Degradation of lucidin: New insights into the fate of this natural pigment present in Dyer's madder (Rubia tinctorum L.) during the extraction of textile artefacts

The complex mixtures of colorants present in different madder species can provide significant information about which plant species or technique was used to dye the fibres of historical textile artefacts, hence, when extracting and analysing colorants from textile artefacts as much of this information as possible should be preserved. Historical textiles are most commonly extracted with 37% hydrochloric acid: methanol: water (2:1:1, v/v/v), but this solvent system hydrolyses dye glycosides and may also induce chemical reactions. One of the primary components in Dyers' madder (Rubia tinctorum L.) is lucidin primeveroside, but it is rarely seen in artefacts, nor is the corresponding aglycon lucidin. It has been demonstrated that the hydrochloric acid method causes hydrolysis of anthraquinone glycosides to their aglycon counterpart. Herein it is demonstrated that lucidin is not stable in such acidic conditions and degrades rapidly to xanthopurpurin. This is confirmed by HPLC, LC-MS and 1H NMR, which also provide evidence of the mechanism of degradation being a retro-aldol process.