Feasibility of analyzing molecular pigments in paint layers using TOF S–SIMS

A first attempt to measure the molecular compositions of pigments in paintings using static SIMS was made. An investigation of pellets of pure pigments such as auripigment and verdigris allowed the detection of numerous high m/z ions useful for molecular identification. Analysis of pigments in embedded paint fragments, on the other hand, only yielded elemental information because of charge build-up and contamination problems. Optimization of the form in which the sample is presented to the analysis method is obviously the price to pay for the ultimate sensitivity and information depth of S-SIMS.     

Analysis of polymeric phenolics in red wines using different techniques combined with gel permeation chromatography fractionation

A multiple-step analytical method was developed to improve the analysis of polymeric phenolics in red wines. With a common initial step based on the fractionation of wine phenolics by gel permeation chromatography (GPC), different analytical techniques were used: high-performance liquid chromatography-diode array detection (HPLC-DAD), HPLC-mass spectrometry (MS), capillary zone electrophoresis (CZE) and spectrophotometry. This method proved to be valid for analyzing different families of phenolic compounds, such as monomeric phenolics and their derivatives, polymeric pigments and proanthocyanidins. The analytical characteristics of fractionation by GPC were studied and the method was fully validated, yielding satisfactory statistical results. GPC fractionation substantially improved the analysis of polymeric pigments by CZE, in terms of response, repeatability and reproducibility. It also represented an improvement in the traditional vanillin assay used for proanthocyanidin (PA) quantification. Astringent proanthocyanidins were also analyzed using a simple combined method that allowed these compounds, for which only general indexes were available, to be quantified.     

Hemisynthesis and structural characterization of flavanol‐(4,8)‐vitisins by mass spectrometry

Vitisins constitute the major group of pyranoanthocyanins naturally occurring in red wines. Regarding their chemical structure, only carboxypyranoanthocyanins have been detected and quantified in red wines, but no vitisin with substitutions in the carbons of the A ring has been identified. However, considering the chemical reactions that take place in red wine, the existence of flavan‐3‐ol‐(4,6/8)‐vitisins is expected. This paper reports for the first time the structural identification of catechin‐vitisin A and catechin‐vitisin B based on their mass data and fragmentation patterns. This work also provides some chromatographic and visible spectroscopic features of these pigments and documents the existence of both in red table wines. Moreover, it is also proposed that Cat‐Vit A pigments arise from the cycloaddition of pyruvic acid to an anthocyanin moiety of a flavanol‐anthocyanin adduct rather than by direct nucleophilic attack of a vitisin A on the carbocation C₄ of catechin. Copyright © 2010 John Wiley & Sons, Ltd.     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.     

Development of High NIR-Reflective Red Li2MnO3 Pigments

In this work, the development of a novel class of eco-friendly red pigments based on doped Li₂MnO₃ is reported. These new compounds offer red color values of a* > 34, which are recognizably higher than the red value provided by the commonly used red pigment iron oxide Bayferrox 4130. However, the real outstanding attribute of these novel substances is their strikingly high NIR-reflectance that gives promise for a new class of materials for the practical utilization as cool pigments in building components and ceramics. We have synthesized the inorganic pigments by conventional solid-state reactions at 900 °C and subsequently carried out the structural characterizations by X-ray powder diffraction (XRPD) and Rietveld analysis. We recorded the diffuse reflectance spectra of the obtained powders and determined the color properties by means of CIE L*a*b* coordinates. Finally, we measured the NIR reflectance and calculated the NIR solar reflection of these compounds affording values above 85 % in the range from 700 to 2500 nm.     

The compositional and mineralogical analysis of fired pigments in Nasca pottery from Cahuachi (Peru) by the combined use of the portable PIXE-alpha and portable XRD techniques

An analytical protocol based on the combined use of the portable PIXE-alpha (Particle Induced X-ray Emission) and XRD (X-ray Diffraction) non destructive techniques developed at the LANDIS laboratory (Laboratorio di Analisi Non Distruttive) of the INFN–CNR (Istituto Nazionale di Fisica Nucleare–Consiglio Nazionale delle Ricerche) in Catania (Italy), was applied for the characterisation of the surface paints of some archaeological fragments of Nasca pottery from the Ceremonial Centre of Cahuachi in Southern Peru.Measurements were carried out on the black, white, red, orange and grey pigments; quantitative information on the chemical composition as well as on the mineralogical phases present on the paints were obtained.Results allowed to make some considerations about the materials and the manufacturing technique used to realise such fired pigments.It should be noted that during firing the precursor minerals composing the pigments undergo a phase transformation and their identification presents some difficulties.     

