Enhanced identification of medicinal caterpillar fungus with structural lipidomic analysis.

Ophiocordyceps sinensis (OS) is a rare and highly valued traditional fungal medicine, and comprehensive component analysis is essential for accurate species identification and the discovery of novel bioactive compounds. In this study, we applied a photochemical derivatization-tandem mass spectrometry workflow to profile the lipidome of OS and related medicinal caterpillar fungi, enabling detailed characterization of five phospholipid classes at the subclass, molecular species, and carbon-carbon double bond (CC) location levels. A total of 185 phospholipid isomers were identified to the CC location level using this approach. Lipid profiling was performed on wild and cultivated OS, as well as ten related medicinal caterpillar fungal species. Several lipid species were found to be closely associated with the authenticity of OS, serving as potential biomarkers for assessing product provenance and further investigating the bioactivity of these lipids based on their relative abundance.