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1.
Poli T Chiantore O Giovagnoli A Piccirillo A 《Analytical and bioanalytical chemistry》2012,402(9):2977-2984
The study of polished cross sections is a well-assessed and practical method to investigate the stratigraphy of paintings
and multilayer polychromies on works of art, in general. Analyses on cross sections allow us to characterize, at once, all
the layers in the stratigraphy, giving information about the artists technique, the number of layers and their composition
and sometimes about the conservation history of the artefact. In this paper, the application of an imaging detector focal
plane array (FPA) coupled to an infrared (IR) microscope has been studied, focusing on the characteristics and potential of
the different working methodologies (attenuated total reflectance (ATR) and total reflection). FPA detector coupled with ATR
crystal can “localize” IR information coming from a 30 × 30μm sample area, in a 64 × 64 dot matrix detector. In particular,
an innovative analysis methodology has been tested for the total reflectance measurements in order to obtain maximum information
with single measurements. Micro-infrared total reflection measurements have been carried out in an extended IR range (from
1,000 to 5,266 cm−1) exploiting the broad spectral response of mercury cadmium telluride detector in order to include overtones and combination
bands from near-infrared spectral range without any modification of the standard mid-infrared micro-FT instrumentation. The
potentialities of this new approach have been successfully transferred in the imaging/mapping investigations with a minimal
tuning of the apparatus. Results obtained on a polished cross section coming from a modern painting and on a micro-sample
of a wood polychromy from an undated historic polyptic are shown for demonstration. 相似文献
2.
M. Vagnini C. Miliani L. Cartechini P. Rocchi B. G. Brunetti A. Sgamellotti 《Analytical and bioanalytical chemistry》2009,395(7):2107-2118
In the present study, the analytical strengths and limitations of near-infrared (NIR) spectroscopy to non-invasively characterize
organic components in painting materials have been investigated. In spite of the increased amount of information available
today from advanced modern analytical instrumentations dedicated to cultural heritage, the non-invasive identification of
materials belonging to the wide class of organic compounds historically used in paintings is still a challenging task. Near-infrared
spectroscopy offers several attractive features that make this technique particularly suitable to this purpose. In fact, it
is non-invasive, allows for non-contact measurements in reflectance mode, gives molecular information on complex macromolecules,
and can be performed on-site by means of portable devices. First-derivative transformation of reflectance spectroscopic data
has been applied to provide a simple and fast way to deduce more information from NIR spectra. This approach has allowed spectral
features to be identified that can be useful to distinguish different compounds belonging to the classes of lipids, proteins,
and resins. To this purpose, at first, a spectral database of pure standard has been collected. Our analytical approach was
then successfully validated on pictorial models reproducing the typical stratigraphy of an easel painting. As final step,
the study of a real painting has been attempted and a drying oil, animal glue, and a terpenic natural resin, as well as an
earth pigment were clearly identified, as cross-validated by GC-MS analysis. 相似文献
3.
Lluveras-Tenorio A Andreotti A Bonaduce I Boularand S Cotte M Roqué J Colombini MP Vendrell-Saz M 《Chemistry Central journal》2012,6(1):45-18
ABSTRACT: BACKGROUND: Establishing the distribution of materials in paintings and that of their degradation products by imaging techniques is fundamental to understand the painting technique and can improve our knowledge on the conservation status of the painting. The combined use of chromatographic-mass spectrometric techniques, such as GC/MS or Py/GC/MS, and the chemical mapping of functional groups by imaging SR FTIR in transmission mode on thin sections and SR XRD line scans will be presented as a suitable approach to have a detailed characterisation of the materials in a paint sample, assuring their localisation in the sample build-up. This analytical approach has been used to study samples from Catalan paintings by Josep Maria Sert y Badia (20th century), a muralist achieving international recognition whose canvases adorned international buildings. RESULTS: The pigments used by the painter as well as the organic materials used as binders and varnishes could be identified by means of conventional techniques. The distribution of these materials by means of Synchrotron Radiation based techniques allowed to establish the mixtures used by the painter depending on the purpose. CONCLUSIONS: Results show the suitability of the combined use of SR FTIR and SR XRD mapping and conventional techniques to unequivocally identify all the materials present in the sample and their localization in the sample build-up. This kind of approach becomes indispensable to solve the challenge of micro heterogeneous samples. The complementary interpretation of the data obtained with all the different techniques allowed the characterization of both organic and inorganic materials in the samples layer by layer as well as to establish the painting techniques used by Sert in the works-of-art under study. 相似文献
4.
