Interband optical absorption in semiconductors with microcrystalline structure

The simplest model concepts are used to calculate the binary correlation function of the intrinsic random field of a semiconductor with microcrystalline structure. The frequency dependence of the absorption coefficient of light in the region of the optical tail formed by the intrinsic random field is investigated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 43–50, May, 1984.In conclusion the author wishes to thank V. L. Bonch-Bruevich for interest in the present work and a number of useful discussions.     

Molybdenum HDS catalysts supported on niobia-silica

The effect of the amount of Nb₂O₅on the dispersion and reductive properties of Mo/Nb₂O₅-SiO₂ catalysts has been studied. Addition of niobium leads to an increase of the dispersion, and the reducibility of molybdenum. A synergetic effect of niobium on the catalytic activity in hydrodesulfurization of thiophene was observed at 5.4 wt.% of Nb₂O₅. This revised version was published online in June 2006 with corrections to the Cover Date.     

Solvation of halogens in fluorous phases. Experimental and simulation data for F2, Cl2, and Br2 in several fluorinated liquids

The solubility of halogen gases--fluorine, chlorine and bromine--has been determined experimentally in several fluorinated solvents between 283 and 323 K at atmospheric pressure. The solubility of chlorine was studied in perfluorooctane, perfluorohexane, perfluorohexylethane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoro-2-butyltetrahydrofuran, and perfluoroperhydrophenanthrene and was found to be on the order of 10(-2) in mole fraction. The solubility of fluorine in the studied fluorinated solvents at 298 K is 1 order of magnitude lower than the solubility of chlorine. The solubility of bromine was studied as a function of temperature in perfluorooctane, and it was found to be higher than that of chlorine but of the same order of magnitude. The experimental studies were complemented by molecular simulation calculations. The molecular force fields used for the halogen gases and for the fluorinated solvents were taken, when possible, from the literature. An intermolecular potential model had to be developed for perfluoro-2-butyltetrahydrofuran, with a functional form of the Lennard-Jones plus point charges type. The solubility of the three gases was calculated by molecular simulation using Widom test-particle insertion. Dissimilar interaction parameters of 0.89 and 0.75 in the Lennard-Jones well depths between the solute and the solvent had to be introduced to reach agreement with the experimental results for chlorine and fluorine solubilities, respectively. The structure of the solutions was studied by analysis of solute-solvent radial distribution functions. It was found that the preferential solvation sites for the halogen gases are the terminal CF3 groups of the different fluorinated solvents.     

Aerobic oxidative iodination of organic molecules activated by sodium nitrite

Aerobic oxidative iodination activated by sodium nitrite occurs effectively and selectively with 100% iodine atom economy with air as the oxidant. Silica-supported sulfuric acid was used for the activation of the catalyst and iodination. Thus, I₂/NaNO₂/air/silica-supported H₂SO₄ in acetonitrile iodinated aromatics, ketones and aldehydes effectively at ambient temperature.     

Iodine as a catalyst for efficient conversion of ketones to gem-dihydroperoxides by aqueous hydrogen peroxide

Iodine has been shown to be an efficient catalyst for the selective dihydroperoxidation of ketones with aqueous hydrogen peroxide. Ketones were directly converted to their corresponding gem-dihydroperoxides using a "green" oxidant (30% aq H(2)O(2)) and a simple catalyst (iodine) under neutral conditions in acetonitrile. The yield of hydroperoxidation of various cyclic ketones was 60-98% including androstane-3,17-dione, and acyclic ketones were converted with a similar efficiency. [reaction: see text]     

Efficient Synthesis of Fluorescent Coumarins and Phosphorous-Containing Coumarin-Type Heterocycles via Palladium Catalyzed Cross-Coupling Reactions

Quantum-chemical calculations on the spectral properties of some aryl substituted 3-phosphonocoumarins were performed, and the effect of the substituents in the aryl moiety was evaluated. The structures possessing promising fluorescent properties were successfully synthesized via Suzuki and Sonogashira cross-coupling. The synthetic protocol was also applied for the phosphorous chemoisomer of 3-phosphonocoumarin, 1,2-benzoxaphosphorin, and their carboxylate analogues. The optical properties of the arylated and alkynylated products were experimentally determined. The obtained quantum-chemical and experimental results give the possibility for a fine tuning of the optical properties of phosphorous-containing coumarin systems by altering the substituent at its C-6 position.     

