Tetracyclic alkaloids of the sparteine group.1H and13C NMR spectroscopy and conformational analysis

The¹H and¹³C chemical shifts of 11 sparteine derivatives are reported. Substituent and group effects are interpreted in terms of structural properties. The conformational equilibrium of aphyllin is determined.Ruhr-Universität Bochum, Fakultät für Chemie, Bochum, Germany. Universität Hannover, Institut für Organische Chemie, Hannover, Germany (present address). Department of Organic Chemistry, Poznan Academy of Economics, Poznan, Poland. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1026–1033, August, 1995. Original article submitted May 10, 1995.Dedicated to Prof. N. S. Zefirov on the occasion of his 60th birthday.     

Neue Spiroverbindungen aus Cyclophosphazenen und Cyclodi[phosphadiazan]en

New Spiro Compounds from Cyclophosphazenes and Cyclodi[phosphadiazanes] Chlorocyclophosphazenes (Cl₂P = N)₃ and (Cl₂p = N)₄ react with dihydrazidophosphoric acid derivatives in THF in the presence of triethylamine to give the spirocyclic compounds Cl₄N₃P₃(NHN(CH₃))₂P(S)OC₆H₅, Cl₆N₄P₄(NHNH)₂P(S)OC₆H₅. Constitutions have been confirmed by MS, NMR, IR and elemental analysis.     

Optical spectra and laser-induced dissociation of supported Na particles

This paper reports new results on the optical spectra of Na particles and on laser-induced photodissociation of Na atoms from the surface of these particles. In continuation of our earlier studies we have performed experiments to elucidate the mechanism of thenonthermal dissociation process. Furthermore, theoretical calculations have been carried out with the goal to correlate the wavelength dependence of the photodissociation yield with the optical absorption spectra of the metal particles. In addition, manipulation of the size distribution of metal particles on supports is outlined as an application of the effect. This allows for the preparation of very special surfaces with novel physical and chemical properties.     

Frequency domain measurements on Na2B4O7−V2O5 semiconducting glass

Summary Dielectric measurements on Na₂B₄O₇(99.5%)−V₂O₅(0.5%) glass system, in the frequency range 10⁻³ to 10⁴ Hz and temperature range 300 to 500 K, have been carried out. The normalized plots of complex capacitance have shown a single mechanism responsible for conduction for both volume and surface measurements with their close values of activation energies (0.67±0.03) eV and (0.64±0.03) eV, respectively. The low-frequency dispersion (LFD) behaviour has been observed to be perturbed by the presence of more than one competing process. The impedance plots have shown a parallel combination of a capacitor (C) and a resistor (R), with some contribution of a dispersive element due to charge accumulation in the vicinity of the electrodes. The values ofR andC were found to be of the same order of magnitude, for both surface and volume measurements. The observedR has shown a decrease with an increase in temperature due to an increase in mobility of Na⁺ ions, whereasC remains practicaly constant. The complex capacitance surface behaviour is dominated by volume, due to hygroscopy of this glass system.     

Analysis of barbiturates in human serum and urine by high-performance capillary electrophoresis-micellar electrokinetic capillary chromatography with on-column multi-wavelength detection

The analysis of barbiturates in human serum (or plasma) and urine by high-performance capillary electrophoresis-electrokinetic capillary chromatography with on-column fast-scanning multi-wavelength detection is discussed. The use of a buffer of ca. pH 8 and containing sodium dodecyl sulphate provides a medium suitable for fast and high-resolution separations of barbiturates. Seven barbiturates are characterized by their retention and absorption spectra between 195 and 320 nm. Comparison of these computer-stored data with those of unknown samples is shown to allow the identification of barbiturates in samples of patients undergoing pharmacotherapy and in toxicological urine and serum specimens. Three-dimensional electropherograms provide reliable information on the requirement and suitability of sample pretreatment procedures. With urine, extraction of barbiturates prior to analysis is necessary. With human serum several barbiturates, including phenobarbital, are shown to elute in an interference-free window in front of uric acid and the proteins, allowing these substances to be determined by direct sample injection. The need for multi-wavelength detection over a relatively wide wavelength range as a means of peak confirmation in electrokinetic capillary analyses is demonstrated and limitations of this technique for compounds with similar retention behaviour and absorption spectra are discussed.     

Inhibitors of prostaglandin biosynthesis from Dalbergia odorifera.

The root heartwood of Dalbergia odorifera T. Chen (Leguminosae) is a Chinese medicinal drug (Japanese name koshinko) used for a stagnant blood syndrome (stagnation of disordered blood; Japanese, oketsu). In addition to 10 known compounds, five new phenolic compounds, isomucronustyrene and hydroxyobtustyrene (cinnamylphenols), (+)-isoduartin (isoflavan), odoriflavene (isoflav-3-ene) and (-)-odoricarpan (pterocarpan) were isolated and their structures were elucidated on the basis of chemical and spectroscopic methods. Of the fifteen compounds isolated, cinnamylphenols, isoflavans, isoflavene and benzoic acid derivative significantly inhibited prostaglandin biosynthesis as well as platelet aggregation induced by arachidonic acid.     

New AlDy(Ni,Co) glasses - the influence of pre-aging on decomposition and modelling of the crystallisation

The decomposition of AlDy₆Ni₁₀ and AlDy₈Ni₆Co₂ glasses prepared by melt spinning after different pre-aging regimes was investigated. The modelling of the transformation at the glass transition and the crystallisation was tested by a more general Johnson-Mehl-Avrami-Kolmogorov model and by the determination of the local kinetic parameter. The relaxation was tested with an lnt kinetic model after Gibbs.     

Determination of mepiquatchloride in animal and plant matrices by ion chromatography with conductivity detection

Summary A new residue method, based on ion chromatography, for the determination of trace amounts of the ionic plant growth regulator mepiquatchloride is described. The method is adapted to plant and animal matrices and does not require any derivatization steps. This new technique provides higher recoveries of the analyte, better reproducibility and increased speed than the previous method. The limit of determination is 0.05 mg/kg.