The natural sepia pigment is based on eumelanin, the most prevalent type of melanin, and can be obtained from the ink sac of different members of the Cephalopoda class, such as cuttlefish and squid. The main components of natural sepia are indole derivatives, but pigments prepared following historical recipes are generally more heterogeneous as they may also contain proteins, polysaccharides, and lipids. Sepia is difficult to identify in works of art owing to its heterogeneity, insolubility in most organic solvents, interference by the binding media, and its poorly defined spectroscopic properties. In the present study, three commercial natural sepia pigments, along with a sample extracted from cuttlefish following a historical recipe in an artists' manual, a relatively more pure commercial melanin, and a synthetic eumelanin obtained by the oxidation of dopamine were characterized by normal Raman and surface‐enhanced Raman scattering (SERS), complemented by Fourier transform infrared, pyrolysis–gas chromatography–mass spectrometry, and X‐ray fluorescence, in order to obtain vibrational signatures for the identification of the pigment in works of art. Pyrolysis–gas chromatography–mass spectrometry and X‐ray fluorescence analysis showed that the pigment composition is strongly influenced by the extraction procedure used. Lipids were identified in the chromatograms of all the natural samples analyzed, and the majority of these also showed the presence of cholesterol derivatives. Additional components resulting from the decomposition of polysaccharides were found to be present in the sepia extracted from cuttlefish in our laboratories. Normal Raman and SERS were also used to study two sepia inks applied on paper and subjected to accelerated aging. In the SERS measurements, a hydroxylamine‐reduced silver colloid was used as this substrate is suitable for the identification of other natural heterogeneous black‐brown pigments. The SERS methodology developed was applied to identify sepia in Waiting for Aaron, a drawing by the 19th century artist Robert Frederick Blum. Copyright © 2014 John Wiley & Sons, Ltd.

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Dyes were used in Mexico since early pre-Hispanic periods for coloring of fibers, codex writing, and mural paintings, among other purposes. From the wide variety of Mexican dyes, only a handful has been studied at length. Moreover, few studies had been devoted to the identification of these substances in artistic or historical objects, in part, because of the lack of a suitable technique that complies with the nondestructive or microdestructive requirements that involves working with such objects. Surface-enhanced Raman spectroscopy (SERS) may provide the tool needed to identify the more than 20 dyes that can be found in Mexico and the first step would be acquiring their SERS spectra in laboratory conditions. To fulfill that goal, carminic acid, cochineal (Dactylopius coccus), achiote (Bixa orellana), muitle (Justicia spicigera), zacatlaxcalli (Cuscuta sp.), brazilwood (Caesalpinia echinata), and cempazuchitl (Tagetes erecta) SERS spectra were recorded in aqueous solution and directly on dyed wool fibers, using silver colloids as SERS substrate. Ag nanoparticles were prepared by chemical reduction with sodium citrate and characterized by UV-Vis spectroscopy and high resolution transmission electronic microscopy. Pure carminic acid was used for control SERS spectra and then samples of cochineal, achiote, muitle, zacatlaxcalli, brazilwood, and cempazuchitl were tested. Samples were prepared either by extraction from their natural sources or by dyeing the fibers; in both cases traditional recipes were followed. The acquired spectra may serve in future research as comparative references for the identification of the dyes present in cultural artifacts, and in the case of cempazuchitl, muitle, and zacatlaxcalli, these are probably the first reported Raman spectra of such plants.

In this work, we have studied the pH-dependence of the formation of DQCB[8] complexes by surface-enhanced Raman scattering (SERS) spectroscopy. The SERS spectra suggest that at acidic pH CB[8] can form a binary complex with the dication DQ(+2) while at higher pH ternary complexes with the radical cation dimer (DQ(+)˙)(2) and the radical cation-dication dimer (DQ(+)˙DQ(+2)) are formed. The pH-enhanced diquat (DQ) dimerization inside the cucurbit[8]uril cavity has not been reported until now. In addition, this study provides very valuable information regarding the use of CB[8] functionalized silver nanoparticles as SERS substrate for sensing applications.

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