The photodegradation of cadmium yellow paints in Henri Matisse’s Le Bonheur de vivre (1905–1906)

Evidence for the alteration of the yellow paints in Henri Matisse’s Le Bonheur de vivre (1905–1906, The Barnes Foundation) has been observed since the 1990s. The changes in this iconic work of Matisse’s Fauvist period include lightening, darkening, and flaking of the yellow paints. Handheld X-ray fluorescence (XRF) and multispectral imaging surveys reveal that the degradation is confined to cadmium yellow (CdS) paints. The discoloration of cadmium yellow paints in Impressionist, Post-Impressionist and early modernist work from the 1880s through the 1920s has been ascribed to the photo-oxidative degradation of CdS. Preliminary investigations of the degraded yellow paints in this work involved Cd L_III-edge X-ray Absorption Near Edge Spectroscopy (XANES) at the Stanford Synchrotron Radiation Light Source (SSRL Menlo Park, California) and Scanning Electron Microscopy-energy dispersive X-ray analysis (SEM-EDS) at the Winterthur Museum Scientific Research and Analysis Laboratory. To determine if the visual changes in the paints did in fact indicate photo-oxidative degradation and if different chemistries could be observed for the lightened versus darkened regions, synchrotron radiation-micro Fourier Transform InfraRed (SR-μFTIR) spectroscopy, X-ray Fluorescence (SR-μXRF) mapping and micro X-ray Absorption Near Edge Spectroscopy (μXANES) mapping at the Cd L_III-edge of the altered paint cross-sections were carried out at the European synchrotron radiation facility (ESRF, Grenoble, France) beamline ID-21. The goal is to elucidate the discoloration mechanisms observed in the paint using elemental and speciation mapping. The μXANES mapping and SR-FTIR imaging showed a substantial enrichment of CdCO₃ in the off-white surface crust of the faded/discolored CdS paint. This suggests that the CdCO₃ is present as an insoluble photodegradation product rather than solely a paint filler or starting reagent. Additionally, oxalates and sulfates were found to be concentrated at the alteration surface.     

Vibrational study on the interactions between yak keratin fibres and glyoxylic acid

Raman and IR spectroscopy were used to investigate the changes induced in yak hair keratin by the straightening treatment based on glyoxylic acid. The amino acidic residues that appeared involved in the reaction with glyoxylic acid were serine and lysine; the involvement of the latter was deduced by the spectroscopic detection of iminic species, resulting from the reaction between the aminic group of lysine and the carbonyl group of glyoxylic acid. The reaction with glyoxylic acid induced conformational rearrangements that mainly involved the fibre bulk rather than the cuticle. Changes in the average tyrosine environment and its hydrogen‐bonding state were detected: at increasing glyoxylic acid incorporation, the tyrosine residues appeared more exposed, probably because of H‐bond interactions with the COOH group. The distribution of the disulfide bridge conformation was also affected, although no cleavage of the S–S bond was detected, in agreement with the shiny and healthy appearance of the fibres. Copyright © 2014 John Wiley & Sons, Ltd.     

Broadening of paramagnetic resonance lines by charged point defects in neodymium-doped scheelites

We study paramagnetic resonance linewidth in a series of CaWO₄ and CaMoO₄ crystals with different concentrations of neodymium ions (0.0031–0.81 at %). Experimental data are interpreted in the framework of the statistical theory of line broadening by charged point defects. In our calculations, three different contributions are singled out: arising from the local electric fields, electric field gradients and magnetic fields of the nearby point defects. The interaction parameters are determined from the spectroscopic data available for Nd:CaWO₄ crystal. Direct calculations of the linewidth are performed for different crystal orientations with respect to external magnetic field. We conclude that major contribution to the broadening comes from the interactions with random electric fields produced by neodymium and charge compensator ions.     