Edith Joseph Silvia Prati Giorgia Sciutto Marcella Ioele Paola Santopadre Rocco Mazzeo 《Analytical and bioanalytical chemistry》2010,396(2):899-910
Different Fourier transform infrared microspectroscopic techniques, using attenuated total reflection (ATR) mode and single-element
mercury–cadmium–telluride (MCT) detector (mapping) or multielement MCT detector (raster scanning), are compared with each
other for the characterisation of inorganic compounds and organic substances in paint cross sections. All measurements have
been performed on paint cross sections embedded in potassium bromide, a transparent salt in the mid-infrared region, in order
to better identify the organic materials without the interference of the usual embedding resin. The limitations and advantages
of the different techniques are presented in terms of spatial resolution, data quality and chemical information achieved.
For all techniques, the chemical information obtained is found to be nearly identical. However, ATR mapping performed with
a recently developed instrumentation shows the best results in terms of spectral quality and spatial resolution. In fact,
thin organic layers (∼10 μm) have been not only identified but also accurately located. This paper also highlights the recent
introduction of multielement detectors, which may represent a good compromise between mapping and imaging systems. 相似文献
5.
Pitarch A Ramón A Álvarez-Pérez A Queralt I 《Analytical and bioanalytical chemistry》2012,402(4):1481-1492
Energy dispersive X-ray fluorescence is a common analytical tool for layer thickness measurements in quality control processes
in the coating industry, but there are scarce microanalytical applications in order to ascertain semi-quantitative or quantitative
information of painted layers. “Oil on copper” painting becomes a suitable material to be analysed by means of X-ray fluorescence
spectrometry, due to the metallic nature of substrate and the possibility of applying layered models as used in coating industry.
The aim of this work is to study the suitability of a quantitative energy dispersive X-ray fluorescence methodology for the
assessment of the areal distribution of pigments and the characterization of painting methods on such kind of pictorial artworks.
The method was calibrated using standard reference materials: dried droplets of monoelemental standard solutions laid on a
metallic plate of copper. As an example of application, we estimated pigment mass distribution of two “oil on copper” paintings
from the sixteenth and eighteenth centuries. Pictorial layers have been complementarily analysed by X-ray diffraction. Apart
of the supporting media made of copper or brass, we could identify two different superimposed layers: (a) a preparation layer
mainly composed by white lead and (b) the pictorial layer of variable composition depending on the pigments used by the artist
on small areas of the painting surface. The areal mass distribution of the different elements identified in the painting pigments
(Ca, Cr, Mn, Fe, Zn, Cd, Hg and Pb) have been determined by elemental mapping of some parts of the artworks. 相似文献
6.
Giulia Festa Claudia Scatigno Francesco Armetta Maria Luisa Saladino Veronica Ciaramitaro Viviana Mollica Nardo Rosina Celeste Ponterio 《Molecules (Basel, Switzerland)》2022,27(1)
Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques (X-ray Fluorescence, Raman, Attenuated Total Reflectance and Total Reflectance Infrared Spectroscopies) and six different spectrometers are tested to evaluate the impact of different setups. The novelty of the work is to use a systematic approach on this initial dataset using the entire spectroscopic energy range without any windows selection to solve problems linked with the manipulation of large analytes/materials to find an indistinct property of one or more spectral bands opening new frontiers in the dataset spectroscopic analyses. 相似文献
7.
