The system BaOGeO2 at high pressures and temperatures,with special reference to high-pressure transformations in BaGeO3, BaGe2O5, and Ba2Ge5O12

Phase relations in the system BaOGeO₂ were investigated in the pressure range 20–70 kbar in the temperature range 750–1200°C. Several new phases were identified in this system: an atmospheric phase of BaGe₂O₅ (monoclinic BaGe₂O₅ I), two high-pressure phases of BaGe₂O₅ (monoclinic BaGe₂O₅ II and tetragonal BaGe₂O₅ III), and a high-pressure phase of Ba₂Ge₅O₁₂. The phase boundary curve between BaGe₂O₅ II and BaGe₂O₅ III was preliminarily determined as P(kbar) = 7.7 + 0.047T (°C). The high-pressure phases of BaGeO₃, which were previously reported by Y. Shimizu, Y. Syono, and S. Akimoto (High Temp.-High Pressures2, 113 (1970)) in the pressure range 15–95 kbar, were interpreted to be not single-phase materials but complicated mixtures of more than two phases in the system BaOGeO₂. X-Ray powder diffraction data for the new compounds synthesized in this study are given.     

Effect of Coriolis force on counter-current chromatographic separation by centrifugal partition chromatography

The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.     

Simple dispersion measurement of a long-span,single-mode fibre using the longitudinal mode spacing of a semiconductor laser

A simple method for measuring dispersion in long-span single-mode fibre, by using directly modulated multi-longitudinal mode semiconductor lasers, is proposed. Experimental values for single-mode fibre dispersion over a 44.3km span at 1.1 and 1.5m are 19 and 17 ps km^–1 nm^–1, respectively, and are in good agreement with Gloge's theory. The zero-dispersion wavelength estimated from the experimental results is about 1.28m, 8 nm shorter than the theoretical value.     

Air-Segmented Continuous-Flow Analysis for Molybdenum in Various Geochemical Samples

 An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L⁻¹ and 17 pmol L⁻¹, and the reproducibilities at 10 nmol L⁻¹ were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our knowledge, and is also convenient for routine analysis of molybdenum in various natural samples. Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp Received October 23, 2002; accepted January 28, 2003 Published online May 19, 2003     

Vinyl polymerization. 275. Polymerization of vinyl monomers photosensitized by tetramethyltetrazene

A study of the photopolymerization of vinyl monomers in the presence of tetramethyltetrazene (TMT) was made. TMT was found to act as an effective sensitizer. In the photopolymerization of vinyl monomers such as methyl methacrylate or styrene the rate of polymerization was expressed by the equation: R_p = k[TMT]^1/2[monomer]. The chain-transfer constant of TMT under ultraviolet irradiation was estimated to be 3.8 × 10^?2 for the above monomers. A linear correlation was found to exist between the reactivity of dimethylamino radical toward the vinyl monomers and e values for the corresponding monomers.     

SYNTHESIS AND CHARACTERIZATION OF KINETICALLY STABILIZED 1,3-DIPHOSPHACYCLOBUTENE DERIVATIVES

1-(2,4,6-Tri-tert-butylphenyl)-2-phosphaethyne (1) was allowed to react with 0.5 equiv of an alkyllithium and subsequently with an alcohol to afford a bulky 1,3-diphosphacyclobutene, and its structure and coordination properties on transition metals were investigated. On the other hand, 1 was allowed to react with an alkyllithium and iodomethane to form a stable biradical, 1,3-diphosphacyclobutane-2,4-diyl.     

Synthesis and Hydrolysis of Polymers Having Anesthetic or Amantadine Residues in Sidechains

The polymerizable derivatives of chemotherapeutic agents such as benzocaine, procaine, and amantadine were prepared and free-radical copolymerized with styrene or methyl methacrylate in order to obtain polymers with pharmacological activity and increased duration of action of the drugs. The monomeric and polymeric derivatives were subjected to hydrolysis in vitro in order to measure the release of the active ingredient.     

Radical Copolymerization of Vinylidene Chloride with 3(2-Methyl)-6-methylpyridazinone in Several Solvents

The radical copolymerization of vinylidene chloride (Vc, M₁) with 3(2-methyl)-6-methylpyridazinone (I, M₂) was carried out in benzene, ethanol, phenol, and acetic acid at 60 and 80°C. The monomer reactivity ratios were found to vary with the reaction conditions. The linear correlationships were obtained by plotting the values of log r₁ against those of ^V C[dbnd]O and ^V C[dbnd]C of monomers determined in the solvents.