Raman scattering of MnOx?CeOx composite catalysts: structural aspects and laser‐heating effects

Composite MnO_x CeO_x catalysts (Mn_at: Ce_at = 1) synthesized via the redox and coprecipitation routes were comparatively characterized by micro‐Raman spectroscopy using a laser irradiation power ranging between 0.6 and 4.2 mW. A quasi‐molecular dispersion of the oxide species determines a major and irreversible structural rearrangement of the redox MnO_x CeO_x system because of severe heating effects for laser power in excess of 0.6 mW. The X‐ray diffraction data of samples calcined in the range of 673 1273 K confirm that the micro‐Raman characterization of the composite MnO_x CeO_x systems requires an adequate minimization of the irradiation power to prevent the strong sintering and restructuring phenomena due to laser‐heating effects. Copyright © 2011 John Wiley & Sons, Ltd.     

Angle of incidence effects in a molecular solid

We investigate the influence of the angle of incidence on the sputter yield when bombarding molecular solid, benzene, with C₆₀. Our simulations show that at normal incidence, essentially all of the projectile energy is deposited into the substrate within ∼2.5 nm of the surface. However, at 75° incident angle, only 35% of the projectile energy is deposited within a depth of less than 1.5 nm of the surface while 65% of the projectile energy is reflected. Therefore, important aspects of the collision process which are dependent upon energy deposition, such as sputter yield, ejection depth, and molecule dissociation, may change as the incident angle changes.     

Transverse spin correlations in a random anisotropy system: Amorphous ErCo2

We provide a coherent interpretation of early small angle scattering experiments performed by some of us on amorphous ErCo₂ [9]. At low temperature the zero field transverse spin-spin correlation function is found to fit a simple exponential for large length scales (l >l_c), supporting the lower critical dimensionality d_c=4. For shorter length scales (l<l_c) the correlation function is of the Ornstein-Zernike type. These results are physically understood in terms of the breaking of ferromagnetism into Imry and Ma domains.A further physical interpretation leads us to consider the localization of ferromagnetic spin waves within Imry and Ma domains in zero field, and their delocalization by application of an external field.     

Structure sensitive factors in molecular cluster formation by ion bombardment of single crystal surfaces

The dynamics of molecular cluster formation from a solid bombarded by a 600 eV Ar⁺ ion have been studied classically by computer simulation. The dimers and trimers are found to establish their identity as clusters within interaction range of the solid, but not by a direct ejection of a bound molecule. The Cu₂/Cu and Cu₃/Cu ratios are found to be strongly dependent on crystal orientation. The (111) face is 2–3 times more likely to produce multimers than the (100) face. We find 9 trimers from (111) but none from (110). The relationship between cluster composition and the original arrangement of those atoms on the surface is presented in detail. We find that each multimer forms from atoms that originate within a roughly circular region of area ～70 Ų or less. This region is not necessarily centered on the ion impact point. A consequence of this observation is that dimers can consist of atoms that were several Ångströms apart on the surface but that most trimers contain at least one nearest neighbor pair of atoms. The calculated energy distribution for the dimers matches well with similar experimental studies.     

Aortic elastin fluorescence afterin vivo labeling with Congo red

Congo red (CR) is an azo dye which not only preferentially binds to elastin, an extracellular matrix protein found in the media of arterial vessel walls, but also fluoresces when it binds to this protein. Protein solubilization data following laser irradiation of elastin:CR suspensions determined that the amount of elastin solubilized by laser irradiation increased with the increase in CR. The saturation point of CR to elastin was attained when 400 g CR was added to 20 mg elastin suspension. When 20 ml of a 5% CR solution in 5% dextrose was administered intravenously, the CR was absorbed in levels sufficient to produce fluorescence of the main arteries in rabbits. Layers of tissue both in the media of the vessels and at the endothelial/intimal interface were clearly differentiated. Therefore, the elastin:CR complex appears to be an ideal system in which the elastin fluorescence could aid in distinguishing between normal and diseased tissue in certain pathological conditions, such as atherosclerosis and some types of breast tumors.