Sciutto G Dolci LS Buragina A Prati S Guardigli M Mazzeo R Roda A 《Analytical and bioanalytical chemistry》2011,399(9):2889-2897
The identification and localization of organic components in the complex stratigraphy of paintings play a crucial role in
studies of painting techniques and authentication, restoration, and conservation of artworks. Much scientific effort has been
expended for the development of analytical approaches suitable for the investigation and characterization of organic substances,
allowing high sensitivity, specificity, and spatial resolution. Proteins (e.g., ovalbumin, casein, and collagen from different
animal sources) are one of the classes of organic substances most widely used as painting materials. The analytical techniques
commonly used for their analysis (micro Fourier transform infrared spectroscopy, chromatographic techniques, and proteomic
approaches) have limits related to the lack of specificity or to the absence of information concerning the stratigraphic localization
of the detected proteins. Immunological techniques are a promising alternative approach for the characterization of proteins
in artworks. Thanks to the high specificity of antigen–antibody reactions, these techniques are widely used for the analysis
of proteins in bioanalytical and clinical chemistry and recently they have been successfully applied in the field of science
for conservation of cultural heritage. The present research aimed to develop an ultrasensitive chemiluminescent immunochemical
procedure for the simultaneous localization of ovalbumin and bovine casein (two common proteins found in binding media or
varnishes of artistic and archaeological samples) in resin-embedded painting micro cross-sections. The possibility of performing
the simultaneous identification of different proteins in painting cross-sections is of particular relevance in the field of
cultural heritage because samples are often small and available in a limited number; therefore, the maximum amount of information
must be obtained from each of them. 相似文献
8.
Summary Thirty standard painting layers were analysed by pyrolysis-gas chromatography/mass spectrometry (Py-GC-MS) and by Py-GC-MS
in the presence of tetramethylammonium hydroxide (pyrolysis/methylation). Painting layers were prepared according to Renaissance
recipes for tempera, employing proteinaceous binders (egg, glue and casein) and six different pigments. Thermal degradation
products of proteins, carbohydrates and lipids were selected for semiquantitative analysis based on single/summed ion monitoring
(SIM) mode. The relative distribution of these products was used to characterise binding media for the purpose of their identification
in painting layers. 相似文献
9.
Francesca Caterina Izzo Elisabetta Zendri Guido Biscontin Eleonora Balliana 《Journal of Thermal Analysis and Calorimetry》2011,104(2):541-546
Thermogravimetry coupled with differential scanning calorimetry (TG–DSC) has been commonly used in the field of conservation
of Cultural Heritage for the study of art objects, especially for the characterisation of inorganic matrixes. In recent years,
thermal analyses have been applied to the study of organic painting materials. The advantages of performing TG–DSC are linked
to the fact that it is micro-destructive technique which does not require any treatment prior the analysis and provide useful
information in relatively short time. The aim of this study is to describe the application of TG–DSC on the study of oil binders
used in contemporary paints. Even if synthetic binders have become increasingly popular in the 20th century, many contemporary
artists still prefer the more traditional media: drying oils. Although the wish of recalling traditional methods, much practical
knowledge in paint preparation by mixing drying oil and pigments and in the behaviour of the mixture has been lost. This is
mainly due to the different composition of contemporary materials in comparison with the traditional ones and may sometimes
lead to different drying properties of the oil paint formulations and consequent problems in the art creation and conservation.
For answer to this artistic need and in particular to the difficulties outlined by artists themselves in producing and employing
oil paints, unpigmented and pigmented oil films were studied after a week, 1 and 2 years of natural drying under laboratory
conditions. Thermal analyses were performed in air flow: the focus of this research was, in fact, to study the thermal and
oxidative behaviours of young films for better understanding the very first processes leading to the formation of the film. 相似文献
10.
