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Identification of chemical markers in Cordyceps sinensis by HPLC-MS/MS


Authentication and quality assessment of Cordyceps sinensis, a precious and pricey natural product that offers a variety of health benefits, is highly significant. To identify effective chemical markers, authentic C. sinensis was thoroughly screened by using HPLC-MS/MS. In addition to many previously reported ingredients, two glycosides, i.e., cyclo-Ala-Leu-rhamnose and Phe-o-glucose, were detected for the first time in this material. Six ingredients detected, including cordycepin, d-mannitol, Phe, Phe-o-glucose, cyclo-Gly-Pro, and cyclo-Ala-Leu-rhamnose, were selected as a collection of chemical markers. An HPLC-MS/MS method was developed to simultaneously quantify them with sensitivity and specificity. The method had limits of detection ranging from 0.008 μg mL−1 for cordycepin to 0.75 μg mL−1 for cyclo-Gly-Pro. Recovery was found between 96 and 103 % in all tests. To evaluate the effectiveness of the marker collection proposed, five authentic C. sinensis samples and five samples of its substitutes were analyzed. Cordycepin, d-mannitol, and Phe were found present in all samples. The contents ranged from 0.0076 to 0.029 % (w/w) for cordycepin, 0.33 to 18.9 % for mannitol, and 0.0013 to 0.642 % for Phe. Interestingly, the two glycosides, Phe-o-glucose and cyclo-Ala-Leu-rhamnose, were detected only in authentic C. sinensis samples. These results indicated that the proposed protocol based on HPLC-MS/MS quantification of the markers might have a great potential in authentication and quality assessment of C. sinensis.

Chemical markers of C. sinensis identified in this work

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The study was supported partially by a grant from the US National Institutes of Health (GM 089557 to YML). LX is a visiting scholar supported by the Hubei Provincial Institute for Food and Drug Control.

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The authors declare that they have no conflict of interest.

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Correspondence to Hankun Hu or Yi-Ming Liu.

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Hu, H., Xiao, L., Zheng, B. et al. Identification of chemical markers in Cordyceps sinensis by HPLC-MS/MS. Anal Bioanal Chem 407, 8059–8066 (2015).

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  • Chemical markers
  • Cordyceps sinensis
  • Cordycepin
  • Glycosides
  • Authentication