Electron energy loss spectroscopy elucidates the elusive darkening of zinc potassium chromate in Georges Seurat's A Sunday on La Grande Jatte--1884.

The color darkening of selected brushstrokes of Georges Seurat's A Sunday on La Grande Jatte--1884 was noted as early as 1892. Artificial aging of model systems containing zinc yellow (K(2)O·4ZnCrO(4)·3H(2)O) mixed with linseed oil successfully replicated the phenomena observed on La Grande Jatte. Electron energy loss spectroscopy measurements performed on the uppermost few microns of thin sections of the paint layers (obtained with focused ion beam milling) determined that samples which turned olive green (aged at 90% RH, with SO(2) and light) contain mostly the altered species Cr(III) and that the ochre-yellow coloration of specimens aged at 50% RH with SO(2) and light is due to the presence of dichromate ions (Cr (VI)). The altered species are only present in the first few microns of paint and are likely poorly crystalline, so that they eluded other types of bulk and surface measurements, but they create a substantial color alteration at the surface of the paint films. A similar phenomenon was confirmed on a sample from La Grande Jatte, where Cr(III) and Cr(VI) dichromate ions were detected in the ochre-colored, altered brushstrokes of zinc yellow. Laboratory simulations demonstrated that the equilibrium between chromate and dichromate ions is reversible within the paint film and that the orange dichromate ions can be transformed back into bright yellow chromates by exposure to highly alkaline gases.

Toward the definition of immunosuppressive regimens with antitumor activity.

Immunosuppressive therapies associated with organ transplantation produce an increased risk of cancer development. Malignancies are increased in transplant recipients because of the impaired immune system. Moreover, experimental data point to a tumor-promoting activity of various immunosuppressive agents. In this study, we compared the effects of 4 immunosuppressive agents with different mechanisms of action (cyclosporine, rapamycin, mycophenolic acid, and leflunomide) on the in vitro growth of various tumor cell lines and umbilical vein endothelial cells. To varying degrees rapamycin (10 ng/mL), mycophenolic acid (300 nmol/L), and leflunomide (30 micromol/L) highly inhibited the growth of human rhabdomyosarcoma, hepatocellular carcinoma, colorectal carcinoma, and endothelial cells. In contrast, cyclosporine (100 ng/mL) did not affect their growth. Our data suggest that regimens containing rapamycin, mycophenolic acid, or leflunomide, which have both immunosuppressive and antitumor activities, should be preferred in transplant recipients to minimize the risk of tumors.

A key factor in modern protection of historic buildings: the assessment of penetration of water-repellent polymers into porous stone-materials.

From the 1960s on, the conservation of monuments and stone masonry has witnessed an increasing use of polymeric products during restoration interventions. Actual penetration depths reached by different polymers within the porous stone matrix are supposed to be key factors in determining the efficacy of the treatments themselves (besides, of course, the chemical-mineralogical nature of the stone and the chemical-physical characteristics of the various polymers). This work presents some preliminary results obtained on specimens of Noto calcarenite treated with various polymeric protective products. Samples were investigated with direct analytical methods (micro-ATR spectroscopy, SEM) in order to assess penetration depths reached by polymers inside the stone while reducing to a minimum the necessary manipulation of specimens. The obtained results highlighted the following trend in penetration depths for the various products tested: siloxane product > partially fluorinated acrylic resin > acrylic resin. Moreover, data obtained allowed to establish direct correlation between long term efficacy of products and relative penetration depths.