Valeria Di Tullio Donatella Capitani Federica Presciutti Gennaro Gentile Brunetto Giovanni Brunetti Noemi Proietti 《Analytical and bioanalytical chemistry》2013,405(26):8669-8675
NMR stratigraphy was used to investigate in situ, non-destructively and non-invasively, the stratigraphy of hydrogen-rich layers of an ancient Nubian detached mural painting. Because of the detachment procedure, a complex multi-layered artefact was obtained, where, besides layers of the original mural painting, also the materials used during the procedure all became constitutive parts of the artefact. NMR measurements in situ enabled monitoring of the state of conservation of the artefact and planning of minimum representative sampling to validate results obtained in situ by solid-state NMR analysis of the samples. This analysis enabled chemical characterization of all organic materials. Use of reference compounds and prepared specimens assisted data interpretation. Figure
Right side, portable NMR scanning an ancient detached mural painting, left side NMR stratigraphy of a region of the painting 相似文献
11.
Leonardo Brizi Villiam Bortolotti Giulia Marmotti Mara Camaiti 《Magnetic resonance in chemistry : MRC》2020,58(9):889-901
Paintings on canvas are complex structures created by superimposing layers of different composition. Investigations on the structure of these artworks can provide essential information on their state of conservation, pictorial technique, possible overpaintings, and in planning a proper conservation plan. Standard methods of investigation consist in sampling a limited number of fragments for stratigraphic analyses. Despite the recognized validity of these methods, they are affected by evident limitations. Nuclear magnetic resonance (NMR) profiling, often named NMR stratigraphy, is an NMR relaxometry technique applied by single-sided portable devices developed to overcome the disadvantages of microinvasive stratigraphic analyses. The potential of this approach on artworks, including wall paintings and a few examples of painted canvas, is described in the literature. In this study, NMR profiles of painting on canvas were examined by analyzing transverse relaxation time data by T2 quasi-continuous distributions and the results compared with standard stratigraphic cross-sections analysis. Combining signal intensity and T2 quasi-continuous distributions, the identification of textile, preparatory, and paint layers was enhanced. The diction “NMR stratigraphy” for these inhomogeneous layered artworks is also discussed. Indeed, unlike the stratigraphic cross-sections, NMR profiles provide information on a volume (flat slice), rather than on a surface, and the collected signal can derive from nonuniform and partially overlapping layers. This study paves the way for extensive investigations on relaxation time quasi-continuous distributions in various binder/pigment mixtures in order to improve the reliability of NMR profile as an innovative, non–invasive, and nondestructive method for analyzing paintings on canvas. 相似文献
12.
Paint cross-sections have been analysed using the attenuated total reflection technique combined with FTIR mapping microspectroscopy in order to characterise the nature of the compounds present and map their localisation in the stratigraphy. The study reveals the possibilities offered by micro-ATR devices for obtaining informations about the organic substances employed in painting techniques and in particular their distribution in the different layers, showing a real improvement over traditional analytical investigations in use for the detection of organic substances. Limitations, such as the contamination of the embedding resin and the typical spectral resolution (20 μm) are presented and alternative methods were proposed to obtain better results. In particular, the use of an infrared transparent salt (KBr) as embedding material for the cross-sections is evaluated and seems to be very promising. Furthermore, ATR mapping represent a useful non-destructive analytical technique complementary to others molecular and elemental analyses to be performed afterwards such as SEM-EDX. 相似文献
13.
Vandenabeele P Castro K Hargreaves M Moens L Madariaga JM Edwards HG 《Analytica chimica acta》2007,588(1):108-116
In archaeometry, one of the main concerns is to extract information from an art object, without damaging it. Raman spectroscopy is being applied in this research field with recent developments in mobile instrumentation facilitating more routine analysis. This research paper evaluates the performances of five mobile Raman instruments (Renishaw RA100, Renishaw Portable Raman Analyser RX210, Ocean Optics RSL-1, Delta Nu Inspector Raman, Mobile Art Analyser - MArtA) in three different laboratories. A set of samples were collected, in order to obtain information on the spectral performances of the instruments including: spectral resolution, calibration, laser cut-off, the ability to record spectra of organic and inorganic pigments through varnish layers and on the possibilities to identify biomaterials. Spectra were recorded from predefined regions on a canvas painting to simulate the investigation of artworks and the capabilities to record spectra from hardly accessible areas was evaluated. 相似文献
14.
