Hydroquinone oxidation catalyzed by pyridine–Cu(II) complexes attached to polyorganosiloxane. II. Elucidation of factors related to catalytic activity

The oxidation of hydroquinone catalyzed by pyridine-Cu(II) complexes attached to polyorganosiloxane was investigated in the mixed solvent of methanol/water (vol. ratio 2/1). The catalytic oxidation followed Michaelis-Menten-like kinetics. The large k₂ term related to a turnover number indicated that the present polymeric catalysts have a remarkable effect on the activation process. The methylene number between the side-chain acid amido and pyridyl groups of the polymeric ligand was shown to be closely related to the appearance of hydrophobic effects in both the substrate-binding and the activation processes as deduced from the Michaelis constant and the thermodynamic and activation parameters. The binding parameters for 4-methoxyphenol with pyridyl-functionalized polyorganosiloxanes supported that the flexible backbone is also effective in the oxidation of hydroquinone. The Cu(II) complexes with pyridyl-functionalized polyorganosiloxane would have the structures distorted from square planar formation, which would promote the reduction of Cu(II) to Cu(I), as concluded from ESR spectroscopy and electrochemical measurement. © 1994 John Wiley & Sons, Inc.     

Chromogenic crown ether reagents for spectrophotometric determinations of sodium and potassium

Crown ethers carrying a phenolic group, 2-hydroxyphenoxymethyl-15-crown-5 and -18-crown-6, were synthesized. Introduction of nitro groups in the 3- and 5-positions of the aromatic nucleus or introduction of a 4-nitrophenylazo group in the 5-position gives a series of chromogenic reagents suitable for the extraction spectrophotometry of sodium and potassium. Sodium in human blood serum was successfully determined by using the (2-hydroxy-3,5-dinitrophenyl)oxymethyl-15-crown-5 reagent. The molar absorptivity of the sodium complex is 14 000 l mol^-1 cm^-1 at 423 nm.     

Hyperfine field and diffusion of μ+ in Fe single crystals

In recent positive-muon spin rotation experiment at TRIUMF on single crystal Fe, a clear temperature dependent change has been observed, for the first time, both in frequency and depolarization rates from 300 K down to 23 K. The μ⁺ depolarization was explained by the μ⁺ diffusion through inhomogeneous dipolar fields and the diffusion constant was found to obey an Arrhenius law (activation energy 17 meV) above 70 K but surprisingly deviated from this at lower temperatures, indicating quantum diffusion. We have also found that the μ⁺ hyperfine field has a temperature dependence slightly stronger than that of the magnetization.     

Thermal and photochemical reactions of a stable thiobenzaldehyde, 2,4,6-tri-t-butylthiobenzaldehyde

Thermal and photochemical reactions of the title compound gave benzothiolane $\text{2}$ in high yield; the reaction with free radicals also afforded $\text{2}$ along with some other products.     

CW Operation of a Submillimeter Wave Gyrotron (Gyrotron Fu IV) for High Stability of the Output Frequency

The first cw operation of our submillimeter wave gyrotron (Gyrotron FU IV) using a 12 T superconducting magnet has been successfully carried out. Output power is more than 20 W at a frequency of 301 GHz in the TE₀₃₁ resonant cavity mode. Time-resolved frequency measurement s shows that the frequency fluctuation of the gyrotron output is smaller than 2 MHz. This frequency fluctuation is mainly due to the fluctuation in the output voltage of the power supply.     

Sedimentation transport method for determination of molecular weight distributions

The sedimentation of the system polystyrene-cyclohexane at the Flory temperature has been studied with emphasis on the effects of pressure as well as concentration. The relation between the molecular weight M and the limiting sedimentation coefficient s₀⁰, is found to be s₀⁰ = 1.50 × 10^?15 M^1/2 (sec.) The concentration dependence parameter k_s has the form, k_s = k′M^1/2 = k″s₀⁰ with k′ = 4.5–5.5 × 10^?4. However, a rather unexpected dependence of k_s on the rotor speed is also found. A procedure is proposed for deducing solute molecular weight distributions from boundary spreading data in sedimentation transport experiments, a so-called “single concentration” method, requiring only one sedimentation run. Application to several polystyrenes (in cyclohexane at 35°C) with narrow, broad, and very broad distributions demonstrates the feasibility of the procedure. Comparisons are made with data from elution chromatography and gel permeation chromatography. The GPC method predicts somewhat broader distributions than those obtained by the other two methods.