Substituent effects on the kinetics for the chemiluminescence reaction of 6-arylimidazo[1,2-a]pyrazin-3(7H)-ones (Cypridina luciferin analogues): support for the single electron transfer (SET)-oxygenation mechanism with triplet molecular oxygen

Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O₂) in the oxygenation process.     

Importance of single electron-transfer in singlet oxygen reaction in aqueous solution : Oxidation of electron-rich thioanisoles

Oxidation of substituted thioanisoles by chemically generated singlet oxygen was investigated in polar aqueous media. The formation of the superoxide ion was observed during sulphoxidation of 4-hydroxythioanisole (4) in phosphate buffer at pH 7.5. Control experiments indicated that the superoxide ion was formed by a direct reaction between singlet oxygen and 4. The kinetics of the trapping reaction by diphenylsulphoxide indicated the involvement of a single intermediate. The overall rate constants of the reaction of thioanisoles with singlet oxygen in methanol-water (1:1) are one order of magnitude larger than those in benzene. On the basis of these results, a mechanism involving a charge-transfer complex has been proposed for the reaction of electron-rich thioanisoles with singlet oxygen, whereby the charge-transfer complex would produce persulphoxide directly or dissociate to the cation radical and superoxide ion in polar aqueous media.     

Chloroprene as a source of fine chemicals: palladium-catalyzed synthesis of terminal allenes

[reaction: see text] Several functionalized terminal allenes were prepared in moderate to excellent yield by a palladium-catalyzed reaction of chloroprene (2-chloro-1,3-butadiene) with soft nucleophiles.     

On the Theory of Gravitational Field in Finsler Spaces

Some structural considerations are made on the Finslerian gravitational field: A Finslerian metrical structure such as g_λχ(x, y) = γ_λχ(x) + h_λχ(x, y) is proposed, where γ_λχ denotes the Riemann metric of Einstein's gravitational field, while hλχ the Finsler metric induced by the Riemann metric h_ij(y) of the internal field; The intrinsic behaviour of the internal variable y, which is expressed as ?ⁱ = K(x, y) y^j in the internal field, is grasped by the Finslerian parallelism δyⁱ (=0), which is reflected in the spatial structure of the external gravitational field by the mapping relation δy^χ = e(x) δyⁱ. The whole metrical Finsler connection D for g_λχ(i.e., Dg_λχ = 0) is determined by taking account of the intrinsic behaviour δy^χ.     

Study of a high-dimensional chaotic attractor

The nature of a very high-dimensional chaotic attractor in an infinite-dimensional phase space is examined for the purpose of studying the relationships between the physical processes occurring in the real space and the characteristics of high-dimensional attractor in the phase space. We introduce two complementary bases from which the attractor is observed, one the Lyapunov basis composed of the Lyapunov vectors and the another the Fourier basis composed of the Fourier modes. We introduce the exterior subspaces on the basis of the Lyapunov vectors and observe the chaotic motion projected onto these exteriors. It is shown that a certain statistical property of the projected motion changes markedly as the exterior subspace goes out of the attractor. The origin of such a phenomenon is attributed to more fundamental features of our attractor, which become manifest when the attractor is observed from the Lyapunov basis. A counterpart of the phenomenon can be observed also on the Fourier basis because there is a statistical one-to-one correspondence between the Lyapunov vectors and the Fourier modes. In particular, a statistical property of the high-pass filtered time series reflects clearly the difference between the interior and the exterior of the attractor.     

Novel synthesis of macrocycles with 1,1′-binaphthalene-2,2′-diol using intramolecular oxidative coupling

A new series of BINOL-based macrocycles with two phenolic protons have been synthesized via oxidative coupling reaction using CuCl(OH)-TMEDA.     

Effect of titanium dioxide on photostability of solid-state mequitazine

TiO(2) has been widely used in pharmaceutical products, and it also has been used as a photocatalyst. In this study, the influence of photocatalytic activity on the stability of solid-state mequitazine, an H(1)-blocker, was investigated. The photo-degradation of mequitazine with TiO(2) occurred under irradiation with both light sources. The degree of degradation of mequitazine with anatase was higher than that of rutile. The degradation was significantly enhanced with increasing relative humidity. The relationship between the apparent degradation rate constant and water vapor pressure could be clearly described by a simple power law. The major photo-degradation products of mequitazine, resulting from photocatalytic activity of TiO(2), were mequitazine-S-oxide and mequitazine-sulphone. A remarkable degradation of mequitadine occurred with addition of TiO(2), and its photocatalytic activity was controlled by water vapor pressure. The photo-degradation of mequitazine with TiO(2) is a different process from mequitazine without TiO(2), because mequitazine-S-oxide and mequitazine-sulphone are not formed with normal photo-degradation of mequitazine.