Biomimetic reduction of benzoylformic acid by an acid stable NADH analogue : a model reaction of lactate dehydrogenase

By the use of an acid-stable NADH analogue (3-carbamoyl-N-benzyl-1,4-dihydroquinoline) NADH model reduction of benzoylformic acid in aqueous solution was achieved, for the first time, at pH region where the carboxyl group is undissociated.     

Pyrolysis of amines: Infrared spectrum of allylimine

Infrared absorption spectrum of allylimine in the gas phase was measured for the first time. The spectrum consisted of two rotational isomers, cis and trans, around the CC bond. The relative population of the trans form was 70–80%, and the rest was for the cis form at room temperature. This intermediate molecule was produced by the thermal decomposition of diallylamine and by the isomerization of propargylamine. The vibrational assignments were made with the help of an ab initio MO calculation. The half-life in the absorption cell was about 20 min.     

Photosensitized decompositions of oxasilacyclopropane ; unusual carbene formation

TCNE photo-sensitized decompositions of oxasilacyclopropane (1) generated carbene and silanone, while the DCA sensitized or direct photolysis of (1) gave silylene and indanone.     

A GENERATIVE MODEL OF INCOME DISTRIBUTION: FORMALIZATION WITH ITERATED INVESTMENT GAME

The purpose of this paper is to formalize a simple model that theoretically connects individuals' rational choice at the micro level to income distribution, which is subject to the Gibrat's law empirically, as social structure at macro level. We use an iterated investment game as a baseline model in which a player has a binary choice between investing and not investing. Given parameters which prescribe the payoff structure of the game are the prize density γ and the rate of return R. Method of analysis is a simulation with computation. We investigate changes in the Gini coefficient and skewness of the total profit distribution, as the parameters varied as follows: 0 ≤ γ ≤ 1, R = 0.5, 1, 2, 3, and n (the number of times that the game is repeated) = 5, 10. As a result of analysis, we derive the implication that the Gini coefficient increases up to critical point, where 0 ≤ γ ≤ 1/(R + 1), then decreases as prize density increases, where 1/(R + 1) < γ ≤ 1. Furthermore, we show that our model, with cumulative effect, generates a lognormal distribution under the condition that 1/(R + 1) < γ ≤ 1.     

Change of zonal flow spectra in the JIPP T-IIU tokamak plasmas

When Ohmically heated low-density plasmas are additionally heated by higher-harmonics ion-cyclotron-range-of frequency heating, heated by neutral beam injection, or strongly gas puffed, the intensity of zonal flows in the geodesic acoustic mode frequency range in the tokamak core plasma decreases sharply and that of low-frequency zonal flow grows drastically. This is accompanied by a damping of the drift wave propagating in the electron diamagnetic drift direction, turbulence by trapped electron mode (TEM), and the increase of the mode propagating to ion diamagnetic drift direction (ITG). In the half-radius region, TEM and high-frequency zonal flows remain intense in both OH and heated phases. ITG and low-frequency zonal flows grow in heated plasmas, suggesting a strong coupling between ITG and low-frequency zonal flow.     

Ultrafast dynamics of photoactive yellow protein via the photoexcitation and emission processes

Pump-dump fluorescence spectroscopy was performed for photoactive yellow protein (PYP) at room temperature. The effect of the dump pulse on the population of the potential energy surface of the electronic excited state was examined as depletion in the stationary fluorescence intensity. The dynamic behavior of the population in the electronic excited state was successfully probed in the various combinations of the pump-dump delay, the dump-pulse wavelength, the dump-pulse energy and the observation wavelength. The experimental results were compared with the results obtained by the femtosecond time-resolved fluorescence spectroscopy.     

Coherent oscillations in ultrafast fluorescence of photoactive yellow protein

The ultrafast photoinduced dynamics of photoactive yellow protein in aqueous solution were studied at room temperature by femtosecond fluorescence spectroscopy using an optical Kerr-gate technique. Coherent oscillations of the wave packet were directly observed in the two-dimensional time-energy map of ultrafast fluorescence with 180 fs time resolution and 5 nm spectral resolution. The two-dimensional map revealed that four or more oscillatory components exist within the broad bandwidth of the fluorescence spectrum, each of which is restricted in the respective narrow spectral region. Typical frequencies of the oscillatory modes are 50 and 120 cm(-1). In the landscape on the map, the oscillatory components were recognized as the ridges which were winding and descending with time. The amplitude of the oscillatory and winding behaviors is a few hundred cm(-1), which is the same order as the frequencies of the oscillations. The mean spectral positions of the oscillatory components in the two-dimensional map are well explained by considering the vibrational energies of intramolecular modes in the electronic ground state of the chromophore. The entire view of the wave packet oscillations and broadening in the electronic excited state, accompanied by fluorescence transitions to the vibrational sublevels belonging to the electronic ground state, was obtained.     

Pd-catalyzed asymmetric allylic amination of Morita-Baylis-Hillman adduct derivatives using chiral diaminophosphine oxides: DIAPHOXs

[reaction: see text] Asymmetric allylic amination of allylic carbonates prepared from racemic Morita-Baylis-Hillman adducts proceeded in the presence of Pd catalyst, chiral diaminophosphine oxide (DIAPHOX), and BSA, affording the corresponding chiral aza-Morita-Baylis-Hillman adduct derivatives in excellent yield with up to 99% ee. The cyclic reaction products could be converted into various synthetically useful compounds such as chiral cyclic beta-amino acids.     

Solvent dependence of absorption intensities and wavenumbers of the fundamental and first overtone of NH stretching vibration of pyrrole studied by near-infrared/infrared spectroscopy and DFT calculations

Near-infrared (NIR) and IR spectra were measured for pyrrole in CCl(4), CHCl(3), and CH(2)Cl(2) to study solvent dependence of absorption intensities and wavenumbers of the fundamental and first overtone of NH stretching vibration. It was found that the wavenumbers of the NH fundamental and its first overtone decrease in the order of CCl(4), CHCl(3), and CH(2)Cl(2), which is the increasing order for of the dielectric constant of the solvents. Their absorption intensities increase in the same order, and the intensity increase is more significant for the fundamental than the overtone. These results for the solvent dependence of the wavenumbers and absorption intensities of NH stretching bands of pyrrole are quite different from those due to the formation of hydrogen bonds. Quantum chemical calculations of the wavenumbers and absorption intensities of NH stretching bands by using the 1D Schr?dinger equation based on the self-consistent reaction field (SCRF)/isodensity surface polarized continuum model (IPCM) suggest that the decreases in the wavenumbers of both the fundamental and the overtone of the NH stretching mode with the increase in the dielectric constant of the solvents arise from the anharmonicity of vibrational potential and their intensity increases come from the gradual increase in the slope of the dipole moment function.