Rapid Profiling and Characterization of the Multicomponents from the Root and Rhizome of Salvia miltiorrhiza by Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry in Combination with Computational Peak Annotation Workflows

Abstract

Herbal components characterization represents a challenging task because of the co-existing of multiple classes of naturally occurring compounds with wide spans of polarity, molecular mass, and the ubiquitous isomerism. The root and rhizome of Salvia miltiorrhiza have been utilized as a reputable traditional Chinese medicine Salviae Miltiorrhizae Radix et Rhizoma (Dan-Shen) in the treatment of cardiovascular disease. Herein, a dimension-enhanced ultra-high performance liquid chromatography/ion mobility/quadrupole time-of-flight mass spectrometry approach in combination with intelligent peak annotation workflows was established aimed to rapidly characterize the multicomponents from S. miltiorrhiza. Due to the sufficient optimization, satisfactory chromatography separation was enabled on an HSS T3 column within 33 min using 0.1% formic acid in water (A) and acetonitrile (B) as the mobile phase, while the data-independent HDMSE in both the negative and positive electrospray ionization modes was utilized for the high-coverage MS2 data acquisition. Streamlined automatic peak annotation by searching an in-house library (recording 198 known compounds) followed by the subsequent confirming steps (e.g., comparison with the reference compounds, fragmentation pathways analysis, and retention behavior comparison, etc.), allowed us to identify or tentatively characterize a total of 86 components (including 50 terpenoids, 21 phenolic acids, and 15 others) from S. miltiorrhiza. Importantly, three-dimensional structure information, such as the retention time, MS1 and MS2 data, and collision cross section (CCS), was provided, which can facilitate the more reliable characterization of herbal components.