{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T14:37:31Z","timestamp":1790001451172,"version":"4.0.1"},"reference-count":19,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2015,10,7]],"date-time":"2015-10-07T00:00:00Z","timestamp":1444176000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100004602","name":"Program for New Century Excellent Talents in University","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100004602","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["81230090"],"award-info":[{"award-number":["81230090"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Mass Spectrom."],"published-print":{"date-parts":[[2015,11]]},"abstract":"<jats:p>Valepotriates, plant secondary metabolites of the family Valerianaceae, contain various acyloxy group linkages to the valepotriate nucleus and exhibit significant biological activities. Identification of valepotriates is important to uncover potential lead compounds for the development of new sedative and antitumor drugs. However, making their structure elucidation by nuclear magnetic resonance (NMR) experiments is too difficult to be realized because of the overlapped carbonyl carbon signals of acyloxy groups substituted at different positions. Thus, the mass spectrometric profiling of these compounds in positive ion mode was developed to unveil the exact linkage of acyloxy group and the core of valepotriate. In this study, electrospray ionization tandem multistage mass spectrometry (ESI\u2010MS\/MS<jats:sup>n<\/jats:sup>) in ion trap and collision\u2010induced dissociation tandem MS were used to investigate the fragmentation pathways of four types of valepotriates in <jats:italic>Valeriana jatamansi<\/jats:italic>, including 5\u2010hydroxy\u20105,6\u2010dihydrovaltrate hydrin (5\u2010hydroxy\u20105,6\u2010dihydrovaltrate chlorohydrin), 5,6\u2010dihydrovaltrate hydrin (5,6\u2010dihydrovaltrate chlorohydrin), 5\u2010hydroxy\u20105,6\u2010dihydrovaltrate and valtrate hydrin (valtrate chlorohydrin). The high\u2010resolution mass spectrum (HRMS) data of all the investigated valepotriates from quadrupole time\u2010of\u2010flight MS\/MS were used as a supportive of the fragmentation rules we hypothesized from ion\u2010trap stepwise MS<jats:italic><jats:sup>n<\/jats:sup><\/jats:italic>. As a result, the loss sequence of acyloxy groups and the abundance of key product ions, in combination with the characteristic product ions corresponding to the valepotriate nucleus, could readily differentiate the four different types of valepotriates. The summarized fragmentation rules were also successfully exploited for the structural characterization of three new trace valepotriates from <jats:italic>V<\/jats:italic>.\u2009<jats:italic>jatamansi<\/jats:italic>. The results indicated that the developed analytical method could be employed as a rapid, effective technique for structural characterization of valepotriates, especially for the trace compounds that could not be identified by NMR techniques. This study may also arouse interest for further structural analysis of other valepotriate\u2010containing type herbal medicines. Copyright \u00a9 2015 John Wiley &amp; Sons, Ltd.<\/jats:p>","DOI":"10.1002\/jms.3697","type":"journal-article","created":{"date-parts":[[2015,10,12]],"date-time":"2015-10-12T17:20:10Z","timestamp":1444670410000},"page":"1294-1304","source":"Crossref","is-referenced-by-count":11,"title":["Mass spectrometric profiling of valepotriates possessing various acyloxy groups from <i>Valeriana jatamansi<\/i>"],"prefix":"10.1002","volume":"50","author":[{"given":"Sheng","family":"Lin","sequence":"first","affiliation":[{"name":"Department of Natural Product Chemistry, School of Pharmacy Second Military Medical University  Shanghai 200433 China"},{"name":"State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica Chinese Academy of Medical Sciences and Peking Union Medical College  Beijing 100050 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ji","family":"Ye","sequence":"additional","affiliation":[{"name":"Department of 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