Rate constants of the O(D) reactions with N2, O2, N2O, and H2O at 295 K

Using a technique of laser flash photolysis coupled with vacuum ultraviolet laser-induced fluorescence spectroscopy, the rate coefficients of O(¹D) reactions with N₂, O₂, N₂O, and H₂O at 295 ± 2 K have been determined to be , k_O2=(4.06±0.24)×10^-11, k_N2O=(1.35±0.08)×10^-10 and . The quoted uncertainties include estimated errors and are the 95% confidence level. The k_N2 and k_N2O values obtained are larger than the current NASA/JPL recommendations by 26% and 16%, respectively, although they are still within the error limits associated with the recommendations.     

NMR Studies on Solution Structures of Methanol and Ethanol Saturated with CO2

²H and ¹⁷O NMR relaxation times, T ₁(²H) and T ₁(¹⁷O), and ²H NMR chemical shifts, δ(²H), in CO₂-saturated CD₃OD and C₂D₅OD solutions were measured at 313.2 K over the pressure range up to ~6 MPa. The rotational correlation times, τ _r, of the CD and OD axes within CD₃OD and C₂D₅OD molecules and the CO axis within the CO₂ molecule were determined from T ₁(²H) and T ₁(¹⁷O), and the magnetic susceptibility-corrected chemical shifts, δ _corr, were derived from δ(²H). The differences in τ _r and δ _corr observed between the two alcohol systems: τ _r and δ _corr of OD in C₂D₅OD, decreased rapidly with increasing CO₂ concentration, while those of OD in CD₃OD remained almost unchanged at mole fractions of CO₂, \( x_{\text CO_{2}} \) , lower than ~0.25 and then slightly decreased at higher \( x_{\text CO_{2}} \) . The hydrogen bonding structure in C₂D₅OD was found to be gradually broken down by CO₂ dissolution. On the other hand, in CD₃OD, it has been revealed that the hydrogen bonding structure can persist at \( x_{\text CO_{2}} \)  < ~0.25 but then collapses at higher \( x_{\text CO_{2}} \) .     

Direct micropatterning of high dielectric BaTiO3 films by laser-induced pyrolysis with a nano-crystalline seeding technique

A direct patterning method of dielectric BaTiO₃ (BT) films is proposed, which applies laser-induced pyrolysis in combination with nano-crystalline seeding technique. A precursor solution of a BT complex alkoxide containing BT nano-crystalline particles with polyvinylpyrollidone (PVP) as dispersion stabilizer was spin-coated on Pt substrate. An Ar⁺ laser beam was focused and scanned on spin-coated BT films, which induced pyrolysis and crystallization of the films with spatial selectivity. Micropatterns were obtained by striping laser-unirradiated regions on the films with HCl aqueous solution. Raman spectra of the micropattern confirmed that the structures were tetragonal crystalline BT. Clear micropatterns with a line width of ca. 3 μm and an interval of 5 μm were formed at PVP concentrations of 25 and 50 kg/m³. The dielectric constant and dissipation factor of the film fabricated at a laser energy density of 27 MW/cm² and a scanning speed of 25 μm/s attained 76.2 and 0.07, respectively, for a measurement frequency of 100 kHz.     

Quantum yield for hydrogen atom formation from H2O2 photolysis in the range 193–240 nm

Photodissociation processes of H₂O₂ in the range 193–240 nm have been studied by pulsed laser photolysis and laser‐induced fluorescence detection of H atom fragments at 121.56 nm. The quantum yield values for H atom formation at 295 ± 2 K have been determined to be 0.20 ± 0.03, 0.038 ± 0.008, 0.029 ± 0.003, 0.015 ± 0.006, 0.007 ± 0.002 at 193, 207, 210, 220, and 230 nm, respectively. At 240 nm, only the upper limit value of <0.002 has been obtained. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 751–754, 2005     

A Study of the Solvation Structure of l‐Leucine in Alcohol–Water Binary Solvents through Molecular Dynamics Simulations and FTIR and NMR Spectroscopy

The solvation structures of l ‐leucine (Leu) in aliphatic‐alcohol–water and fluorinated‐alcohol–water solvents are elucidated for various alcohol contents by using molecular dynamics (MD) simulations and IR, and ¹H and ¹³C NMR spectroscopy. The aliphatic alcohols included methanol, ethanol, and 2‐propanol, whereas the fluorinated alcohols were 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol. The MD results show that the hydrophobic alkyl moiety of Leu is surrounded by the alkyl or fluoroalkyl groups of the alcohol molecules. In particular, TFE and HFIP significantly solvate the alkyl group of Leu. IR spectra reveal that the Leu C?H stretching vibration blueshifts in fluorinated alcohol solutions with increasing alcohol content, whereas the vibration redshifts in aliphatic alcohol solutions. When the C?H stretching vibration blueshifts in the fluorinated alcohol solutions, the hydrogen and carbon atoms of the Leu alkyl group are magnetically shielded. Consequently, TFE and HFIP molecules may solvate the Leu alkyl group through the blue‐shifting hydrogen bonds.     

