Preparation, crystal structure and photoluminescence of garnet-type calcium tin titanium aluminates

Colorless and transparent single crystals of Ca₃Sn_2.2Ti_0.8Al₂O₁₂, which emit blue-white light under ultraviolet light, were prepared by heating a mixture of oxides and calcium carbonate with a calcium and aluminum-rich composition at 1500 °C. Single crystal X-ray diffraction revealed that the crystal structure is the garnet-type with a cubic cell parameter (a=12.5309(3) Å) and the space group, Ia 3¯d (R1=0.0277, wR2=0.0663, and S=1.367 for all data). The structural formula is presented as Ca₃[Sn_0.96Ti_0.04]_octa[Al_0.67Ti_0.24Sn_0.09]_tetraO₁₂. Polycrystalline solid solutions of Ca₃Sn_3−xTi_xAl₂O₁₂ were prepared by solid state reaction in air at 1370 °C with nominal titanium contents from x=0.6 to 1.4. The refined unit cell parameter decreased with increasing x. A broad blue-white emission with a peak wavelength of 465 nm was observed for the solid solutions at room temperature.     

A set of two diastereomers of cyanogenic glycosides from Passiflora quadrangularis

A set of two diastereomers of phenylcyano glycosides, (7S)- and (7R)-phenylcyanomethyl 1'-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (1, 2), were isolated from the methanol extract of dried vines of P. quadrangularis. The absolute configurations of the benzylic methine centers were determined mainly by the comparison of 13C NMR spectra of these compounds, prunasin (3) and sambunigrin (4), of which the last two cyanoglycosides are known to have (R)- and (S)-configurations, respectively.     

A collisional-radiative code for computing air plasma in high enthalpy flow

A time-dependent collisional-radiative model for air plasma has been developed to study the effects of nonequilibrium atomic and molecular processes on population densities in a weakly ionized high enthalpy flow. This model consists of 15 species: e^-,N, N⁺,N²⁺,O, O⁺,O²⁺,O^-,N₂,N₂⁺,NO, NO⁺,O₂,O₂⁺{{\rm e}^{-},{\rm N, N}^{+},{\rm N}^{2+},{\rm O, O}^{+},{\rm O}^{2+},{\rm O}^{-},{\rm N}_{2},{{\rm N}_{2}}^{+},{\rm NO, NO}^{+},{\rm O}_{2},{{\rm O}_{2}}^{+}}, and O₂^-{{{\rm O}_{2}}^{-}} with their major electronic excited states. Many elementary processes are considered in the number density range of 10¹²/cm³ ≤ N ≤ 10¹⁹/cm³ and the temperature range of 300 K ≤ T ≤ 40,000 K. We then compare our results with an existing collisional-radiative code to validate our model. Additionally, the unsteady nature of pulsively heated air plasma is investigated. When the ionization relaxation time is of the same order as the time scale of a heating pulse, the effects of unsteady ionization are important for estimating air plasma states. From parametric computations, we determine the appropriate conditions for the collisional-radiative steady state, local thermodynamic equilibrium, and corona equilibrium models in that density and temperature range.     

Thermal decomposition of 2-butanol as a potential nonfossil fuel: a computational study

The thermochemistry and kinetics of the pyrolysis of 2-butanol have been conducted using ab initio methods (CBS-QB3 and CCSD(T)) and density functional theory (DFT). The enthalpies of formation and bond dissociation energies of some alcohols including 2-butanol and its derived radicals have been calculated. A variety of simple and complex dissociations have been examined. The results indicated that dehydration to 1- and 2-butene through four-center transition states is the most dominant channel at low to moderate temperatures (T ≤ 700 K), where formation of butenes is kinetically and thermodynamically more favorable than other complex and simple bond scission reactions. Although the C-C bond fission channels require more energy than needed for some complex decomposition reactions, the former pathways predominate at higher temperatures (T ≥ 800 K) due to the higher values of the pre-exponential factors. The progress of the complex decomposition reactions has been followed through intrinsic reaction coordinate (IRC) calculations to understand the mechanism of transformation of 2-butanol to different products.     

Living Radical Polymerization of Styrene with Diphenyl Diselenide as a Photoiniferter. Synthesis of Polystyrene with Carbon-Carbon Double Bonds at Both Chain Ends

Abstract

Photopolymerization of styrene in the presence of diphenyl diselenide proceeded smoothly. The polymer yields and the number average molecular weight (Mn) of the polymers increased with reaction time. Further, a linear relationship was found for a plot of Mn for polystyrene versus polymer yield. These results indicate that this polymerization proceeds through a living radical mechanism. Photopolymerization of styrene with bis(p-tertbutylphenyl) diselenide afforded a telechelic polystyrene with terminal arylseleno groups. The resulting polymer underwent the reductive elimination of terminal seleno groups by the reaction with tri-n-butyltin hydride. Moreover, this telechelic polymer was treated with hydrogen peroxide to afford polystyrene with carbon-carbon double bonds at both chain ends.     