This work presents a preliminary study on the ageing process of proteinaceous binder materials used in painting under UV light. With this aim, two sets of model samples were prepared: samples prepared using a single protein material and complex samples prepared in a similar way to the sequence of layers in a real painting from lowest to highest complexity (protein, drying oils, pigment and varnish). The study focuses on acquiring information about the possible degradation process of proteinaceous binders due to ageing and how this process be affected by the presence of characteristic non-proteinaceous painting materials, such as lipids from linseed oil, terpenic compounds from varnish and inorganic pigments. Samples simulated the accelerated ageing process, as did the UV light exposition. The FT-IR spectra were recorded after 100, 500, 1000 and 1500 h of exposition. The study of the accelerated ageing process was performed by means of principal component analysis (PCA) using the FT-IR spectra obtained. Loadings from the significant principal components were analysed to find the FT-IR frequency (cm−1) involved in the degradation process. The study showed the lack of any relevant modification on the proteins in the single model samples. On the contrary, the complex model samples showed the ageing process. The accelerated ageing process can be explained by a principal component from PCA. The most affected IR region was 2900-3600 cm−1, where the amide band was included. 相似文献
15.
Sarmiento A Pérez-Alonso M Olivares M Castro K Martínez-Arkarazo I Fernández LA Madariaga JM 《Analytical and bioanalytical chemistry》2011,399(10):3601-3611
Fourier transform infrared spectroscopy is a powerful analytical technique to study organic materials. However, in Cultural
Heritage, since the sample under analysis is always a complicated matrix of several materials, data analysis performed through
peak-by-peak comparisons of sample spectra with those of standard compounds is a tedious method that does not always provide
good results. To overcome this problem, a chemometric model based on principal component analysis was developed to classify
and identify organic binding media in artworks. The model allows the differentiation of five families of binders: drying oils,
waxes, proteins, gums, and resins, taking into account the absorption bands in two characteristic spectral windows: C–H stretching
and carbonyl band. This new methodology was applied in the characterization of binders in three kinds of artworks: papers
of historical, archeological, and artistic value, easel paintings, and polychromed stone-based sculptures. 相似文献
16.
Kuckova S Nemec I Hynek R Hradilova J Grygar T 《Analytical and bioanalytical chemistry》2005,382(2):275-282
Two methods of analysis of organic components of colour layers of art works have been tested: IR microspectroscopy of indigo, Cu-phthalocyanine, and Prussian blue, and MALDI-TOF-MS of proteinaceous binders and a protein-containing red dye. The IR spectra distortion common for smooth outer surfaces and polished cross sections of colour layer of art works is suppressed by reflectance measurement of microtome slices. The detection limit of the three blue pigments examined is ~0.3 wt% in reference colour layers in linseed oil binder with calcite as extender and lead white as a drying agent. The sensitivity has been sufficient to identify Prussian blue in repaints on a Gothic painting. MALDI-TOF-MS has been used to identify proteinaceous binders in two historical paintings, namely isinglass (fish glue) and rabbit glue. MALDI-TOF-MS has also been proposed for identification of an insect red dye, cochineal carmine, according to its specific protein component. The enzymatic cleavage with trypsin before MALDI-TOF-MS seems to be a very gentle and specific way of dissolution of the colour layers highly polymerised due to very long aging of old, e.g. medieval, samples. 相似文献
17.
Gaetano Corso Monica Gelzo Angela Chambery Valeria Severino Antimo Di Maro Filomena Schiano Lomoriello Oceania D'Apolito Antonio Dello Russo Patrizia Gargiulo Ciro Piccioli Paolo Arcari 《Journal of separation science》2012,35(21):2986-2993
Spectroscopic and MS techniques were used to characterize the pigments and the composition of polar and nonpolar binders of a stray wall painting fragment from Liternum (Italy) archaeological excavation. X‐ray fluorescence and diffraction analysis of the decorations indicated mainly the presence of calcite, quartz, hematite, cinnabar, and cuprorivaite. Infrared spectroscopy, GC coupled to flame‐ionization detector, and MS analysis of the polar and nonpolar components extracted from paint layers from three different color regions revealed the presence of free amino acids, sugars, and fatty acids. Interestingly, LC‐MS shotgun analysis of the red painting region showed the presence of αS1‐casein of buffalo origin. Compared to our previous results from Pompeii's wall paintings, even though the Liternum painting mixture contained also binders of animal origin, the data strongly suggest that in both cases a tempera painting technique was utilized. 相似文献
18.
