Tracing the biological origin of animal glues used in paintings through mitochondrial DNA analysis (original) (raw)
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Scientific Reports
Undertaking the conservation of artworks informed by the results of molecular analyses has gained growing importance over the last decades, and today it can take advantage of state-of-the-art analytical techniques, such as mass spectrometry-based proteomics. Protein-based binders are among the most common organic materials used in artworks, having been used in their production for centuries. However, the applications of proteomics to these materials are still limited. In this work, a palaeoproteomic workflow was successfully tested on paint reconstructions, and subsequently applied to micro-samples from a 15th-century panel painting, attributed to the workshop of Sandro Botticelli. This method allowed the confident identification of the protein-based binders and their biological origin, as well as the discrimination of the binder used in the ground and paint layers of the painting. These results show that the approach is accurate, highly sensitive, and broadly applicable in the cult...
is published by Morana RTD d.o.o. www.Morana-rtd.com e-PRESERVATIONScience This paper is based on a presentation at the sixth international meeting of the Users'Group for Mass Spectrometry and Chromatography (MASC) in Pisa, Italy, 5th – 6th June 2013. Abstract Romano-Egyptian panels in the collections of the J. Paul Getty Museum dating to 180-200 A.D. were found to contain proteinaceous paint media. Animal glue was detected in the ground layers of all three panels using Enzyme-linked immunosorbent assay (ELISA) and mass spectrom-etry. Results were verified with gas chromatography/mass spectrometry (GC/MS) by the identification of 4-hydroxyproline, the major amino acid that occurs in animal glue collagen but not egg albumin. The animal species used to make the glue was identified as cow (Bos taurus) by using nano-liquid chromatography-electrospray ionization-tandem MS (nanoLC-ESI-MS/MS). A paint fragment from the Bearded Man contained tryptic peptides, type III collagen α1 chain,...
Analytical Chemistry, 2011
This study proposes a proteomic-based strategy for the identification of the origin species of glues used as binding media and adhesives in artworks. The methodology, based on FTICR high resolution mass spectrometry, was evaluated on glues from different animal origin (i.e., bovine, rabbit, and fish). The analysis of the peptide mixture resulting from the enzymatic hydrolysis of the proteins led to the identification of species-specific peptides. Up to 15 specific peptides were identified for the bovine species and three for the rabbit species and, in the case of sturgeon glue, three fish-specific peptides were found by sequence homology to the rainbow trout. Then, the method was applied to authenticate different rabbit skin glue samples, including a 100 year-old sample named "Colle a Doreurs" coming from the "Maison Totin-Fr eres". For this sample, two specific peptides of rabbit collagen were identified. To evaluate the method in a complex matrix, model paints composed of lead white, linseed oil, and animal glue were prepared. Species-specific peptides were identified in each paint sample. Finally, a gilt sample from St Maximin church dating from the eighteenth century was analyzed, and 13 peptides specific to bovine collagens were identified starting from very low sample amount (50 μg).
Palaeoproteomic Profiling of Conservation Layers on a 14th Century Italian Wall Painting
Angewandte Chemie, 2018
Ahead of display, a non-original layer was observed on the surface of a fragment of a wall painting by Ambrogio Lorenzetti (active 1319, died 1348/9). FTIR analysis suggested proteinaceous content. Mass spectrometry was used to better characterise this layer and revealed two protein components: sheep and cow glue and chicken and duck egg white. Analysis of post-translational modifications detected several photo-oxidation products, which suggest that the egg experienced prolonged exposure to UV light and was likely applied long before the glue layer. Additionally, glycation products detected may indicate naturally occurring glycoprotein degradation or reaction with a carbohydrate material such as starch, identified by ATR-FTIR in a cross-section of a sample taken from the painting. Palaeoproteomics is shown to provide detailed characterisation of organic layers associated with mural paintings and therefore aids reconstruction of the conservation history of these objects.