Effect of yeast extract on growth kinetics of Monascus purpureus

Growth kinetics and red pigment production of Monascus purpureus CCT 3802 was studied. A reproducible inoculum with extremely dispersed hyphae for bioreactor runs was obtained through a two-step cultivation in a shaker. First, the spores were cultivated in a complex medium rendering a suspension of vegetative cells. In the second step these cells were grown in a semisynthetic medium. Two types of media were employed in the bioreactor runs: a semisynthetic (glucose, salts, and yeast extract), and a synthetic, without yeast extract. The inclusion of yeast extract, caused an increase in cell yield on glucose (Y_s/s) as high as 40%. Also, yeast extract probably yielded a higher proportion of red pigment associated with the cell, relative to the synthetic medium. On the other hand, cells grown on the synthetic medium were slightly higher producers of red soluble pigments.     

Study of mural paintings using in situ XRF, confocal synchrotron-μ-XRF, μ-XRD, optical microscopy, and SEM-EDS--the case of the frescoes from Misericordia Church of Odemira

In this work, we present the results of an analytical method developed for detailed pigment identification, stratigraphy, and degradation of the paint layers of mural paintings applied in the study of the 17th century frescoes from the Misericordia Church of Odemira (Southwest Portugal). In situ X-ray fluorescence spectrometry analyses were performed on three panels of the mural paintings and complemented by colorimetric measurements. The different color areas were also sampled as microfragments (approx. 1 mm2) that were studied as taken or mounted in epoxy resin to expose the different paint layers. The microfragments of paint layers and their cross sections were characterized by optical microscopy and scanning electron microscopy coupled with energy dispersive X-ray spectrometry. Furthermore, elemental analysis was obtained with spatially resolved confocal synchrotron radiation μ-X-ray fluorescence spectrometry performed at ANKA synchrotron FLUO beamline. Occasionally, phase analysis by μ-X-ray diffraction was also performed. Results from the different techniques allowed pigment identification and, in some cases, the evaluation of color changes due to degradation processes and, considering the Southern Portugal geology, the identification of their possible provenance. The pigments used were essentially yellow, brown and red ochres, smalt blue, copper green, and black earths, probably from local sources.     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non-degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X-ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.     

Two azo pigments based on β‐naphthol

There has been much discussion in the literature of the azo–hydrazone tautomerism of pigments. All commercial azo pigments with β‐naphthol as the coupling compound adopt the hydrazone tautomeric form (Ph—NH—N=C) in the solid state. In contrast, the red pigments 1‐[4‐(dimethylamino)phenyldiazenyl]‐2‐naphthol, C₁₈H₁₇N₃O, (1a), and 1‐[4‐(diethylamino)phenyldiazenyl]‐2‐naphthol, C₂₀H₂₁N₃O, (1b), have been reported to be azo tautomers or a mixture of azo and hydrazone tautomers in the solid state. To prove these observations, both compounds were synthesized, recrystallized and their crystal structures redetermined by single‐crystal structure analysis. Difference electron‐density maps show that the H atoms of the hydroxyl groups are indeed bonded to the O atoms. Nevertheless, a small amount of the hydrazone form seems to be present. Hence, the compounds are close to being `real' azo compounds. Compound (1a) crystallizes with a herring‐bone structure and compound (1b) forms a rare double herring‐bone structure.     

An Insight to the Composition of Pre-Hispanic Mayan Funerary Pigments by 1H-NMR Analysis

The funerary rites of particular members of the pre-Hispanic Mayan society included the pigmentation of the corpse with a red color. In order to understand this ritual, it is first necessary to identify the constituents of the pigment mixture and then, based on its properties, analyze the possible form and moment of application. In the present approach, ¹H-NMR analysis was carried to detect organic components in the funerary pigments of Xcambó, a small Maya settlement in the Yucatan Peninsula. The comparison of the spectra belonging to the pigment found in the bone remains of seven individuals, and those from natural materials, led to the identification of beeswax and an abietane resin as constituents of the pigment, thus conferring it agglutinant and aromatic properties, respectively. The ¹H-NMR analysis also allowed to rule out the presence of copal, a resin found in the pigment cover from paramount chiefs from the Mayan society. Additionally, a protocol for the extraction of the organic fraction from the bone segment without visible signs of analysis was developed, thus broadening the techniques available to investigate these valuable samples.     

