Convergence in [2+2+2] synthesis of β-phenylnaphthalene motif in polyaromatic natural products

Two optional routes to β-phenylnaphthalene structure are developed by introducing α- and β-styryl groups onto different positions in the benzocyclobutene ring followed by ring enlargement.     

Status of heavy element research using a gas-filled recoil separator at RIKEN

A gas-filled type of recoil separator for heavy element research was installed at an experimental hall of RIKEN Linear Accelerator facility to realize getting higher intensity of primary beam and long beam time. Performance of the separator was studied using target recoils and various nuclear reactions. The results show the high performance of the separator for heave element research. As an application of the GARIS, production and identification of an isotope of the 110th element ²⁷¹[110] have been performed using the ²⁰⁸Pb(⁶⁴Ni,1n)²⁷¹[110] reaction. Three decay chains coincide well both in decay times and energies with the ones reported by the group of SHIP experiment at GSI, Germany. Our results provide a confirmation of the synthesis of an isotope ²⁷¹[110] of element 110.     

Structural characterization of polypyrrole in the solid state by high resolution 15N NMR spectroscopy [II]

The solid-state ¹⁵N CP/MAS NMR spectra and ¹⁵N spin-lattice relaxation times (T₁) of doped and dedoped ¹⁵N-labeled polypyrroles prepared by electrochemical polymerization, have been measured by means of high-resolution solid-state ¹⁵N NMR. The ¹⁵N signal of polypyrrole consists of four peaks decomposed by line shape analysis. The four peaks obtained have been assigned to the various structures of polypyrrole. Further, the half-width of the ¹⁵N NMR spectra of polypyrroles is discussed as related to the electrical conductivity. © 1995 John Wiley & Sons, Inc.     

Development and features of hydro-membrane gas chromatography.

Hydro-membrane gas chromatography (HMGC) is achieved by the annular condensation of water in a capillary column at less than 70 degrees C. The annular membrane of water is formed as a result of the wettability of the stationary phase, which is induced at a water contact angle ranging from 75 degrees to 79 degrees, as derived from a solubility parameter (delta) range of 15.7 +/- 0.3 MPa(1/2) of the coated resin. The range of the liquid to gas volume ratio (beta) required to support the annular membrane should be kept between 0.00005 and 0.0003. In the case of a 0.25-mm i.d. column, the ratio can be set by the combination of a 0.1 to 0.2 microl min(-1) water supply rate and helium gas flow rate. Separation by HMGC develops not only a gas-solid partition but also a focusing effect on the water membrane. One feature of HMGC is that it gives a non-adsorption chromatogram based on the blocking effect of pre-adsorbed water; furthermore, despite the presence of a relatively large quantity of water, the electron impact ionization efficiency is kept the same as in the usual GC/MS condition. The detection limit with the injection of 1 microl of aquatic solution was estimated to be less than 0.1 ppb of low-molecular-weight fatty acids with s/n = 5 on a mass chromatogram at m/z 45. The HMGC/EI-MS system can be applied to the trace analysis of C1 to C3 volatile acids, volatile inorganic acids, and halogenated organic acids in water.     

A convergent approach to the formal total synthesis of hemibrevetoxin B

A convergent synthesis of the key synthetic intermediate of hemibrevetoxin B was achieved via the intramolecular allylation of an α-chloroacetoxy ether and subsequent ring-closing metathesis.     

Two-mass models of the vocal cords for natural sounding voice synthesis

Three new two-mass models of the vocal cords are treated. First, the features, structure, and differential equations of motion are described for each of the new models and compared with those of previous models. Second, performances of the models are discussed in terms of glottal volume flow, glottal area, radiated sound pressure, trajectories of mass movement, running spectra of the output sound pressure, and perceptual naturalness of the output sound. Finally, the major effects of glottal source-vocal tract interaction including skewing, truncation, and superposition are investigated, using one of the simplest types of two-mass models and two types of load representing the vocal tract.     

Durch Bromierung ausgelöste Umlagerung tertiärer Allylalkohole: Der Einfluss eines Fluor-Substituenten auf Reaktionsgeschwindigkeit und Reaktionsverlauf

Rearrangement of Tertiary Allyl Alcohols Induced by Bromination: The Effect of a Fluorine Substituent on the Rate and the Outcome of the Reaction The allyl alcohol bearing a methyl and a t-butyl group at the hydroxylated position was found to undergo a rearrangement when treated with bromine (or N-bromosuccinimide) in an aqueous medium and to afford a product mixture containing two regioisomeric ketones and one oxirane. Introduction of an additional methyl group or a fluorine atom at the non-terminal olefinic center led to a more selective discrimination between potential migratory groups. As the result of an exclusive t-butyl shift only one product, a ketone, was formed in both cases. Whereas the reaction rate was only slightly affected by the additional methyl group, it was substantially decreased by the fluorine atom.     

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.