Molecular Tracing of the Biological Origin of Drying Oils Used in Works of Art
2020
Until recent times, artists have used a variety of binding media obtained from biological materials of animal or plant origin. Seed or nut oils capable to form a protective film when drying were an essential component of paints. Current methods such as gas chromatography coupled with mass spectrometry allow identifying biological origin of a specific drying oil, but chemical composition is a highly variable factor and can change with plant cultivar, soil, season or weather conditions of harvesting increasing the possibility of error. In addition, mixing oil from different biological species can mislead the analyses because it alters the composition of chemical compounds used in species identification. We report the development of a protocol for the identification of the biological source of drying oils used to prepare binding media for paints. Chloroplast DNA sequences were successfully amplified from tiny oil samples, both fresh and from aged pictorial models. Sequencing of the trn...
Heritage
This article presents results from a binding media survey of 61 Romano-Egyptian paintings. Most of the paintings (51) are the better-known funerary mummy portraits created using either encaustic or tempera paint medium. Samples from all the paintings (on wooden panels or linen shrouds) were analyzed with gas chromatography/mass spectrometry (GC/MS) to identify waxes, fatty acids, resins, oils, and proteins in one sample. Analytical protocols that utilized three separate derivatization techniques were developed. The first analysis identified free fatty acids, waxes, and fatty acid soaps, the second characterized oils and plant resins, and the third identified proteins. The identification of plant gums required a separate sample. Results showed that fatty acids in beeswax were present as lead soaps and dicarboxylic fatty acids in some samples was consistent with an oxidized oil. The tempera portraits were found to contain predominantly animal glue, revising the belief that egg was the...
The aim of this study was to examine whether DNA was degraded in the manufacturing of animal glue. To test this, two different types of sturgeon glue (Acipenser sp.) were manufactured using historic recipes. One glue was boiled for a substantial amount of time and the other was kept under 75°C. DNA samples were collected from both glues in order to test whether the DNA was degraded in the heating process of making the glue. It was also tested whether two different kinds of flex canvas (for paintings), one coarse and one fine weaved would inhibit the PCR reaction. To do this the glue were applied onto the canvas and samples were collected. To examine the sample size needed to get an amplifiable DNA sample, different sizes were collected of the canvas, 1.0cm 2 ; 0,5cm 2 and 0,5cm of a single thread. It was possible to get amplifiable DNA in 11 out of 12 samples collected after the manufacturing of the glue and in 18 out of 24 samples collected of the canvas. In four out of the five ca...
2021
A stony sculptural composition of the Nativity Scene is preserved in Altamura’s Cathedral (Apulia, Italy). This commonly called Apulian “presepe”, attributed to an unknown stonemason, is composed of polychrome carbonate white stone sculptures. While earlier stratigraphic tests have unveiled a complex superimposition of painting layers—meaning that several editions of the sculptures succeeded from the 16th to 20th century—a chemical investigation intended to identify the organic binding media used in painting layers was undertaken. Drawing on current literature, two strategies were exploited: a non-invasive in situ digestion analysis and an approach based on micro-removal of painting film followed by the Bligh and Dyer extraction protocol. Both peptide and lipid mixtures were analyzed by matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) and reversed-phase liquid chromatography coupled to mass spectrometry by electrospray ionization (RPLC-ESI-MS). Attenuated tot...
GC/MS Characterization of Beeswax, Protein, Gum, Resin, and Oil in Romano-Egyptian Paintings
Heritage, 2019
This article presents results from a binding media survey of 61 Romano-Egyptian paintings. Most of the paintings (51) are the better-known funerary mummy portraits created using either encaustic or tempera paint medium. Samples from all the paintings (on wooden panels or linen shrouds) were analyzed with gas chromatography/mass spectrometry (GC/MS) to identify waxes, fatty acids, resins, oils, and proteins in one sample. Analytical protocols that utilized three separate derivatization techniques were developed. The first analysis identified free fatty acids, waxes, and fatty acid soaps, the second characterized oils and plant resins, and the third identified proteins. The identification of plant gums required a separate sample. Results showed that fatty acids in beeswax were present as lead soaps and dicarboxylic fatty acids in some samples was consistent with an oxidized oil. The tempera portraits were found to contain predominantly animal glue, revising the belief that egg was the...