On the class numbers of certain Hilbert class fields

LetL/k be a finite Galois extension with Galois groupG, and a group extension. We study the existence of the Galois extensionM/L/k such that the canonical projection Gal(M/k)→Gal(L/k) coincides with the given homomorphismj:E→G and thatM/L is unramified.     

Base-labile tert-butoxycarbonyl (Boc) group on phenols

Phenols are deprotected with weak bases from their tert-butoxycarbonyl (Boc) derivatives. Boc deprotection with bases can avoid side reactions during the deprotection with acids. We note the lability of the Boc to bases and are able to utilize it as a new cleavage condition for synthetic studies.     

Initiation of cationic polymerization of n-butyl vinyl ether by stable cation radicals of substituted phenothiazines

3,7-Diethyl- 10-phenylphenothiazine (DEPPT), a phenothiazine derivative whose 3,7- and 10-positions are blocked, was synthesized. Potentiostatic electrolysis of DEPPT in acetonitrile (ACN) in the presence of 0.1M of LiClO₄ at 0.7 V (vs. Ag/Ag/Cl) yielded the stable cation radical of DEPPT (DEPPT^+·) which was characterized by cyclic voltammetry, UV-visible spectroscopy, and ESR spectrometry. Stable cation radicals of 10-phenylphenothiazine and 3,7-diethyl-10-methylphenothiazine were also prepared. The cationic polymerization of n-butyl vinyl ether was initiated by these cation radicals, including DEPPT^·+. The electron transfer mechanism for the initiation step, which we proposed previously, was supported by the fact that DEPPT^·+ was capable of initiating the polymerization; dimerization of DEPPT^·+ by releasing protons is precluded because 3,7- and 10-positions are all blocked. © 1994 John Wiley & Sons, Inc.     

Complexation of Fluvastatin Sodium with β-Cyclodextrin: NMR Spectroscopic Study in Solution

¹H NMR spectroscopic study of fluvastatin sodium (FLU), β-Cyclodextrin (β-CD) and their mixtures confirmed the formation of FLU/β-CD inclusion complex in solution. The stoichiometry of the complex was determined to be 1:1 and the overall binding constant (K _s) was calculated to be 340 M⁻¹. Two dimensional COSY, ROESY and DEPTO experiments were performed for the unambiguous assignment of aromatic proton resonances and it was found that two isomeric forms of FLU are present in solution. It was confirmed with the help of ROESY spectral data that only F-substituted aromatic ring penetrates the β-CD cavity and there is chiral differentiation by the β-CD as one of the isomer binds more strongly, which is indicated by the intensity of correlation peaks. The mode of penetration of the guest into the β-CD cavity was also established and structure of the complex has been proposed.     

Photophysical properties of oligo(2,3-thienyleneethynylene)s

Photophysical properties of oligo(2,3-thienyleneethynylene)s (nTE, n denotes the number of thiophene rings, n = 2, 3) in benzene were investigated using steady-state, time-resolved fluorescence, and transient absorption spectroscopies. For 2TE, generation of the radiative S2 and nonradiative S1 states was confirmed. Upon excitation, the S2 state was initially generated and deactivated to the S1 state within 10 ps. The S1 state exhibited the transient absorption band at 470 nm, of which the lifetime was estimated to be 5.3 ns. In the case of 3TE, on the other hand, it was revealed that the radiative S1 state with a transient absorption peak at 650 nm was generated upon excitation. The T1 states of nTE were generated from the S1 states. The quantum yields were estimated to be 0.52 and 0.54 for 2TE and 3TE, respectively. Extremely fast reactions in the higher triplet excited state were indicated for both 2TE and 3TE.     

