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It is thereby crucial for isomer differentiation to facilitate quality control.\n                    <\/jats:p>\n                  <\/jats:sec>\n                  <jats:sec>\n                    <jats:title>Objective<\/jats:title>\n                    <jats:p>\n                      To pursue a program enabling 20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010 and 20(\n                      <jats:italic>S<\/jats:italic>\n                      )\u2010ginsenosides discrimination in complicated matrices using MS\/MS, red ginseng, the processed form of ginseng, was deployed as a representative.\n                    <\/jats:p>\n                  <\/jats:sec>\n                  <jats:sec>\n                    <jats:title>Methods<\/jats:title>\n                    <jats:p>\n                      Five pairs of ginsenoside epimers were collected for method development. MS\n                      <jats:sup>1<\/jats:sup>\n                      and MS\n                      <jats:sup>2<\/jats:sup>\n                      spectra of every trimeric complex ion formed by complexation of ginsenoside,\n                      <jats:sc>l<\/jats:sc>\n                      \u2010Phe, and Cu\n                      <jats:sup>2+<\/jats:sup>\n                      were recorded using direct infusion (DI)\u2013MS\/MS, and the abundance ratio between the two dimeric fragment ions was termed\n                      <jats:italic>R<\/jats:italic>\n                      . Moreover, energy\u2010resolved MS (ER\u2010MS) was deployed to monitor fragmentation trajectories of precursor and concerned fragment ions and to determine the\n                      <jats:italic>R<\/jats:italic>\n                      feature at optimal collision energy, denoted\n                      <jats:italic>R<\/jats:italic>\n                      <jats:sup>max<\/jats:sup>\n                      . To validate the applicability for differentiating epimers in complicated matrices, e.g., red ginseng extract, post\u2010column infusion (PCI) was introduced to configure PCI\u2010LC\u2013ER\u2010MS.\n                    <\/jats:p>\n                  <\/jats:sec>\n                  <jats:sec>\n                    <jats:title>Results<\/jats:title>\n                    <jats:p>\n                      20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010 vs. 20(\n                      <jats:italic>S<\/jats:italic>\n                      )\u2010Rg3 as representatives, [Cu\u1d35\u1d35(\n                      <jats:sc>l<\/jats:sc>\n                      \u2010Phe)\n                      <jats:sub>2<\/jats:sub>\n                      (20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010\/20(\n                      <jats:italic>S<\/jats:italic>\n                      ))\u2010Rg3)\u2212H]\n                      <jats:sup>+<\/jats:sup>\n                      complex ions were observed and\n                      <jats:italic>R<\/jats:italic>\n                      values of the dimeric fragment ions such as [Cu\u1d35\u1d35(\n                      <jats:sc>l<\/jats:sc>\n                      \u2010Phe)(20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010\/20(\n                      <jats:italic>S<\/jats:italic>\n                      ))\u2010Rg3)\u2212H]\n                      <jats:sup>+<\/jats:sup>\n                      and [Cu\u1d35\u1d35(\n                      <jats:sc>l<\/jats:sc>\n                      \u2010Phe)\n                      <jats:sub>2<\/jats:sub>\n                      \u2212H]\n                      <jats:sup>+<\/jats:sup>\n                      , exhibited differences.\n                      <jats:italic>R<\/jats:italic>\n                      <jats:sup>max<\/jats:sup>\n                      features obtained by DI\u2013ER\u2010MS showed significant differences when comparing other 20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010 and 20(\n                      <jats:italic>S<\/jats:italic>\n                      )\u2010configurational isomers, leading to a reliable way for epimer discrimination. The reproducibility of recognition capability on PCI\u2010LC\u2013ER\u2010MS platform was justified and applied to epimer differentiation in red ginseng extract. Successes were reached for the differentiation of two pairs of epimers, 20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010 and 20(\n                      <jats:italic>S<\/jats:italic>\n                      )\u2010Rg3, and 20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010 and 20(\n                      <jats:italic>S<\/jats:italic>\n                      )\u2010Rh1.\n                    <\/jats:p>\n                  <\/jats:sec>\n                  <jats:sec>\n                    <jats:title>Conclusion<\/jats:title>\n                    <jats:p>\n                      In summary, the proposed strategy combined the complexation driven by [Cu\n                      <jats:sup>II<\/jats:sup>\n                      (\n                      <jats:sc>l<\/jats:sc>\n                      \u2010Phe)\n                      <jats:sub>2<\/jats:sub>\n                      \u2212H]\n                      <jats:sup>+<\/jats:sup>\n                      with PCI\u2010LC\u2013ER\u2010MS enables the differentiation of 20(\n                      <jats:italic>R<\/jats:italic>\n                      )\u2010 and 20(\n                      <jats:italic>S<\/jats:italic>\n                      )\u2010configurational ginsenoside isomers in complicated matrices.\n                    <\/jats:p>\n                  <\/jats:sec>","DOI":"10.1002\/pca.70081","type":"journal-article","created":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T02:39:19Z","timestamp":1782873559000},"page":"856-874","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Configurational Isomer Differentiation Between 20(\n                    <i>S<\/i>\n                    )\u2010 and 20(\n                    <i>R<\/i>\n                    )\u2010Ginsenosides in Red Ginseng via Applying [Cu\n                    <sup>II<\/sup>\n                    (\n                    <scp>l<\/scp>\n                    \u2010Phe)\n                    <sub>2<\/sub>\n                    \u2212H]\n                    <sup>+<\/sup>\n                    to Post\u2010Column Infusion LC\u2013MS\/MS"],"prefix":"10.1002","volume":"37","author":[{"given":"Maodong","family":"Wang","sequence":"first","affiliation":[{"name":"Modern Research Center for Traditional Chinese Medicine, Beijing Research Institute of Chinese Medicine Beijing University of Chinese Medicine  Beijing China"},{"name":"School of Chinese Materia Medica Beijing University of Chinese Medicine  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hangyun","family":"He","sequence":"additional","affiliation":[{"name":"Modern Research Center for Traditional Chinese Medicine, Beijing Research Institute of Chinese Medicine Beijing University of Chinese Medicine  Beijing China"},{"name":"School of Chinese Materia Medica Beijing University of Chinese Medicine  Beijing 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