HPLC-DAD-MS analysis of colorant and resinous components of lac-dye: A comparison between Kerria and Paratachardina genera

The sources and structures of dyes used to colour Western historical textiles are described in this tutorial review. Most blue and purple colours were derived from indigo--obtained either from woad or from the indigo plant--though some other sources (e.g. shellfish and lichens) were used. Reds were often anthraquinone derivatives obtained from plants or insects. Yellows were almost always flavonoid derivatives obtained from a variety of plant species. Most other colours were produced by over-dyeing--e.g. greens were obtained by over-dyeing a blue with a yellow dye. Direct analysis of dyes isolated from artefacts allows comparison with the historical record.

Analysis of dyes extracted from textiles of historical interest can give valuable information as to where, when, and how the textiles were made. The most widely used method for extraction of colorants involves heating with HCl, which frequently decomposes glycosidic dye components to their parent aglycons, with consequent loss of information about the source of the dye. This is particularly true for flavonoid dyes, many of which are glycosides. We have developed or improved upon two mild textile extraction methods that use ethylenediaminetetraacetic acid (EDTA) and formic acid and are efficient in extracting dyes, but preserve glycosidic linkages. The relative efficiencies of the HCl, EDTA, and formic acid extraction methods are compared by analyzing extracts of dyed samples of silk using HPLC coupled with diode array and mass spectrometric detection. HPLC profiles of EDTA or formic acid extracts of silk dyed, for example, with pagoda tree buds and onionskins are clearly distinguishable as to the plant material used, whereas profiles of HCl extracts are not. Thus, extraction of textiles with EDTA or formic acid reagents can yield significantly more information about the original dyestuff than can extraction with a strong acid.

This review discusses the characterisation of natural organic dyestuffs of historical interest by liquid chromatography-mass spectrometry. The structures of the most important natural organic dyestuffs traditionally used are presented and discussed from the perspective of their analytical chemical determination. The practical aspects of the determination of this inhomogeneous range of compounds with different structures, such as anthraquinones, flavonoids, indigoids or tannins, are discussed with their implications for sample preparation, liquid chromatographic separation and mass spectrometric detection. The particular focus of this review is the discussion of the mass spectral fragmentation patterns of the different classes of natural organic dyestuffs, which in the ideal case allow the identification of the dyestuff actually used, and thereby provide a key to the better characterisation and understanding of historical objects dyed with natural organic dyestuffs.