A facile protocol for the preparation of 5-alkylidene and 5-imino substituted hydantoins from N,N′-disubstituted parabanic acids

A convenient procedure for the preparation of various substituted (thio)hydantoins is described. The method is based on Wittig and aza-Wittig reactions of parabanic acids with phosphonium ylides. The reactions occurred both regio- and stereo-selectively.     

Isobaric (vapour + liquid) equilibria for the binary system of glycidyl butyrate (1) and epichlorohydrin (2) at (100, 88.66, and 56) kPa

The (vapour + liquid) equilibria (VLE) data for the binary system of glycidyl butyrate (1) and epichlorohydrin (2) was studied at (100, 88.66, and 56) kPa. Azeotropic behaviour has not been found in this work. The activity coefficients were obtained by the non-linear least squares method based on minimization from the equilibrium data. Average relative deviations between calculated values and the experimental data of temperature are all lower than 0.99% for the three models at the three different pressures investigated. The root mean square deviations (RMSD) of gas phase compositions y₁ and temperatures are all lower than 0.0099 and 1.1 K for 100 kPa, 0.0094 and 4.5 K for 88.66 kPa and 0.0095 and 3.7 K for 56 kPa. The thermodynamic consistency of the calculated data is checked by the Herrington method. The experimental VLE data are compared with the correlated values obtained by means of the NRTL, UNIQUAC, and Wilson models.     

Ultra-slow muon facility for surface HFI studies

A concept, a design, a construction and an account of commissioning experiments are given for the recently completed ultra-slow muon facility at the pulsed muon facility of UT-MSL/KEK. The intense (more than 10³/s) slow ⁺ beam with an extremely narrow phase-space volume (0.2 eV×(3 cm)²) to be produced in this facility will open a new muon science including surface physics and chemistry and fundamental atomic physics.Post-doctoral fellow of Swiss National Science Foundation.     

Potential of a piezoelectric energy harvester from sea waves

A sea wave energy harvester from the longitudinal wave motion of water particles is developed. The harvester consisting of a cantilever substrate attached by piezoelectric patches and a proof mass is used to collect electrical energy owing to the electromechanical coupling effect of the piezoelectric patches from the longitudinal wave motion. To describe the energy harvesting process, a mathematical model is developed to calculate the output charge and voltage from the piezoelectric patches according to the Airy linear wave theory and classical elastic beam model. Results show that the mean value of the generated power increases with the increase in the ratio of the width to the thickness of the cantilever, the wave height, the sea depth (which equals to the cantilever height in this study), the ratio of the proof mass to the cantilever mass, and the ratio of the sea depth to the wave length. A value of the power up to 55 W can be realized for a practical sea wave with the values of the sea depth, wave height and wave length to be 3 m, 2 m, and 15 m, respectively. The collected power harvesting with respect to different categories of the sea waves are provided. Our simulations also show the generated electric power can be further increased by an increase in dimensions of the harvester considering the scale effect. This research develops a new technique for energy harvesting from sea waves by piezoelectric energy harvesters.     

Molecular structure, spectroscopic properties and DFT calculations of 2-(methylthio)nicotinic acid

The analyses of possible conformations, molecular structures, vibrational and electronic properties of 2-(methylthio)nicotinic acid molecule, C₇H₇NO₂S, with the synonym 2-(methylsulfanyl)nicotinic acid have been first presented theoretically. At the same time, FT-IR and micro-Raman spectra of 2-(methylthio)nicotinic acid were recorded in the regions 400–4000 cm^?1 and 100–4000 cm^?1, respectively. In our calculations, the DFTB3LYP method with 6–311G(d, p) basis set was used to have the structural and spectroscopic data about the mentioned molecule in the ground state and the results obtained were compared with experimental values. Furthermore, gauge invariant atomic orbital (GIAO) ¹H and ¹³C NMR chemical shifts in different solvents, UV-vis TD-DFT calculations, the highest occupied molecular orbitals (HOMO-2, HOMO-1, HOMO), lowest unoccupied molecular orbital (LUMO), molecular electrostatic potantial (MEP) surface, atomic charges and thermodynamic properties of molecule have been theoretically verified and simulated at the mentioned level. The energetic behavior of title molecule in different solvent media was investigated by using DFT/B3LYP method with 6–311G(d, p) basis set in terms of integral equation formalism polarizable continuum model (IEFPCM). In addition, the calculated infrared intensities, Raman activities, reduce masses and force constants of the compound under study have been also reported.     

