No abstract

Vincent van Gogh's still lifes Irises and Roses were investigated to shed light onto the degree to which the paintings had changed, both individually and in relation to each other since they were painted, particularly in regard to the fading of the red lakes. Non-invasive techniques, including macroscopic X-ray fluorescence mapping, reflectance imaging spectroscopy, and X-radiography, were combined with microanalytical techniques in a select number of samples. The in-depth microchemical analysis was necessary to overcome the complications that arise when evaluating by non-invasive methods alone the compositions of passages with complex layering and mixing of paints. The results obtained by these two approaches were complemented by color measurements performed on paint cross-sections and on protected edges, and with historical information provided by the artist's own descriptions, early reviews and reproductions, and the data was used to carry out digital color simulations that provided, to a certain extent, a visualization of how the paintings may have originally appeared.

Surface-enhanced Raman spectroscopy (SERS) has found increasing acceptance in art conservation and forensic science for its great potential in detecting trace amounts of material. However, SERS is not a separation technique, and, therefore, it is not always suitable for distinguishing different components in a mixture. Coupling of thin layer chromatography (TLC) and SERS has been investigated in this article as a tool for the separation and identification of four alkaloids, namely harmalol, harmaline, harmane and harmine, from the seed extract of Syrian rue (Peganum harmala). The alkaloids contained in this plant were historically used as a dye and for medicinal purposes and have recently drawn attention due to their antitumor activity. The use of TLC over high-performance liquid chromatography (HPLC) is a convenient way to reduce the amount of material, equipment and time needed for the analysis, and coupling of TLC with SERS provides vibrational information on each compound in the mixture. HPLC analyses with diode array detection were also carried out as a test of our technique, to ascertain the composition of Syrian rue extract and validate the results obtained from TLC-SERS investigations. In addition, Syrian rue extract and its commercial alkaloid components were characterized by SERS and normal Raman spectroscopy here for the first time, in order to provide valuable reference data to be used for identification purposes.

A surface‐enhanced Raman spectroscopy (SERS) substrate made of agar gel coupled with silver nanoparticles has been applied to the micro‐extraction and the ultra‐sensitive detection of dyes on pieces of textile of different nature (silk, wool, and printed cotton) and on a mock‐up panel painting. In particular, the Ag‐agar gel substrate previously developed has been improved by the addition of the chelating agent ethylenediaminetetraacetic acid (EDTA), which has been found to play an important role as a stabilizer of the nanocomposite matrix and for the improvement of the micro‐extractive performances of the gel. The system has been confirmed to be non‐destructive and minimally invasive, showing a better capability of trapping the dye molecules inside its structure. Ag‐agar gel‐EDTA has been an invaluable and powerful tool for the characterization of the dye present in a printed cotton sample of unknown chemical composition. SERS analyses, performed on the dried cube of gel following extraction on the sample, have allowed for the identification of the dye. SERS results have been corroborated by high‐performance liquid chromatography analyses. The possibility of easily detecting compounds at very low concentration coupled with the high sensitivity of SERS makes this technique a valid and versatile method for the non‐destructive recognition of chemicals in works of art. Copyright © 2014 John Wiley & Sons, Ltd.

In this work, we present a complete Raman investigation of a class of compounds that has not received great attention yet, the red naphthol‐based azo dyes. We selected a group of red azo dyes often used by artists in inks and lake pigments: acid red 1, acid red 14, acid red 18, acid red 26, acid red 27, and acid red 73. A set of reference materials was studied by dispersive Raman, FT‐Raman, and surface‐enhanced Raman spectroscopy. The reference spectra were used in the study of late 19th century Japanese polychrome woodblock prints. The azo dyes selected for this study generally gave good Raman spectra at all excitation wavelengths. The results obtained by the various Raman techniques are compared, and the main difficulties in the identification of the compounds in works of art are illustrated and discussed. The fluorescence coming from the matrix in which the colorants are embedded can obscure their Raman signal. For this reason, the advantages and drawbacks of surface‐enhanced Raman spectroscopy with non‐sampling extraction of the colorants have been evaluated. Copyright © 2017 John Wiley & Sons, Ltd.