HPLC–MS/MS authentication of the eighteenth century liquorice drug remains and mass spectrometry of selected liquorice-specific compounds

In this work, more than 200-year-old historical remains of liquorice root powder and a current liquorice root as a reference material were analyzed by HPLC–MS/MS to confirm the botanical authenticity of the historical material by comparing the results obtained. Combining extraction with different solvents with HPLC–MS/MS successfully identified nine chemotaxonomic markers in the historical material, thus confirming its identity as liquorice. In the current reference material, 32 chemotaxonomic markers of liquorice were successfully identified. Therefore, several liquorice-specific compounds in the historical remains analyzed were shown to have degraded over time. In addition, possible fragmentation mechanisms for five liquorice-specific compounds that have not been previously published in the literature were proposed.