Salvianolic acid derivatives-focused characterization in Salviae miltiorrhizae Radix et Rhizoma by LC×LC coupled with tandem energy-resolved mass spectrometry.

Authors

Hangyun He, Han Li, Maodong Wang, Lijuan Wu, Ke Zhang, Yuelin Song

Published in

Analytica chimica acta. Volume 1417. Pages 345795. Oct 01, 2026. Epub Jun 03, 2026.

Abstract

Salvianolic acid derivatives (SADs) represent a cluster of hydrosoluble phenolic acids and typically exist as monomer and oligomer forms in Salviae miltiorrhizae Radix et Rhizoma (Chinese name: Danshen). Because of the high-level structural similarity, even isomerism, it is technically challenging to achieve satisfactory separation and confidence-enhanced identification using conventional LC-MS/MS approaches. Here, an integrated strategy was proposed through simultaneously advancing LC separation, MS/MS information acquisition, and post-acquisition data processing. LC×LC was configured using HSS T3 and 5C₁₈-AR-II columns for 1^st and 2^nd-dimensional separations, respectively, attributing to their sufficient complementary capabilities. By applying several data acquisition modes on the hybrid triple quadrupole-linear ion trap (QTRAP)-MS platform, including precursor ion scan, neutral loss scan, predictive multiple reaction monitoring, and step-wise multiple ion monitoring, a total of 143 SADs were captured. To facilitate structural identification, high-resolution mass values of all concerned SADs were obtained by LC-QTOF-MS. Meanwhile, a bottom-up structural annotation workflow was constructed by applying a tandem energy-resolved MS program. For signals-of-interest, the substructures were identified by matching full exciting energy ramp (FEER)-MS³ spectra with FEER-MSⁿ (n = 2 or 3) spectra of known structures or fragments, and the linkage patterns amongst substructures were deciphered by incorporating full collision energy ramp (FCER)-MS² spectra with quantum chemical calculation. As a result, confidence-enhanced structure identification was reached for 11 monomers, 19 dimers, 59 trimers, and 54 tetramers. Together, the strategy integrating LC×LC, diverse MS/MS modes, and bottom-up structural annotation enabled in-depth SADs-focused characterization in Danshen, providing a promising tool for chemical characterization of herbal medicines.

PMID:
42508896
Bibliographic data and abstract were imported from PubMed on 28 Jul 2026.

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