Time segment scanning-based quasi-multiple reaction monitoring mode by ultra-performance liquid chromatography coupled with quadrupole/time-of-flight mass spectrometry for quantitative determination of herbal medicines: Moutan Cortex, a case study.

In this study, a time segment scanning-based quasi-multiple reaction monitoring (quasi-MRM) mode was proposed to improve the quantitative performance of UPLC-QTOF-MS/MS. To achieve the quasi-MRM mode, a strategy to select the ion pair (precursor and product ions) of each analyte was adopted as follows. First, a stable and abundant ion by quadrupole was set as precursor ion in MS scan mode. Second, the fragment ions of the precursor ion formed via collision-induced dissociation were measured by time-of-flight (TOF) in MS/MS scan mode; a characteristic, stable and abundant fragment ion (or precursor ion in case of fragment ion unavailable) was designated as the product ion. Third, the detection specificity and sensitivity of the product ion by TOF were strengthened through time segment scanning over a narrowed mass scan range. The proposed quasi-MRM mode achieved simultaneous quantification of fifteen major components in Moutan Cortex, a widely used medicinal herb, as well as its sulfur-fumigated samples. The quasi-MRM mode was methodologically compared with the other two quantitative modes commonly used in the UPLC-PDA-QTOF-MS/MS apparatus, namely UPLC-PDA and extracted ion analysis. The results demonstrated that the quasi-MRM mode performed better in specificity, sensitivity and linearity. The quasi-MRM mode was further validated with regard to precision, accuracy and stability. The research deliverables indicate that the proposed mode improved the quantitative capability of UPLC-QTOF-MS/MS, and therefore could serve as a potential mode for QTOF-MS/MS-based quantification of herbal medicines.