Methyl groups as probes for proteins and complexes in in-cell NMR experiments

Studying protein components of large intracellular complexes by in-cell NMR has so far been impossible because the backbone resonances are unobservable due to their slow tumbling rates. We describe a methodology that overcomes this difficulty through selective labeling of methyl groups, which possess more favorable relaxation behavior. Comparison of different in-cell labeling schemes with three different proteins, calmodulin, NmerA, and FKBP, shows that selective labeling with [(13)C]methyl groups on methionine and alanine provides excellent sensitivity with low background levels at very low costs.     

Kinetics of transient end-to-end contact of single-stranded DNAs

The formation of the pyrene (Py) dimer radical cation (Py(2)(*+)) was used to measure the kinetics of the intrastrand end-to-end contact rates of single-stranded DNAs (ssDNAs) in the 10 nanoseconds to the tens of microseconds time range. ssDNAs labeled with Py at both ends with the lengths of 3, 6, and 9 mer were synthesized, and the two-photon ionization method was employed to generate a Py(*+), which enables the measurements of the end-to-end contact rates from 10 ns. The formation rate of Py(2)(*+) depended on the length and the sequence of the ssDNAs, and about 1 order of magnitude faster rates were observed for the T-rich ssDNAs compared to those for the corresponding length of A-rich ssDNAs, showing that ssDNA made from adenines is much more rigid than that composed of thymidines. As for the T-rich ssDNAs, the formation of Py(2)(*+) attributed to the misfolded structures was also observed, which is consistent with the configurational diffusion model suggested by Ansari and co-workers.     

Tensammetric determination of microgram amounts of vanadium by catalytic oxidation of o-aminophenol

A tensammetric method is proposed for the determination of microgram amounts of vanadium, based on catalysis of the oxidation of o-aminophenol with sodium chlorate in acidic solution (pH 2.0). The oxidation product gives a very sensitive tensammetric wave; under optimum conditions, the wave-height is proportional to the concentration of va vanadium. From 0.2 to 3.0 mug of vanadium can be determined in a final volume of 50 ml. Mo(VI), W(VI), Mn(VII), Ce(IV) and large amounts of Al(III) and Fe(III) cause positive errors, and Hg(II) and thiosulphate negative errors. Interference from Fe(III), Al(III) and Cu(II) can be eliminated by solvent with oxine at about pH 8.0.     

Photocatalytic Reduction of NO with C2H6 on a Hollandite-Type Catalyst

The photocatalytic reduction of nitrogen monoxide (NO) with ethane on the hollandite type catalyst (K₂Ga₂Sn₆O₁₆KGSO) was investigated. Using a closed-gas circulating system equipped with a Q-MASS detector and in-situ diffuse reflectance FT-IR spectroscopy. The reactant gases of NO and ¹³C₂H₆ decreased with the increasing irradiation time. In contrast, the N₂ yield increased proportionally to the conversion of ¹³C₂H₆. Nitrogen oxides such as N₂O did not reach their detectable levels. The NO adsorbed on KGSO was found to change to its activated species by UV irradiation. The oxidized products of C₂H₆ such as CH₃CHO increased in proportion to the reaction time. The present results strongly suggest that KGSO has remarkable photocatalytic activity for the reduction of NO with C₂H₆.     

Inhibitory effects of 1,3-selenazol-4-one derivatives on mushroom tyrosinase

This study reports depigmenting potency of 1,3-selenazol-4-one derivatives, which would be based upon the finding of direct inhibition to mushroom tyrosinase. 1,3-Selenazol-4-one derivatives exhibited inhibitory effect on dopa oxidase activity of mushroom tyrosinase. In this study, inhibitory effects of six kinds of 1,3-selenazol-4-one derivatives (A, B, C, D, E and F) on mushroom tyrosinase were investigated. Compounds at a concentration of 500 microM exhibited 33.4-62.1% of inhibition on dopa oxidase activity of mushroom tyrosinase. Their inhibitory effects were higher than that of kojic acid (31.7%), a well known tyrosinase inhibitor. 2-(4-Methylphenyl)-1,3-selenazol-4-one (A) exhibited the strongest inhibitory effect among them dose-dependently and in competitive inhibition manner.