Rapid fingerprint analysis for herbal polysaccharides using direct analysis in real‐time ionization mass spectrometry

RATIONALE: Herbal polysaccharides have various potential medicinal values. Development of reliable analytical method for the fingerprint analysis of polysaccharides is critical for their quality assessment, origin identification, and authenticity evaluation. METHODS: Mechanochemical extraction (MCE) was used to extract polysaccharide components from different herbal species. Intact polysaccharides were then directly analyzed by direct analysis in real-time mass spectrometry (DART-MS). Standard addition method with isotope-labeled internal standard was used to quantify polysaccharide amounts directly from liquid extract. Multivariate data analysis was further conducted for species classification. RESULTS: The intact and large polysaccharides were decomposed into small fragment ions less than m/z 350 instantaneously using DART ion source. Different polysaccharides showed distinguished fingerprint DART-MS spectra using both individual and mixed herbal species. The liquid supernatant from MCE was validated to be used as direct sample for DART-MS analysis. Quantitation was successfully achieved for polysaccharide contents in Dendrobium officinale from different locations. CONCLUSIONS: A rapid fingerprint protocol in combination of MCE and DART-MS for herbal polysaccharides was developed. The whole process could be accomplished within a few minutes, from raw materials to final spectra, without requirements of pre-digestion and additional sample purification.