New insights into the composition of Indian yellow and its use in a Rajasthani wall painting

The widespread occurrence of Indian yellow on an early 17th-century wall painting in Rajasthan (India) was initially indicated by photo-induced luminescence imaging of the painted scheme in the Badal Mahal within the Garh Palace (Bundi). The presence of the organic pigment was subsequently confirmed by HPLC-ESI-Q-ToF. The results of a multi-analytical study focusing on two samples from the wall painting and two reference pigments from the British Museum and National Gallery (London, UK) are presented here. The research focused on the possible causes for the different yellow/orange hues observed in the painting samples. Analysis of cross-sections with SEM-EDS revealed similar elemental composition for the Indian yellow paint layers, but different underlying layers, indicating a variation in painting technique. The composition of the Indian yellow samples was investigated by HPLC-ESI-Q-ToF with both positive and negative ionisation. In addition to euxanthic acid and euxanthone, a sulphonate derivative of euxanthone was found to be present in all samples, while relative amounts of the three components varied. Flavonoid molecules—morin, kaempferol, quercetin and luteolin—were also detected in one wall painting sample (characterised by a brighter yellow colour) and not in the sample that was more orange. The optical properties of the samples were characterised by photoluminescence spectroscopy in both solid state and aqueous solution. The contribution of each organic compound to the emission spectrum of Indian yellow in solution was also investigated by time-dependent density functional theory (TDDFT) calculations. Small differences in terms of spectral shift were observed in solid state experiments, but not in solution, suggesting that the spectral differences in the emission spectrum were mostly due to different contributions of solid-state arrangements, most likely driven by π-π stacking and/or hydrogen bonds. However, a slight difference at high energies was observed in the spectra acquired in solution and TDDFT calculations permitted this to be ascribed to the different chemical composition of the samples. Time-resolved measurements highlighted di-exponential lifetime decays, confirming the presence of at least two molecular arrangements. Py(HMDS)-GC–MS was also used for the first time to characterise Indian yellow and the trimethylsilyl derivative of euxanthone was identified in the pyrograms, demonstrating it to be a suitable marker for the identification of the pigment in complex historic samples.