A hybrid organic–inorganic sol–gel coating for protecting aluminium alloy 7075-T6 against corrosion in Harrison’s solution

A two-step procedure for synthesizing a new type of hybrid coating is presented. Coatings were synthesized from tetraethyl orthosilicate, 3-(trimethoxysilyl)propyl methacrylate and zirconium(IV) propoxide (ZTP). Zirconium(IV) propoxide was chelated with methacrylic acid. The synthesis, which proceeded at room temperature, was optimized using in situ Fourier transform infrared spectroscopy (FTIR). The effects of ZTP content, ageing and Zr/Si ratio were investigated. The viscosity of the sols increased with the ratio of Zr to Si. The terminal stability of the hybrid coatings was determined by thermogravimetric analysis and their composition and morphology analyzed by FTIR and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. Sols were deposited on the aluminium AA7075-T6 substrate by spin-coating. The corrosion properties in dilute Harrison’s solution of samples coated by hybrid coatings were determined by electrochemical polarization methods. The coatings substantially improved the corrosion resistance of the substrate, as shown by a broad range of passivity extending up to high electrode potentials. The degree of protection was dependent on the content of zirconium and the time of ageing. The strong corrosion protection was ascribed to the bonding between silicon, oxygen and zirconium (Si–O–Si, Si–O–Zr), as proved by the FTIR analysis.     

The effect of iodine on the peroxidation of carbonyl compounds

Peroxidation of ketones and aldehydes with iodine as a catalyst was studied. Ketones reacted with 30% aq hydrogen peroxide in the presence of 10 mol % of iodine to yield gem-dihydroperoxides in acetonitrile and hydroperoxyketals in methanol. The yield of hydroperoxidation of various cyclic ketones was 60-98%, including androstane-3,17-dione, while acyclic ketones were converted with a similar efficiency. Aromatic aldehydes were also converted to gem-dihydroperoxides with hydrogen peroxide and iodine as catalyst in acetonitrile and to hydroperoxyacetal in methanol, while the reactivity of aliphatic ones remained the same as in noncatalyzed reactions. tert-Butylhydroperoxide reacted in a similar manner, giving the corresponding perether derivatives. A study was also made of the relative kinetics of dihydroperoxidation from which the Hammet equation gave a reaction constant (rho) of -2.76, indicating the strong positive charge development in the transition state and the important role of rehybridization in the conversion of hydroperoxyhemiketal to gem-dihydroperoxide. In acetonitrile, the iodine catalyst is apparently able to discriminate between the elimination of a hydroxy, methoxy, and hydroperoxy group and addition of water, methanol, and H2O2 to a carbonyl group.     

Comparative study of the ring opening of 1-CF3-epoxy ethers mediated by Brönsted acids and hexafluoro-2-propanol

In order to evaluate more deeply the nature of the activation of oxirane ring opening reactions by HFIP, ring opening of both CF₃-epoxy ethers 1a (R = Ph) and 1b (R = CH₂CH₂Ph) with HFIP alone, and with hard (MeOH) or soft (PhSH) nucleophiles in HFIP, were investigated and compared to reactions performed with Brönsted acids. Nucleophilic ring opening reactions in HFIP were facilitated with PhSH and only α-substituted trifluoromethyl ketone 5 was isolated (nucleophilic ring opening), while with MeOH, both processes, nucleophile and electrophile-assisted ring opening were in competition. In the Brönsted acid-catalysed ring opening of 1-CF₃-epoxy ethers 1 in HFIP, only the acid-catalysed ring opening process occurred with an inversed regioselectivity.