To date, it is still not possible to obtain exhaustive information about organic materials in cultural heritage without sampling. Nonetheless, when studying unique objects with invaluable artistic or historical significance, preserving their integrity is a priority. In particular, organic dye identification is of significant interest for history and conservation research, but it is still hindered by analytes’ low concentration and poor fastness. In this work, a minimally invasive approach for dye identification is presented. The procedure is designed to accompany noninvasive analyses of inorganic substances for comprehensive studies of complex cultural heritage matrices, in compliance with their soundness. Liquid extraction of madder, turmeric, and indigo dyes was performed directly from paint layers and textiles. The extraction was supported by hydrogels, which themselves can undergo multitechnique analyses in the place of samples. After extraction, Ag colloid pastes were applied on the gels for SERS analyses, allowing for the identification of the three dyes. For the HPLC-MS/MS analyses, re-extraction of the dyes was followed by a clean-up step that was successfully applied on madder and turmeric. The colour change perceptivity after extraction was measured with colorimetry. The results showed ΔE values mostly below the upper limit of rigorous colour change, confirming the gentleness of the procedure.

The identification of the dyes present on a linen fragment from the tomb of Pharaoh Tutankhamun is the objective of the present study. Fiber optic reflectance spectroscopy (FORS) was applied to the archaeological sample for preliminary identification of the dyes and to better choose the extraction methodology for different areas of the sample. The innovative gel-supported micro-extraction with agar gel and the Nanorestore Gel^® High Water Retention (HWR) gel were applied to the archaeological sample after testing of the best concentration for the extraction of the agar gels substrates, performed on laboratory mock-ups by means of UV–Vis transmittance spectroscopy. Immediately after extraction, Ag colloidal pastes were applied on the gel surface and Surface Enhanced Raman Scattering (SERS) analysis was performed directly on them. The combination of information deriving from FORS and SERS spectra resulted in the successful identification of both indigo and madder and, in hypothesis, of their degradation products.

Tholu Bommalu are typical leather puppets of the traditional Indian shadow theatre. Two of these objects are part of a collection in the International Puppets Museum “Antonio Pasqualino” (Palermo, Sicily, Italy), which can count on one hundred-seventy-three of artifacts. These Indian puppets were investigated to obtain information related to the use of dyes for their manufacturing through a multi-technical approach exploiting the combination of highly sensitive spectroscopic techniques. Wet cotton stubbons were used to entrap small particles of dyes on the fibers from the art objects for the consequent analyses. Visible Light Micro-Reflectance spectroscopy was employed for the preliminary identification of the molecular class of dyes directly on the swabs, while Surface Enhanced Raman Scattering allowed the identification of the specific dye. Several synthetic dyes belonging to different typologies of coloring compounds were identified. The study resulted in an interesting overview of dyes used in recent Tholu Bommalata manufacturing through the combination of micro-invasive techniques directly on the sampling substrate.

The introduction of synthetic dyes completely changed the industrial production and use of colorants for art materials. From the synthesis of the first synthetic dye, mauveine, in 1856 until today, artists have enjoyed a wider range of colors and selection of chemical properties than was ever available before. However, the introduction of synthetic dyes introduced a wider variety and increased the complexity of the chemical structures of marketed dyes. This work looks towards the analysis of synthetically dyed objects in heritage collections, applying an extraction protocol based on the use of ammonia, which is considered favorable for natural anthraquinone dyes but has never before been applied to acid synthetic dyes. This work also presents an innovative cleanup step based on the use of an ion pair dispersive liquid–liquid microextraction for the purification and preconcentration of historical synthetic dyes before analysis. This approach was adapted from food science analysis and is applied to synthetic dyes in heritage science for the first time in this paper. The results showed adequate recovery of analytes and allowed for the ammonia-based extraction method to be applied successfully to 15 samples of suspected azo dyes from the Azienda Coloranti Nazionali e Affini (ACNA) synthetic dye collection, identified through untargeted HPLC-HRMS analyses.

The study of organic colourants employed in artworks is a fundamental topic for history and conservation research; however, the most critical aspect in such matter arises from the necessity of sampling. Instead of binding media and inorganic components, natural organic colourants often exhibit weak signals during non-invasive analyses, which can be easily masked in complex mixtures, such as paint layers. To overcome this problem, the preferred approach is to take a sample, extract the colourants and analyse them using specific analytical techniques. The proposed method of direct agar gel-supported liquid extraction, performed using a Pasteur pipette tip, offers a promising solution to this challenge. By extracting colourants without the need for paint sample removal, it minimises visible impact on the artwork while still providing sufficient material for spectroscopic and mass spectrometric characterization. The experimental approach, which involved mock-up of mixing different organic and inorganic pigments with different binders and subjecting them to artificial ageing, simulates real-world complex matrices and assesses the effectiveness of the extraction method. Photomicrographs were used to document the procedure's visible impact. Mass spectrometry and surface-enhanced Raman scattering spectroscopy, the techniques of choice for invasive analysis of organic colourants, were used on the analytes extracted from the gel. The method application on paint patches from historical catalogues, housed in the Stiftung Preußischer Kulturbesitz collection, adds practical relevance to the study and demonstrates the applicability of the technique to authentic artworks. The procedure enabled the identification of natural and synthetic colourants without compromising the integrity of the paint systems.