Micro-Raman analysis of coloured lithographs

Raman micro-spectroscopy was chosen for analysis and identification of the pigments present in four nineteenth-century hand-coloured lithographs, as this technique has several advantages over others for this purpose. The possibility of performing completely non-destructive analysis without any sampling is probably one of its most favourable qualities for art analysis. Raman spectroscopy can also be used to determine some pigments that cannot be detected using FTIR, such as vermilion, carbon blacks, cadmium pigments, etc. Among others, Prussian blue, ultramarine blue, carbon black, chrome yellow, yellow ochre, red lead, red iron oxide, burnt Sienna, indigo blue, chrome orange, phthalocyanine green, and some other organic pigments, were determined in the specimens. The results obtained have led to doubts about the age of the lithographs.     

Non-destructive characterization of fifty various species of pigments of archaeological and artistic interest by using the portable X-ray diffraction system of the LANDIS laboratory of Catania (Italy)

In recent years a portable XRD system with high angular resolution and rapid measurement time was realized at the LANDIS laboratory of the LNS-INFN and IBAM-CNR of Catania (Italy) for application in the cultural heritage field. The system was previously used for the characterization of some pigments present in ancient frescoes. The main task of this work is to show the possibility of using the above portable diffractometer in the identification of a large variety of pigments commonly used to realize archaeological and artistic masterpieces.50 reference standards of pigments with a known mineralogical composition were prepared and measured; analytical results evidenced both the advantages and the limitations of using such a system in the analysis of different typologies of pigments and allowed to realize a raw database to be used during the characterization of real samples.     

Characterization of Wallpaintings from the Caliphal Baths of Cordoba (Spain) by X-Ray Diffraction and Raman Microspectroscopy

Wallpainting fragments from the Caliphal Baths of Cordoba, Spain, were studied in this work for the first time. X-ray diffraction (XRD) and Raman microspectroscopy allowed the chemical nature of the pigments used by the Arabic artists of the time to be identified. All pigments were applied over a gypsum priming layer. The white, red, and yellow colors used were obtained from gypsum, hematite, and goethite, respectively. Some pigments were prepared by mixing these materials. The analytical techniques used also allowed the mortar material to be identified. The results of this study may be useful to develop effective conservation strategies for archaeological remains.     

Studies on the Stability of the Human Cone Visual Pigments†

The retina of vertebrates contains two kinds of photoreceptor cells, rods and cones, which contain their specific visual pigments that are responsible for scotopic and photopic vision, respectively. In cone photoreceptor cells, there are three types of color pigments: blue, green and red, each with a distinctive absorption maximum. The goal of this investigation was to identify optimal conditions under which these pigments could be obtained and isolated in a stable form, thereby facilitating structural studies using high‐resolution approaches. For this purpose, all three human cone opsins were initially expressed in mammalian cells, reconstituted with 11‐cis retinal, detergent solubilized, purified and their stability compared with rod rhodopsin. As all three pigments showed dramatically reduced stability relative to rhodopsin, site‐directed mutagenesis was used in an attempt to engineer stability into the green cone pigment. The mutations introduced some structural motifs and sites of posttranslational modification present in rhodopsin, as well as amino acid substitutions that have been found to stabilize the rod opsin apo‐protein. We also modified the hydrophobic environment of the green cone pigment by varying the detergent and detergent/lipid composition used during solubilization and purification, and compared them with the retinal reconstituted pigment in membranes. Our results show that these changes do not significantly improve the inherent instability of the human cone pigments, and in some cases, lead to a decrease in stability and protein aggregation. We conclude that further efforts are required to stabilize the human cone pigments in a form suitable for high‐resolution structural studies.     

FIBER-OPTIC PLANT TISSUES: SPECTRAL DEPENDENCE IN DARK-GROWN AND GREEN TISSUES*

Abstract— The fiber-optic properties of etiolated plant tissues can be used to detect and characterize pigment absorption in vivo. Transmission spectra of light guided through several monocot and dicot etiolated tissues show a decreasing red/far red ratio with increasing tissue length. Absorption bands attributable both to vacuolar pigments such as anthocyanins and to chloroplast pigments lead to the conclusion that the guided light passes through both vacuole and cytoplasm. As etiolated tissue becomes green under white light treatment, the red/far red ratio also changes, the nature of the change depending upon the tissue involved. The blue/red ratio also changes both with increasing length of etiolated tissue and during the greening process, with the changes again dependent on the tissue involved. The spectral dependence of the light-guiding phenomenon in dark grown and green plants may have implications for physiological responses mediated by phytochrome.