Phase transition in ammonium hexafluorovanadate (III)

Heat capacity of ammonium hexafluorovanadate (NH₄)₃ [VF₆] has been measured with a miniaturized adiabatic calorimeter from 20 to 300 K. A phase transition was found at 280.44 ± 0.05 K with the associated entropy change Δ_trs S = 24.9 ± 0.5 JK^?1 mol^?1. The entropy transition is accounted for by the orientational order-disorder changes of hexafluorovanadate ion and ammonium ion occupying respective octahedral sites, as in the cases of (NH₄)₃AlF₆ and (NH₄)₃FeF₆ crystals. Changes in infrared spectra relative to v₃ vibrational mode of [VF₆]^3? ion can be explained by an orientational disorder of the anions in the high-temperature phase (HTP). The dependence of cubic root of the unit-cell volume of a family of ammonium cryolites on their transition temperatures is discussed in relation to the nature of interactions which induce the phase transition.     

Regularized determinants for quantum field theories with fermions

A new type of regularized determinant for the ratio of two Dirac operators is presented. Some of its properties with application to the chiral anomaly are given.     

Radical cyclopolymerizations of diallylsilanes and triallylsilanes

The radical polymerizations of diallylsilanes such as diallyldimethylsilane ( 1 ) and diallylmethylphenylsilane ( 2 ) have been conducted. Both poly(diallyldimethylsilane) ( 3 ) and poly(diallylmethylphenylsilane) ( 4 ) are soluble in benzene, methyl ethyl keton (MEK), and chloroform, slightly soluble in acetone, and insoluble in methanol and ethanol. No insoluble fraction of either polymer was obtained. Very little evidence of vinyl protons in the ¹H-NMR spectra can indicate that both polymerizations predominantly proceed with intramolecular cyclization. In order to study the ring size of cyclic structure in the repeating unit of the polymers, a model compound, allyl(2-chloropropyl)dimethylsilane ( 5 ), was synthesized and cyclized with Bu₃SnH in the presence of azobisisobutyronitrile (AIBN) in benzene, under similar condition of those for the cyclopolymerizations. The product was analyzed with GC–MS which showed that the five-membered ring compound, 1,1,3,4-tetramethylsilacyclopentane, was not formed. From the result of the cyclization of the model compound, it can be suggested that the polymerizations undergo with only h–t intramolecular cyclization to form a six-membered ring in the repeated unit. The ¹³C-NMR spectra of 3 and 4 were measured to study the ring size and the configuration of the cyclic structures. The two peaks at ?1.6 and ?3.4 ppm of the spectrum of 3 show that there are two kinds of methyl carbons in the repeating unit. From consideration of the model reaction and the number of the peaks of the NMR spectrum, it can be considered that the polymer main chain is assembled with the six-membered ring in cis-form, and the two signals are assigned to equatorial and axial methyl carbons, respectively. The two peaks at -1.5 and -5.1 ppm of the ¹³C-NMR spectrum of 4 can be assigned similarly. The radical cyclopolymerizations of triallylsilanes such as methyltriallylsilane ( 6 ) and phenyltriallylsilane ( 7 ) were conducted. The ¹H-NMR spectra of poly(methyltriallylsilane) ( 8 ) and poly(phenyltriallylsilane) ( 9 ) show broad peak around 5 ppm for vinyl protons and around 2 ppm for alkyl protons. Comparisons of the relative intensities of the peaks indicate that both polymerizations undergo with single ring closure to form a polymer with monocyclic structure moiety, cyclosilahexane, and an allyl group in a repeating unit of 8 and 9 .     

The absorption spectrum of localized electrons in crystalline 1,8-octanediol, γ-irradiated at 4.2 K

Crystalline 1.8-octanediol has been γ-irradiated and its optical absorption spectrum has been measured at 4.2 K. The spectrum consists of three partially resolved peaks with maxima at 740, 590, and 490 nm. The peaks cannot be separated by photobleaching or annealing. It is suggested that they arise from transitions inherent in each localized electron.     

E 6,7,8 magnetized extra-dimensional models

We study 10D super Yang–Mills theory with the gauge groups E ₆, E ₇ and E ₈. We consider the torus/orbifold compactification with magnetic fluxes and Wilson lines. They lead to 4D interesting models with three families of quarks and leptons, whose profiles in extra dimensions are quasi-localized because of magnetic fluxes.     

Links in an open book decomposition and in the standard contact structure

We study a relationship between arc presentations of links in and Legendrian links in with the standard tight contact structure. We determine the arc indices of torus knots.

     

Transition Semi–groups on a Local Field Induced by Galois Group and their Representation

For a given map defined on the field of p-adic numbers satisfying

Two new bioactive sesquiterpenes from the soft coral Sinularia sp

Two new sesquiterpenes, 1S*, 4R*, 5S*, 6R*, 7S*, 10S*-1(5), 6(7)-diepoxy-4-guaiol (1) and 1S*, 4S*, 5S*, 10R*-4,10-guaianediol (2) have been isolated from the ethyl acetate soluble portion of the soft coral Sinularia sp., and their stereostructure were determined by spectroscopic methods and by X-ray single crystal analysis. Both compounds showed antioxidant and cytotoxic activities.     

Visible light-induced degradation of ethylene glycol on nitrogen-doped TiO2 powders

The photocatalytic degradation processes of ethylene glycol (EG) during the UV or visible light irradiation of pure anatase and nitrogen (N)-doped TiO2 powders (TiO(2-x)N(x), x = 0, 0.002, 0.003, and 0.007) were investigated using time-resolved diffuse reflectance (TDR) and solid-state NMR spectroscopies. The TDR spectra and time traces observed for the charge carriers indicated that the scavenging of photogenerated holes (h+) by EG occurred during the 355-nm laser photolysis of the N-doped TiO2 powders, while no direct oxidation reaction of EG by h+ occurred during the 460-nm laser photolysis, although the charge carriers were sufficiently generated upon excitation. The solid-state magic-angle spinning (MAS) NMR measurements revealed that EG is preferentially chemisorbed on the surface of the N-doped TiO2 powders, in contrast to the pure TiO2, and degrades under visible light irradiation.     

Acoustic multibubble cavitation in water: A new aspect of the effect of a rare gas atmosphere on bubble temperature and its relevance to sonochemistry

Acoustic cavitation generates transient microbubbles with extremely high temperatures and high pressures, which can provide unique reaction routes. The maximum bubble temperature attained is widely known to be dependent on the polytropic index and thermal conductivity of the dissolved gas. Here, we show for the first time experimental evidence that the bubble temperature induced by a high frequency ultrasound is almost the same among different rare gases and the chemical efficiency is in proportion to the gas solubility of rare gases, which would be closely related to the number of active bubbles.