Palmieri M Vagnini M Pitzurra L Rocchi P Brunetti BG Sgamellotti A Cartechini L 《Analytical and bioanalytical chemistry》2011,399(9):3011-3023
Enzyme-linked immunosorbent assay (ELISA) analysis of proteins offers a particularly promising approach for investigations
in cultural heritage on account of its appreciated properties of being highly specific, sensitive, relatively fast, and cost-affordable
with respect to other conventional techniques. In spite of that, it has never been fully exploited for routine analyses of
painting materials in consideration of several analytical issues that inhibited its diffusion in conservation science: limited
sample dimensions, decrease of binder solubility and reduced availability of antibody bonding sites occurring with protein
degradation. In this study, an ELISA analytical protocol suited for the identification of aged denatured proteins in ancient
painting micro-samples has been developed. We focused on the detection of bovine β-casein and chicken ovalbumin as markers
of bovine milk (or casein) and chicken albumen, respectively. A systematic experimentation of the ELISA protocol has been
carried out on mock-ups of mural and easel painting prepared with 13 different pigments to assess limits and strengths of
the method when applied for the identification of proteins in presence of a predominant inorganic matrix. The analytical procedure
has been optimized with respect to protein extraction, antibodies’ concentrations, incubation time and temperature; it allows
the detection of the investigated proteins with sensitivity down to nanograms. The optimized protocol was then tested on artificially
aged painting models. Analytical results were very encouraging and demonstrated that ELISA allows for protein analysis also
in degraded painting samples. To address the feasibility of the developed ELISA methodology, we positively investigated real
painting samples and results have been cross-validated by gas chromatography–mass spectrometry. 相似文献
19.
Victor Burakov Vasilii Kiris Alena Klyachkovskaya Natalia Kozhukh Sergei Raikov 《Mikrochimica acta》2006,156(3-4):337-342
Laser-induced breakdown spectroscopy has been applied to layer-by-layer pigment material microanalysis from the different
sections of Hubert Robert’s (1733–1808) painting “Landscape of a Pool with an Obelisk and Ruins of an Aqueduct”. This painting
consists of two sections and, therefore, requires thorough examination of the pigments from both sections in order to identify
their authenticity. The data obtained on the elemental composition of the paint layers including the ground layer alongside
with art examination have formed the basis for the identification, attribution and restoration of both investigated sections
of the painting. 相似文献
20.
Duce C Ghezzi L Onor M Bonaduce I Colombini MP Tine' MR Bramanti E 《Analytical and bioanalytical chemistry》2012,402(6):2183-2193
In this work, we characterized paint reconstructions using ovalbumin and casein as binders, and cinnabar (HgS) as a pigment,
before and after artificial ageing. Egg and casein are common paint binders that were used historically in the technique of
tempera painting. Despite extensive research on the identification of proteinaceous binders in paintings, there is a substantial
lack of knowledge regarding the ageing pathway of their protein content, and their chemical interaction with inorganic pigments.
Thermogravimetric analysis, infrared spectroscopy and size-exclusion chromatography (SEC) were used to reveal the physico-chemical
processes involved in the ageing of proteins in paintings. Taken together, the three techniques highlighted that proteins
are subject to both cross-linking and hydrolysis upon ageing, and to a lesser extent, to oxidation of the side chains. Mercury–protein
interactions were also revealed using a cold vapour generation atomic fluorescence spectrometer mercury-specific detector
coupled to SEC. The study clearly showed that HgS forms stable complexes with proteins and acts as a sensitizer in cross-linking,
hydrolysis and oxidation. 相似文献