Hydrobromic acid-dimethyl sulfoxide reagent for dealkylation of 5,10-dialkyl-5,10-dihydrophenazines: Synthesis of 10-alkyl-2(10H)-phenazinones

By the reaction of 5,10-dialkyl-substituted 5,10-dihydrophenazine with hydrobromic acid in dimethyl sulfoxide at 90–110°, 10-alkyl-2(10H)-phenazinone was obtained as a major product. Brominated dihydrophenazine was isolated in the case of 1,6-dichloro-5,10-dimethyl-5,10-dihydrophenazine.     

The most favorable condition for lipid hydrolysis by Rhizopus delemar lipase in combination with a sugar–ester and alcohol W/O microemulsion system

The hydrophobic interfacial characterization of sugar–ester alcohol W/O microemulsion was investigated in order to develop a suitable design for reaction media. A W/O microemulsion system was prepared as a combination of sugar–ester, DK-ester-F-110 with alcohol as a cosolvent. The diameter of the sub-micron-sized water pool, the hydrophobicity of the water pool, and the fluidity of the micro-interface were studied to analyze the reactivity of Rhizopus delemar lipase in lipid hydrolysis. The diameter of the sub-micron sized water pool was measured by dynamic laser light scattering. It was proportional to the 0.33 power of W_soln and decayed with increasing alcohol concentration. The initial reaction rate of the hydrolysis of triolein in W/O microemulsion depended on the solubilized water content. The hydrophilic character of the micro-water pool was estimated from the fluorescence wavelength indicated by Coumarin 343. The maximum initial reaction rate appeared at 450–460 nm. The fluidity of the micro-interface was investigated by fluorescence anisotropy using TMA-DPH. A suitable physicochemical reaction condition for high reactivity to occur was found, satisfying both the hydrophilicity and the fluidity of the micro-interface.     

Chelation of cadmium ions by phytochelatin synthase: role of the cysteine-rich C-terminal.

The interactions between Cd(2+) and the C-terminal region of phytochelatin (PC) synthase using recombinant wild-type and mutant PC synthase were studied. We show that site-directed mutagenesis of Cys residues at C(358)C(359)XXXC(363)XXC(366) motif decreases the number of Cd(2+) and other heavy metal ions interacting with the enzyme, and that the motif binds the metals discriminatingly. The optimum binding ratio of PC synthase to Cd(2+) was also determined. The findings indicate that Cys exists as a free SH residue and that it is involved in the regulation of PC enzyme activity by transferring the metals into closer proximity with the catalytic domain. These results are important in understanding heavy metal detoxification mechanisms in higher plants, a step towards phytoremediated-applications.     

Kinetics of hydrogen abstraction reaction between trifluoromethyl formate and OH radical: A theoretical investigation

Kinetics and mechanism of the hydrogen abstraction reaction between trifluoromethyl formate, CF₃OCHO, and OH radical have been investigated by using ab initio molecular orbital theory up to G2(MP2) level. The hydrogen abstraction rate constant has been calculated for the first time over a temperature range of 250–450 K by using standard transition state theory including the tunneling correction. Arrhenius parameters of the reaction have been estimated from the temperature dependence of the calculated rate constant. The calculated value for the rate constant (2.0 × 10^?14 cm³ molecule^?1 s^?1) at 298 K is found to be in very good agreement with the recent experimental results. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 500–507, 2002     

In situ monitoring of the H concentration change near an electrode surface through electrolysis using slab optical waveguide pH sensor

The H⁺ concentration change was monitored near an electrode surface through an electrolysis using a slab optical waveguide technique. Indium tin oxide transparent electrode modified by porous insulating polymer to which methyl red was covalently immobilized was used as a guiding layer, and the absorbance change of the polymer film was monitored. H⁺ generation at the vicinity of the electrode through the oxidation of ascorbic acid could be monitored by this technique.     

Anisotropic catalytic activity of the orientation controlled Nd2NiO4 + δ/YSZ hetero-epitaxial system for SOFC cathode

Electrode–electrolyte hetero-epitaxial systems for solid oxide fuel cells (SOFCs) with two different configuration of Nd₂NiO_4 + δ(110)//YSZ(100) and Nd₂NiO_4 + δ(100)//YSZ(110) were successfully fabricated by pulsed laser deposition. Thin films of Nd₂NiO_4 + δ approximately 20 nm thick were grown on a commercial single crystal of YSZ. The preferred two-dimensional diffusion paths of the oxide ions were perpendicular to the substrate for both configurations and showed oxygen reduction capability different from each other. This opens up new research direction focusing on the details of anisotropic catalytic activity of SOFC cathode depending on the crystalline surface.     

Formation mechanism of element distribution in glass under femtosecond laser irradiation

We report on the formation mechanism of element distribution in glass under high-repetition-rate femtosecond laser irradiation. We simultaneously focused two beams of femtosecond laser pulses inside a glass and confirmed the formation of characteristically shaped element distributions. The results of the numerical simulation in which we considered concentration- and temperature-gradient-driven diffusions were in excellent qualitative agreement with the experimental results, indicating that the main driving force is the sharp temperature gradient. Since the composition of a glass affects its refractive index, absorption, and luminescence property, the results in this study provide a framework to fabricate a functional optical device such as optical circuits with a high-repetition-rate femtosecond laser.     

Axially chiral dicarboxylic acid catalyzed asymmetric semipinacol rearrangement of cyclic β-hydroxy-α-diazo esters

The development of axially chiral dicarboxylic acid catalyzed desymmetrizing asymmetric semipinacol rearrangement of symmetrically substituted six-membered cyclic β-hydroxy-α-diazo esters is reported as a means to give chiral cycloheptanones with good enantioselectivities.