Experimental study of the relationships between the spectral emissivity of brass and the temperature in the oxidizing environment

Effect of surface oxidization on the spectral emissivity of brass is studied over the temperature range from 800 to 1070 K at the wavelength of 1.5 μm. The temperature of brass surface is measured by averaging the two R-type platinum–rhodium thermocouples. The radiant energy emitted by the brass surface is received by an InGaAs photodiode detector. Two kinds of relationships between the spectral emissivity and the temperature are investigated in the oxidizing environment at the elevated temperature. One is the variation of spectral emissivity with the heating-duration time at the given temperature. The other is the variation of spectral emissivity with the temperature at the given heating-duration time. The interference effect of radiation coming from the brass surface and coming from the oxidization film is discussed when the oxidation film on the surface is grown. The resonant structures of spectral emissivity are observed during the whole heating period, in particular at the early stage of heating duration. The analytic formula of spectral emissivity versus the temperature is derived at the heating-duration time of 30, 60, 90, 120, 150, 180, 210, 240, 270 and 300 min, respectively. The conclusion is obtained that coefficients of analytic expressions between the spectral emissivity and the temperature are different from each other for the experimental results obtained at the different heating-duration time, though the polynomial functional form is suitable to fit all the measurements obtained in the present work.     

Electron Transport in Ga-Rich InxGa1-xN Alloys

Resistivity and Hall effect measurements on n-type undoped Ga-rich InxGa1-xN （0.06 ≤ x ≤ 0.135） alloys grown by metal-organic vapour phase epitaxy （MOVPE） technique are carried out as a function of temperature （15-350 K）. Within the experimental error, the electron concentration in Inx Ga1-x N alloys is independent of temperature while the resistivity decreases as the temperature increases. Therefore, Inx Ga1-xN （0.06 ≤ x ≤0.135） alloys are considered in the metallic phase near the Mort transition. It has been shown that the temperaturedependent metallic conductivity can be well explained by the Mort model that takes into account electron-electron interactions and weak localization effects.     

Substituent effects on the ring‐opening mechanism of gem‐dibromospiropentanes to related allenes: a theoretical study

Density functional theory computations at B3LYP and X3LYP levels were performed for ring openings of substituted gem‐dibromospiropentanes (R = ―H, ―Cl, ―Br, ―CH₃, ―SiH₃, ―OH, ―OCH₃, ―CF₃, ―BF₂, and ―SH) to related allenes. The conversion of spiropentanoids 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j to the corresponding allenes 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h , 7i , 7j can proceed in both concerted and stepwise mechanism except for R = ―H. Both ring‐opening mechanisms have similar activation energy barriers to open the spiropentanylidene ring and generate the structure of allene at all theoretical levels used herein. Generally the π electron‐donating group (―OH or ―SH) decreases the activation barrier for the follow‐up reaction of 1‐bromo‐1‐lithiospiropentanoid and free spiropentanylidene. Hence, both bearing electron‐donating substituents are more reactive than those with electron‐withdrawing group, and the first one to open the ring to the LiBr–allene complex does so more readily than the second. The sEDA index used to measure sigma‐electron excess/deficiency of the cyclopropylidene ring is mutually correlated for the studied systems. Copyright © 2015 John Wiley & Sons, Ltd.     

A paradigm shift in rate determining step from single electron transfer between phenylsulfinylacetic acids and iron(III) polypyridyl complexes to nucleophilic attack of water to the produced sulfoxide radical cation: a non‐linear Hammett

Mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAAs) by iron(III) polypyridyl complexes in aqueous acetonitrile medium has been investigated spectrophotometrically. An initial intermediate formation between PSAA and [Fe(NN)₃]³⁺ is confirmed from the observed Michaelis–Menten kinetics and fractional order dependence on PSAA. Significant rate retardation with concentration of [Fe(NN)₃]³⁺ is rationalized on the basis of coordination of a water molecule at the carbon atom adjacent to the ring nitrogen of the metal polypyridyl complexes by nucleophilic attack at higher concentrations. Electron‐withdrawing and electron‐releasing substituents in PSAA facilitate the reaction and Hammett correlation gives an upward ‘V’ shaped curve. The apparent upward curvature is rationalized based on the change in the rate determining step from electron transfer to nucleophilic attack, by changing the substituents from electron‐releasing to electron‐withdrawing groups. Electron‐releasing substituents in PSAA accelerate the electron transfer from PSAA to the complex and also stabilize the intermediate through resonance interaction leading to negative reaction constants (ρ). Conversely, electron‐withdrawing groups, while retarding the electron transfer exert an accelerating effect on the nucleophilic attack of H₂O which leading to low magnitude of ρ⁺ compared to high ρ^? values of electron‐releasing groups. Marcus theory is applied, and a fair agreement is seen with the experimental values. Copyright © 2016 John Wiley & Sons, Ltd.