A masked-alkene metathesis-based synthesis of isopulo’upone

A metathesis-based formal synthesis of (±)-isopulo’upone has been completed featuring a masked olefin metathesis/elimination sequence followed by an intramolecular Diels-Alder reaction to construct the 5,6-fused bicyclic core.     

Rapid optimized separation of bromide in serum samples with capillary zone electrophoresis by using glycerol as additive to the background electrolyte

After decades of neglect, bromide has recently been re-introduced in therapy as an effective anti-epileptic drug. The present paper describes the methodological optimization and validation of a method based on capillary zone electrophoresis for the rapid determination of bromide in serum using a high-viscosity buffer and a short capillary (10 cm). The optimized running buffer was composed of 90 mM sodium tetraborate, 10 mM sodium chloride, pH 9.24 and 25% glycerol. The separation was carried out at 25 kV at a temperature of 20 °C. Detection was by direct UV absorption at 200 nm wavelength. The limit of detection (signal-to-noise ratio = 5) in serum was 0.017 mM. The precision of the method was verified in blank serum samples spiked with bromide, obtaining intra-day and day-to-day tests, relative standard deviation values ≤0.2% in terms of migration times and values <2% in terms of peaks areas, respectively.     

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.     

1D lead iodide crystals encapsulated within single walled carbon nanotubes

The structure and binding energies of lead iodide crystals encapsulated within single‐walled carbon noanotubes are studied using density functional theory. Calculations were performed on the simulated PbI₂ structure encapsulated within a (12,12) single‐walled nanotube, to investigate the perturbations on the PbI₂ crystal and tube structure and electronic structure, and to estimate the binding energy. The calculation confirms the structure as a single chain of PbI₆ octahedra bound by two chains of PbI₅ square pyramids. The calculated binding energy shows that the encapsulation is noncovalent. Minimal charge transfer is observed between nanotube and the PbI₂ crystals. The band gap is shown to increase from the bulk to the encapsulated structure. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009