Comparison of Lycium barbarum fruits polysaccharide from different regions of China by acidic hydrolysate fingerprinting‐based HILIC‐ELSD‐ESI‐TOF‐MS combined with chemometrics analysis

Abstract Introduction Lycium barbarum is an edible fruit widely used in herbal medicines and as a functional food. Polysaccharide is one of the most important active ingredients. Only L. barbarum grown in the Ningxia region of China are officially recognised as suitable for use in traditional Chinese medicine, but the systematic comparison of L. barbarum polysaccharide between Ningxia and the other growing regions of China has been rarely reported. Objective To compare the difference of L. barbarum polysaccharide from different grown regions of China. Methods A chemical fingerprint of L. barbarum polysaccharide hydrolysates was established based on controlled acidolysis combined with hydrophilic interaction liquid chromatography‐evaporative light scattering detection‐electrospray ionisation‐time‐of‐flight‐mass spectrometry (HILIC‐ELSD‐ESI‐TOF‐MS). Then, it was employed for the comparison of L. barbarum samples from different geographical origins of China combined with chemometrics analysis. Results Six monosaccharides [rhamnose (Rha), xylose (Xyl), arabinose (Ara), mannose (Man), glucose (Glu), galactose (Gal)] were qualitatively and quantitatively determined and four glycoconjugates were preliminarily identified from the hydrolysates. Content determination for the polysaccharide and monosaccharide indicated obvious geographical features. The HILIC‐ELSD fingerprint combined with partial least squares‐discriminant analysis (PLS‐DA) was able to differentiate L. barbarum samples from Ningxia, Xinjiang, Gansu and Qinghai regions with 89.19% classification accuracy. Orthogonal projection to latent structure discriminant analysis (OPLS‐DA) was able to differentiate between samples from Ningxia and those from the other three growing regions, polysaccharide and Ara were the potential chemical markers. Conclusions These findings form the basis of a reliable method to trace the region of origin of L. barbarum sample and thereby, improve the quality control of L. barbarum therapeutic polysaccharides.