A new hierarchy system on the basis of a “Master” Boltzmann equation for microscopic density

It is shown that Boltzmann's equation written in terms of microscopic density (namely the unaveraged Boltzmann function) has a wider range of validity as well as finer resolvability for fluctuations than the conventional Boltzmann equation governing Boltzmann's function. In fact the new Boltzmann equation for ideal gases has implications as a microscopically exact continuity equation like Klimontovich's equation for plasmas, and can be derived without invoking any statistical concepts, e.g., distribution functions, or molecular chaos. The Boltzmann equation in the older formalism is obtained by averaging this equation only under a restricted condition of the molecular chaos. The new Boltzmann equation is seen to contain information comparable with Liouville's equation, and serves as a master kinetic equation. A new hierarchy system is formulated in a certain parallelism to the BBGKY hierarchy. They are shown to yield an identical one-particle equation. The difference between the two hierarchy systems first appears in the two-particle equation. The difference is twofold. First, the present formalism includes thermal fluctuations that are missing in the BBGKY formalism. Second, the former allows us to formulate multi-time correlations as well, whereas the latter is restricted to simultaneous correlation. These two features are favorably utilized in deriving the Landau-Lifshitz fluctuation law in a most straightforward manner. Also, equations describing the nonequilibrium interaction between thermal and fluid-dynamical fluctuations are derived.     

CHLORPROMAZINE PHOTOSENSITIZATION–II. FAILURE TO DETECT ANY EVIDENCE FOR INVOLVEMENT OF DNA DAMAGE IN THE PHOTODYNAMIC KILLING OF ESCHERICHIA COLI IN THE PRESENCE OF CHLORPROMAZINE

Abstract— When a suspension of Escherichia coli was irradiated with near-UV light in the presence of chlorpromazine (at a concentration below a cytotoxic level), the cells were killed. Efficiency of the photodynamic killing was not influenced by the deficiency of the uvrA gene or the recA gene. Neither phenotypic reversion of E. coli Hs30R (arginine auxotroph) nor induction of lambda prophage in lysogenic bacteria was detected after this treatment.     

Liquid structure of room-temperature ionic liquid, 1-Ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl) imide

The liquid structure of 1-ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl) imide (EMI(+)TFSI(-)) has been studied by means of large-angle X-ray scattering (LAXS), (1)H, (13)C, and (19)F NMR, and molecular dynamics (MD) simulations. LAXS measurements show that the ionic liquid is highly structured with intermolecular interactions at around 6, 9, and 15 A. The intermolecular interactions at around 6, 9, and 15 A are ascribed, on the basis of the MD simulation, to the nearest neighbor EMI(+)...TFSI(-) interaction, the EMI(+)...EMI(+) and TFSI(-)...TFSI(-) interactions, and the second neighbor EMI+...TFSI(-) interaction, respectively. The ionic liquid involves two conformers, C(1) (cis) and C(2) (trans), for TFSI(-), and two conformers, planar cis and nonplanar staggered, for EMI(+), and thus the system involves four types of the EMI(+)...TFSI(-) interactions in the liquid state by taking into account the conformers. However, the EMI(+)...TFSI(-) interaction is not largely different for all combinations of the conformers. The same applies alsoto the EMI(+)...EMI(+) and TFSI(-)...TFSI(-) interactions. It is suggested from the 13C NMR that the imidazolium C(2) proton of EMI(+) strongly interacts with the O atom of the -SO(2)(CF(3)) group of TFSI(-). The interaction is not ascribed to hydrogen-bonding, according to the MD simulation. It is shown that the liquid structure is significantly different from the layered crystal structure that involves only the nonplanar staggered EMI(+) and C(1) TFSI(-) conformers.     

Liquid structure of acetic acid-water and trifluoroacetic acid-water mixtures studied by large-angle X-ray scattering and NMR

The structures of acetic acid (AA), trifluoroacetic acid (TFA), and their aqueous mixtures over the entire range of acid mole fraction xA have been investigated by using large-angle X-ray scattering (LAXS) and NMR techniques. The results from the LAXS experiments have shown that acetic acid molecules mainly form a chain structure via hydrogen bonding in the pure liquid. In acetic acid-water mixtures hydrogen bonds of acetic acid-water and water-water gradually increase with decreasing xA, while the chain structure of acetic acid molecules is moderately ruptured. Hydrogen bonds among water molecules are remarkably formed in acetic acid-water mixtures at xA相似文献