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.     

trans-cis Photoisomerization of a photoactive yellow protein model chromophore in crystalline phase

We have studied the photoinduced trans/cis isomerization of the protonated form of p-hydroxycinnamic thiophenyl ester, a model chromophore of the photoactive yellow protein (PYP), in crystalline phase, by both fluorescence and infrared spectroscopies. The conversion from trans to cis configuration is revealed by a shift of the fluorescence peak and by inspection of the infrared maker bands. The crystal packing apparently stabilizes the cis photoproduct, suggesting different environmental effects from the solvent molecules for this model chromophore in liquid solutions or from the amino acid residues for the PYP chromophore.     

Current-voltage characteristics of charge-ordered organic crystals

The current-voltage characteristics of layered organic crystals theta-(BEDT-TTF)2MZn(SCN)4 (M = Cs, Rb) follow the power law with a large exponent (e.g., 8.4 at 0.29 K for M = Cs) over a wide range of currents in the low-temperature insulating state. The power-law characteristics are attributed to electric field-induced unbinding of electron-hole pairs that are thermally excited in the background of the two-dimensional charge order. The magnitude of crossover electric fields from Ohmic to the power-law characteristics indicates that the electron-electron Coulomb interaction is significantly long-ranged: The screening length is greater than 10 molecule sites.     

Buffer-gas pressure broadening for the (3 0(0) 1)III <-- (0 0 0) band of CO2 measured with continuous-wave cavity ring-down spectroscopy

Buffer-gas pressure broadening for the (3 0(0) 1)(III)<--(0 0 0) band of CO(2) in the 1600 nm region was investigated with continuous wave cavity ring-down spectroscopy within the temperature range 263-326 K. The measured absorption profiles were analyzed with Voigt functions. Pressure broadening coefficient, gamma(gas), and the temperature dependent parameter (broadening exponent), n, were determined for a variety of buffer gases: N(2), O(2), He, Ne, Ar, Kr and Xe. gamma(air) values estimated subsequently are 0.096(2) for R(0), 0.085(5) for P(8), 0.075(2) for P(16), 0.070(4) for P(26), and 0.069(2) for P(38) in units of cm(-1) atm(-1), where numbers in parentheses are one standard deviation in units of the last digits quoted. n(air) values are 0.77(4) for R(0), and 0.73(11) for P(8).     

Radicals masquerading as electrophiles: a computational study of the intramolecular addition reactions of acyl radicals to imines

Ab initio calculations using 6-311G**, cc-pVDZ, and aug-cc-pVDZ, with (MP2, QCISD, CCSD(T)) and without (UHF) electron correlation, and density functional methods (BHandHLYP and B3LYP) predict that cyclization of the 5-aza-5-hexenoyl and (E)-6-aza-5-hexenoyl radicals proceed to afford the 5-exo products. At the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory, energy barriers (deltaE(double dagger)) of 36.1 and 47.0 kJ mol(-1) were calculated for the 5-exo and 6-endo pathways for the cyclization of the 5-aza-5-hexenoyl radical. On the other hand, at the same level of theory, deltaE(double dagger) of 38.9 and 45.4 kJ mol(-1) were obtained for the 5-exo and 6-endo cyclization modes of (E)-6-aza-5-hexenoyl radical, with exothermicities of about 27 and 110 kJ mol(-1) calculated for the exo and endo modes, respectively. Under suitable experimental conditions, the 6-endo cyclization product is likely to dominate. Analysis of the molecular orbitals involved in these ring-closure reactions indicate that both reactions at nitrogen are assisted by dual orbital interactions involving simultaneous SOMO-pi* and LP-pi* overlap in the transitions states. Interestingly, the (Z)-6-aza-5-hexenoyl radical, that cannot benefit from these dual orbital effects is predicted to ring-close exclusively in the 5-exo fashion.