A simple and rapid capillary electrophoretic method with UV detection (CE-UV) has been developed for the identification of five natural dyes namely, carmine, indigo, saffron, gamboge and Rubia tinctoria root. The separation was performed in a fused-silica capillary of 64.5 cm length and 50 microm id. The running buffer was 40 mM sodium tetraborate buffer solution (pH 9.25). The applied potential was 30 kV, the temperature was 25 degrees C and detections were performed at 196, 232, 252, 300 and 356 nm. The injections were under pressure of 50 mbar during 13 s. The method was applied to the identification of carminic acid, gambogic acid, crocetin, indigotin, alizarin and purpurin in the collection of drawings and maps at the Royal Chancellery Archives in Granada (Spain). The method was validated by using HPLC as a reference method.
Capillary electrophoresis with photodiode array detection (CE-PDA) and with electrospray ionisation-mass spectrometry (CE-ESI-MS) was used for the separation and the identification of 23 synthetic organic dyes, among those used in early 20th century colour photographs such as autochromes. Both cationic and anionic dyes could be separated within 15min using a single CE-PDA method. The method was used as the basis to develop a CE-ESI-MS methodology through the optimisation of the relevant ESI and MS parameters. Sheath liquid composition, nebulising gas pressure, drying gas flow rate and drying gas temperature were found to influence the sensitivity of the detection. These parameters were optimised in positive and negative ion modes for cationic dyes and anionic dyes, respectively. The two analyses could be carried out successively on a single sample. In view of the application to cultural heritage objects, the CE-ESI-MS analytical procedure was applied to identify the dyes in a Filmcolor artefact, late version of the autochrome. The results complemented and enhanced current knowledge as four cationic dyes and three anionic dyes were identified. Four additional dyes are proposed as possibly present as traces.
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