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Despite their versatility, only a few single-crystal X-ray structures of lead carboxylates exist, due to difficulties with solubility. In particular, the structures of long-chain metal carboxylates have not been reported. The lone electron pair in Pb(ii) can be stereochemically active or inactive, leading to two types of coordination geometries commonly referred to as hemidirected and holodirected structures, respectively. We report (13)C and (207)Pb solid-state NMR and infrared spectra for a series of lead carboxylates, ranging from lead hexanoate (C6) to lead hexadecanoate (C18). The lead carboxylates based on consistent NMR parameters can be divided in two groups, shorter-chain (C6, C7, and C8) and longer-chain (C9, C10, C11, C12, C14, C16, and C18) carboxylates. This dichotomy suggests two modes of packing in these solids, one for the short-chain lead carboxylates and one for long-chain lead carboxylates. The consistency of the (13)C and (207)Pb NMR parameters, as well as the IR data, in each group suggests that each motif represents a structure characteristic of each subgroup. We also report the single-crystal X-ray diffraction structure of lead nonanoate (C9), the first single-crystal structure to have been reported for the longer-chain subgroup. Taken together the evidence suggests that the coordination geometry of C6-C8 lead carboxylates is hemidirected, and that of C9-C14, C16 and C18 lead carboxylates is holodirected.

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.

The aim of the present article is to highlight publications that illustrate some advances in the application of Raman spectroscopy to investigate materials typically observed in manuscripts, drawings, prints, and paintings in museums' and cultural institutions' collections, and to discuss some of the challenges and future prospects. Copyright © 2015 John Wiley & Sons, Ltd.

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.

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The colorants and additives present in lithographic inks used in a group of posters manufactured during the period between 1890 and 1920, an extremely fruitful period regarding the development of the synthetic dye and pigment industry, were identified by Raman spectroscopy. Synthetic organic pigments and dyes were detected along with inorganic pigments. Red, blue and yellow synthetic organic pigments were more frequently observed in posters manufactured by the end of the 1890-1920 period, reflecting that lithographers were actively experimenting to achieve hues not accessible using inorganic pigments alone. The water-sensitivity of the inks containing synthetic organic colorants is discussed in relation to the potential application of aqueous conservation treatments to early posters.