Mixed crystals containing the dioxo complex [[Ph3SiO]2VO2]- and novel pentacoordinated oxoperoxo complex [[Ph3SiO]2VO(O2)]-: X-ray crystal structure and assessment as oxidation catalysts

[n-Bu4N][[Ph3SiO]2VO2] reacts with H2O2 to yield an oxoperoxo complex which crystallizes as a mixed-crystal compound, [P(C6H5)4][[(C6H5)3 SiO]2VO2]x[[(C6H5)3 SiO]2VO(O2)](1-x), 1(x = 0.57). It has been characterized by elemental analysis and spectroscopy (51V NMR, UV-visible and IR). The X-ray structure analysis reveals the presence of two interrelated anions: [[Ph3SiO]2VVO2]-, 1a, and [[Ph3SiO]2VVO(O2)]-, 1b with a cisoid geometry of the [VO(O2)]+ moiety. The two structures differ only slightly: anion 1a exhibits unusual tetrahedral coordination around the vanadium centre found in the precursor, whereas the geometry at the metal ion in 1b can be described as a trapezoidal pyramid. Steric constraints due to Ph3SiO- ligands and PPh4+ cations are responsible for this geometry. The reactivity of 1 in the C-C bond cleavage of 2-methylcyclohexanone under anaerobic conditions has been studied. The results suggest that peroxygen species are involved in the oxidative cleavage of C-C bonds of cycloalkanones.     

Des3PI: a fragment-based approach to design cyclic peptides targeting protein–protein interactions

Journal of Computer-Aided Molecular Design - Protein–protein interactions (PPIs) play crucial roles in many cellular processes and their deregulation often leads to cellular dysfunctions. One...     

Towards a Comprehensive Characterization of the Low-Temperature Autoxidation of Di-n-Butyl Ether

In the present study, we investigated the oxidation of 2500 ppm of di-n-butyl ether under fuel-rich conditions (φ = 2) at low temperatures (460–780 K), a residence time of 1 s, and 10 atm. The experiments were carried out in a fused silica jet-stirred reactor. Oxidation products were identified and quantified in gas samples by gas chromatography and Fourier transform infrared spectrometry. Samples were also trapped through bubbling in cool acetonitrile for high-pressure liquid chromatography (HPLC) analyses. 2,4-dinitro-phenylhydrazine was used to derivatize carbonyl products and distinguish them from other isomers. HPLC coupled to high resolution mass spectrometry (Orbitrap Q-Exactive^®) allowed for the detection of oxygenated species never observed before, i.e., low-temperature oxidation products (C₈H₁₂O_4,6, C₈H₁₆O_3,5,7, and C₈H₁₈O₂,₅) and species that are more specific products of atmospheric oxidation, i.e., C₁₆H₃₄O₄, C₁₁H₂₄O₃, C₁₁H₂₂O₃, and C₁₀H₂₂O₃. Flow injection analyses indicated the presence of high molecular weight oxygenated products (m/z > 550). These results highlight the strong similitude in terms of classes of oxidation products of combustion and atmospheric oxidation, and through autoxidation processes. A kinetic modeling of the present experiments indicated some discrepancies with the present data.     

Effect of high pressure treatment on the characteristics of a model emulsion

The aim of this study was to investigate the use of HP (high pressure) technology as a possible alternative method for decontamination of non-food medium. HP (500?MPa) did not modify significantly the physicochemical characteristics of a model non-food emulsion. A 10?min HP treatment inactivated totally Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Aspergillus niger and Candida albicans even if all the five microorganisms were inoculated together, regardless of the initial load. No recovery was observed until six months of storage at 25°C.     

Defect assisted subwavelength resolution in III-V semiconductor photonic crystal flat lenses with n = −1

We propose a III-V semiconductor photonic crystal slab designed to operate as a n = −1 superlens at λ₀ = 1.55 μm. The structure consists of air holes arranged in a two-dimensional triangular lattice, of period a, nanopatterned in an InP/InGaAsP/InP slab. Exploiting the second pass-band regime (a/λ₀ ∼ 0.31), subwavelength resolutions as low as 0.38λ₀ for planar lenses have been obtained by the insertion of hexagonal nanocavities within the crystal.     

Modifications of in vitro skin penetration under solar irradiation: evaluation on flow-through diffusion cells

The effect of solar irradiation on ex vivo dermatomed hairless rat skin samples maintained in culture on flow-through diffusion cells for at least 24 h was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay and by histological observations. Transepidermal water loss (TEWL) measurements and kinetic analysis of the permeation of both tritiated water and 14C caffeine through the skin were performed after full-spectrum solar exposure involving the use of a xenon arc solar simulator. After a UV exposure of less than 420 mJ/cm2, skin integrity and permeation of both water and caffeine did not change significantly. In contrast, after a 420 mJ/cm2 UV exposure, the epidermis appeared more contracted, associated with an increase of 55% of TEWL and 220% of the skin permeation of tritiated water after 6 h. The data suggested a dramatic alteration of the skin barrier integrity. Moreover, the flux of 14C caffeine increased rapidly by 338% of the absorption of water 12 h after irradiation. These results reveal the presence of a threshold UV exposure that would not modify skin penetration.     

Supramolecular click chemistry for the self-assembly of a stable Zn(II)-porphyrin-C60 conjugate

Owing to the complementarity between a bis-Zn(II)-porphyrin receptor and a fullerene ligand bearing two pyridine substituents, the substrate can be clicked onto the ditopic receptor, thus leading to a stable non-covalent macrocyclic 1 ratio 1 complex.     

Restricted rotation in a tetrakis(para-substituted phenyl) porphyrin bearing four porphyrin-fullerene substituents

A porphyrin substituted with four porphyrin-fullerene moieties has been prepared and variable-temperature NMR studies revealed a high barrier to free rotation about the four para-substituted phenyl groups of the central porphyrin core.