Condensation of all-cis-tetraphenylcyclotetrasiloxanetetraol in ammonia: new method for preparation of ladder-like polyphenylsilsesquioxanes

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Variants of closing the nuclear fuel cycle

Influence of the nuclear energy structure, the conditions of fuel burnup, and accumulation of new fissile isotopes from the raw isotopes on the main parameters of a closed fuel cycle is considered. The effects of the breeding ratio, the cooling time of the spent fuel in the external fuel cycle, and the separation of the breeding area and the fissile isotope burning area on the parameters of the fuel cycle are analyzed.     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.     

Multicriteria decision making under uncertainty

Formalization for problems of multicriteria decision making under uncertainty is constructed in terms of guaranteed and weak estimates. A relevant definition of the vector maximinimax value is given. Parameterization and approximation of maximum, minimax, and maximinimax values based on the inverse logical convolution are suggested. An application for multicommodity networks is considered. Received: December 13, 2000 / Accepted: August 21, 2001?Published online May 8, 2002     

Searches for single-spin asymmetry in the inclusive production of neutral pions in the central region at a proton beam energy of 70 GeV

Results are presented that were obtained by measuring single-spin asymmetry in the inclusive production of neutral pions in the reaction p+p ↑→ π ⁰+X at x _F≈0. A beam of 70-GeV protons was extracted directly from the vacuum chamber of the accelerator by means of a bent single crystal. For transverse momenta in the range 1.0<p _T<3.0 GeV/c, the single-spin asymmetry independently measured by two detectors is zero within the errors. This result is in agreement with Fermilab data obtained at 200 GeV, but it is at odds with CERN data measured at 24 GeV.     

Photosensitivity of holographic recording media based on films of polymer compositions with cadmium sulfide nanoparticles

The effect of doping with CdS nanoparticles of recording medium films for the thermoplastic holographic recording process, which are based on photosemiconductors (oligomers and cooligomers of glycidylcarbazole) and a dielectric (a styrene copolymer with octyl methacrylate) containing a photoconductivity sensitizer, on their photosensitivity was studied. The enhancement of photosensitivity of films by doping with nanoparticles is associated with the appearance of an additional channel for transport of electrons generated from sensitizer molecules. A difference in informational properties between the oligomer and the polymer films was revealed.     

Mechanism of the cyclization of dimethyl diethynyl silane with selenium tetrabromide: Computational and structural studies, and monitoring

The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr₄ to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr₄ conversion into bimolecular complex Br₂?SeBr₂, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using ¹H NMR method.     

Effects of the Structural Rigidity of Polymethine Dye Molecules on Quenching of Their Photoluminescence by an Electric Field and Charge Photogeneration in Poly(N-epoxypropylcarbazole)

For photoconducting poly(N-epoxypropylcarbazole) films doped with cationic polymethine dyes used as an example, it was found that an increase in dye molecular rigidity increased the photoconductivity of the films in the region of dye absorption, quenching effect of an electric field on photoluminescence, and concentration ratio of photogenerated triplet electron–hole pairs to singlet pairs. The effects were enhanced by an increase in the quantum energy of excitation light. The results are explained by a decrease in the dissipation rate of the electronic excitation energy of dye molecules upon growing their rigidity, which accelerates singlet–triplet intersystem crossing in the photogenerated electron–hole pairs via the spin–lattice relaxation mechanism.     

Electrochemical and spectral studies on the reductive nitrosylation of water-soluble iron porphyrin

The reaction of iron(III) (meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (Fe(III)TMPyP) with nitric oxide (NO) was studied by electronic absorption spectroscopy, ESR, and electrochemical and spectroelectrochemical techniques in aqueous solutions with pH from 2.2 to 12.0. Fe(III)TMPyP has been found to undergo a reductive nitrosylation in all pHs, and the product of nitric oxide binding to the porphyrin has been determined as iron(II) porphyrin nitrosyl complex ([Fe(II)(NO)TMPyP]). The rate of the reductive nitrosylation exhibits a tendency to get faster with increase in pH. An intermediate species was observed around neutral pH by spectroelectrochemical technique and was proposed to be the iron(II) nitrosyl complex of the mu-oxo dimeric form of FeTMPyP, which is known to be a predominant in neutral solutions.     

Synthesis of hydroporphyrins based on comparative studies of palladium-catalyzed and non-catalyzed approaches

Hydroporphyrins have been synthesized using both Pd-catalyzed and non-catalyzed approaches. Comparative studies of the reaction of tetrasubstituted porphyrins with organolithium reagents in the presence of and without palladium catalysts showed that depending on reagents, the catalyst structure and reactivity of the corresponding porphyrins, chlorins (β-hydroporphyrins) and/or porphodimethenes (meso hydroporphyrins) of 5,10-type can be prepared in reasonable yields. In the absence of Pd catalysts, the formation of chlorins is predominant in the reactions with aliphatic RLi while porphodimethenes are the main products in reactions with PhLi. The use of a palladium catalyst resulted in the formation of both types of hydroporphyrins and the selective formation of either β-mono- or disubstituted chlorins. Of special interest was the reaction of octaethylporphyrin. Here, reaction with t-BuLi in the presence of Pd(PPh₃)₄/CuI proceeded with complete regioselectivity for 5,10-porphodimethenes.