Microanalysis of Organic Pigments in Ancient Textiles by Surface-Enhanced Raman Scattering on Agar Gel Matrices

We review some new methods based on surface-enhanced Raman scattering (SERS) for the nondestructive/minimally invasive identification of organic colorants in objects whose value or function precludes sampling, such as historic and archeological textiles, paintings, and drawing. We discuss in detail the methodology we developed for the selective extraction and identification of anthraquinones and indigoids in the typical concentration used in textiles by means of an ecocompatible homogeneous nanostructured agar matrix. The extraction system was modulated according to the chemical properties of the target analyte by choosing appropriate reagents for the extraction and optimizing the extraction time. The system has been found to be extremely stable, easy to use and produce, easy to store, and at the same time able to be analyzed even after long time intervals, maintaining its enhancement properties unaltered, without the detriment of the extracted compound. Highly structured SERS band intensities have been obtained from the extracted dyes adopting laser light excitations at 514.5 and 785 nm of a micro-Raman setup. This analytical method has been found to be extremely safe for the analyzed substrates, thus being a promising procedure for the selective analysis and detection of molecules at low concentration in the field of artworks conservation

New Insights on the Raman and SERS Spectra of Luteolin under Different Excitation Conditions: Experiments and DFT Calculations

We have studied, by density functional theory, the interaction between luteolin and Ag, devising two complexes where an Ag14 cluster faces two different sites of the molecule. The two sites are identified as quinoid-like and cathecol-like, and the complexes are CPLX1 and CPLX2, respectively. Raman and SERS spectra of luteolin were measured at different excitation wavelengths. Luteolin solid samples from different suppliers have different Raman spectra, possibly associated with different arrangements in the solids. These spectra are well reproduced by our DFT calculations. Assignment of the vibrational modes of luteolin and of the two luteolin–Ag14 complexes is obtained thanks to decomposition of the normal coordinates in terms of internal coordinates. The calculated Raman spectrum for CPLX1 seems to better reproduce the experimental SERS spectra. CPLX2 furnishes a spectrum still resembling that of luteolin in the high frequency region and is possibly responsible for some weak bands in the 1400–1700 cm−1 range that cannot be accounted by the CPLX1 system. SERS spectra are dependent on the Raman excitation wavelength. The calculation of the electronic spectrum suggests the presence of charge-transfer states, which might be responsible for the changes in the SERS spectra

Study on the technique of the Roman age mural paintings by micro-XRF with Polycapillary Conic Collimator and micro-Raman analyses

XRF and micro-Raman stratigraphic microanalyses of fragments of some mural paintings, belonging to the Archaeological Site of Oplonti (Napoli) and the Vigna Barberini site in the Palatino (Roma), were performed. In order to collimate the fluorescence X-rays emitted by the samples, an X-ray polycapillary conic collimator (PCC) has been used in front of the detector. This device arrangement is compact, versatile, and portable. The nature of the pigments, the compositional elements, and the thickness of the fragment layers have been studied. The stratigraphic analysis partially confirms the preparation techniques described by Plinius and Vitruvius; moreover it confirms the hypothesis that the artifacts are not fresco paintings. This work has been conducted within the context of a wider research on the Roman age mural paintings. (c) 2005 Elsevier SAS. All rights reserved