propolis. The eleven polyphenols were fast eluted out within 7.0 min, and then they were detected by mass spectrometry operated in the full scan mode. The acquired second-order data of LC–MS were resolved by two well-known chemometrics tools including alternating trilinear decomposition (ATLD) and multivariate curve resolution-alternating least squares (MCR-ALS). With the aid of the distinctive “second-order advantage”, satisfactory resolution and reliable results were obtained in the presence of chromatographic shifts, serious co-eluted peaks and diverse unknown interferences. The mean   value of spiked recoveries obtained by the ATLD and MCR-ALS methods for eleven polyphenols in propolis samples were in the range of 81.2–109.1% and 75.8–107.1%, respectively, which have verified by the LC–MS/MS method. Statistical parameters and analytical figures of merit were also used to assess the performances of the proposed strategy. All these results demonstrated that the proposed strategy opened a new avenue for quantification of the targeted polyphenols in complex propolis samples for quality monitoring, which does not require toilsome sample pretreatments, elaborate experimental conditions and more advanced high cost instrumentations.