Sulfur-Containing Vinyl Monomers. XIX. Radical Polymerization of 2-Mercaptobenzothiazolyl Methacrylate

2-Mercaptobenzothiazolyl methacrylate (MBTM) was synthesized by the reaction of 2-mercaptobenzothiazole and methacrylyl chloride in tetrahydrofuran at -18°C. MBTM was found to polymerize in the presence of 2,2′-azobisisobutyronitrile (AIBN), n-BuLi, and UV light. From the kinetic studies of radical polymerization of MBTM with AIBN in benzene at 60°C, the overall activation energy was determined to be 18.9 kcal/mole, and the rate of polymerization (R) was expressed as R_p = k[AIBN]^0.5 [MBTM], where k is the overall polymerization rate constant. From these results this polymerization was confirmed to proceed via an ordinary radical mechanism. This monomer (M₂) was also copolymerized radically with styrene (M₁) at 60°C, and the resulting copolymerization parameters were determined as r₁ = 0.042, r₂ = 0.20, Q₂ = 4.09, and e₂ = 1.39. The thermal stability and the photodegradation behavior of the polymers were examined, and they were compared with those of the related polymers.     

Sulfur-Containing Vinyl Monomers. XIV. Radical Polymerizations and Copolymerizations of Vinyl Mercaptobenzazoles

Vinyl mercaptobenzazoles [thiazole (VMBT), oxazole (VMBO), and imidazole (VMBI)] were prepared through dehydrochlorination of the respective β-chloroethyl mercaptobenzazoles. These monomers were found to undergo vinyl polymerization in the presence of light or radical initiator, α,α'-azobisisobutyonitrile, to give relatively high molecular weight homopolymers. From the results of radical copolymerizations of these monomers with various monomers, the copolymerization parameters were determined as follows: VMBT(M₂): r₁ styrene(M₁): r₁ = 2.12 ± 0.09, r₂ = 0.336 ± 0.028, Q₂ = 0.75, e_z = ?1.38; VMBO(M₂)-styrene(M₁): r₁ = 2.61 ± 0.13, r₂ = 0.274 ± 0.03, Q₂ = 0.61, e₂ = ?1.38; VBMI(M₂)-styrene(M₁) r₁ =4.0, r₂ = 0.2, Q₂ = 0.37, e₂ = ?1.17. The polymerization reactivities of these monomers obtained from these parameters were compared with those of other vinyl sulfide monomers and discussed.     

Catalytic Transfer Hydrogenation by a Trivalent Phosphorus Compound: Phosphorus‐Ligand Cooperation Pathway or PIII/PV Redox Pathway?

Main‐group‐element catalysts are a desirable alternative to transition‐metal catalysts because of natural abundance and cost. However, the examples are very limited. Catalytic cycles involving a redox process and E‐ligand cooperation (E=main‐group element), which are often found in catalytic cycles of transition‐metal catalysts, have not been reported. Herein theoretical investigations of a catalytic hydrogenation of azobenzene with ammonia–borane using a trivalent phosphorus compound, which was experimentally proposed to occur through P^III/P^V redox processes via an unusual pentavalent dihydridophosphorane, were performed. DFT and ONIOM(CCSD(T):MP2) calculations disclosed that this catalytic reaction occurs through a P‐O cooperation mechanism, which resembles the metal‐ligand cooperation mechanism of transition‐metal catalysts.     

The investigation of short-range 3He, 3H and deuteron spin structure via the measurement of the angular distributions of the analyzing power in the \vec dd \to {}^3Hen and \vec dd \to Hp reactions at 140, 200 and 270 MeV

The results on the vector A _y and tensor A _yy , A _xx and A _xz analyzing powers of the $\vec dd \to {}^3Hen$ and $\vec dd \to {}^3Hp$ reactions obtained at intermediate energies at RARF(RIKEN, Japan) are presented. The high precision experimental data are compared with the theoretical calculation within the one nucleon exchange model by using standard ³He, ³H and deuteron wave functions. The data demonstrate the sensitivity to the short-range ³He, ³H and deuteron spin structure.     

Characterization of heat-wave propagation through laser-driven Ti-doped underdense plasma

The propagation of a laser-driven heat-wave into a Ti-doped aerogel target was investigated. The temporal evolution of the electron temperature was derived by means of Ti K-shell X-ray spectroscopy, and compared with two-dimensional radiation hydrodynamic simulations. Reasonable agreement was obtained in the early stage of the heat-wave propagation. In the later phase, laser absorption, the propagation of the heat-wave, and hydrodynamic motion interact in a complex manner, and the plasma is mostly re-heated by collision and stagnation at the target central axis.