Synthesen von Heterocyclen, 124. Mitt.: Über Reaktionen des Isatosäureanhydrids mit Thioamiden und Amiden

Zusammenfassung Beim Verschmelzen von Isatosäureanhydrid (1) mit Thioamiden bilden sich 2-substit.-4(3H)-Chinazolinone (3a-h).

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Syntheses of heterocycles, CXXIV.: Reaction of isatoic anhydride with thioamides and amides

The reaction of isatoic anhydride with thioamides yields 2-substituted 4(3H)-quinazolinones (3a-h).

     

Synthesen von Heterocyclen, 146. Mitt.: Zur Synthese polymerer Indigofarbstoffe mit potentiellen Halbleitereigenschaften

Zusammenfassung Die Darstellung von polymeren Indigofarbstoffen (PI) nach dem Verfahren vonZiegler undKappe ^{2, 3} wird beschrieben. Ausgehend von Benzidin (1 a) und Tolidin (1 b) erhält man so diePI 6 a bzw.6 b. In analoger Weise wird aus Tetrahydrochinoxalin (7), der N,N-überbrücktePI 12 gewonnen.

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Syntheses of heterocycles, CXLVI: The synthesis of polymeric indigos with potential semiconductor properties

The synthesis of polymeric indigos (PI) according to the procedure ofZiegler andKappe ^{2, 3} is described. Starting with benzidine (1 a) or tolidine (1 b) thePI 6 a and6 b, resp., are obtained. In a similar way the N,N-bridgedPI 12 is synthesized from tetrahydroquinoxaline (7).

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Aus den Dissertationen vonH. G. Foraita undL. F. Werner, Universität Graz, Januar bzw. Juni 1963.     

The electronic spectrum of VCr

The electronic spectrum of VCr has been studied using the complete-active-space self-consistent field complete-active-space second-order perturbation theory approach. Potential-energy curves for 12 electronic states have been computed. Transition energies, with respect to the X² ground state, for some of the calculated electronic states are (with possible experimental values within parentheses) 0.53 eV (0.56) for A²⁺, 1.03 eV (1.14) for A⁴, 1.20 eV (1.14) for B², 1.45 eV (1.51) for B⁴, 1.60 eV (1.51, 1.78) for C², and 1.61 eV (1.63) for A^4–. AcknowledgementsThe research reported in this communication was supported by a grant from the Swedish Natural Science Research Council (NFR). S. Alex and D.G. Leopold are acknowledged for providing results from their negative ion photoelectron spectroscopy on VCr.Contribution to Björn Roos Honorary Issue     

Cathodic adsorptive stripping square-wave voltammetric determination of nifedipine drug in bulk,pharmaceutical formulation and human serum

Nifedipine is a calcium-channel antagonist drug used in the management of angina pectoris and hypertension through inhibition of calcium influx. A fully validated sensitive cathodic adsorptive stripping square-wave voltammetry procedure was optimized for the determination of the drug at trace levels. The procedure was based on the reduction of the nitrophenyl group after the interfacial accumulation of the drug onto a hanging mercury drop electrode in Britton-Robinson buffer of pH 11.0. The optimal conditions of the procedure were found to be: accumulation potential=-0.9 V vs. Ag/AgCl/KCl(s)), accumulation time=30 s, scan increment=10 mV, pulse amplitude=50 mV and frequency=120 Hz. Under these conditions, a well-defined peak was obtained; its peak current showed a linear dependence on drug concentration in the range of 2x10(-9)-2x10(-7) mol L(-1) bulk nifedipine. The mean recoveries based on eight replicate measurements for 1x10(-8) and 5x10(-8) mol L(-1) bulk nifedipine solutions were 98.46+/-0.86% and 98.23+/-0.92%, respectively. A detection limit of 3.42x10(-10) mol L(-1) bulk nifedipine was achieved. The procedure was successfully applied for assay of the drug in tablets and spiked human serum with mean recoveries of 101.95+/-1.42% and 98.70+/-0.63%, respectively. The limit of detection of the drug in spiked human serum was found to be 3.90x10(-10) mol L(-1).     

Determination of affinity constants and response factors of the noncovalent dimer of gramicidin by electrospray ionization mass spectrometry and mathematical modeling

The dimerization of gramicidin, a 15-residue membrane peptide, in solution can be viewed as a model for protein-protein interactions. We reported previously that the dimer can be observed when electrosprayed from organic solvents and that the abundances of the dimer depends on the dielectric constant of the solvent. Here, we report an effort to determine an affinity constant for the dimerization of gramicidin by using gas-phase abundance. Two issues affecting the determination are the electrospray-induced dissociation of the dimer and discrimination in the electrospray of the dimer compared with the monomer. Other methods developed for the purpose of determining affinity from mass spectral abundance do not address the dissociation of the complex in the gas phase or can not be applied for cases of low affinity constant, K(a). We present a mathematical model that uses the ratio of the signal intensities of the dimer and the monomer during a titration. The model also incorporates the dissociation and an electrospray ionization-response factor of the dimer for extracting the affinity constant for the dimerization of gramicidin. The dimerization constants from the new method agree within a factor of two with values reported in the literature.     

Crystal structure of the ceramic superconductor BaPb0.75Bi0.25O3

The ceramic superconductor BaPb_0.75Bi_0.25O₃ is monoclinic atT<430 K with space groupI2/m. Lattice constants and the atomic coordinates result from 20 reflection groups (12<2<120°, =1.1267 Å) collected with a high resolution powder diffractometer using a synchrotron radiation source and a full neutron powder pattern (6<2<140, =1.909 Å). Synchrotron and neutron data were simtultaneously refined with SIMREF, a new profile refinement program, based on the Rietveld method. Group theoretical analysis of the distortion field leading from the ideal perovskite structure toI2/m exhibitsR ₄ ⁺ symmetry. A comparison is made with the corresponding distortions in nonsuperconducting BaBiO₃ where three different symmetry types are identified. The space groupI2/m found for BaPb_0.75Bi_0.25O₃ allows only one type of averaged (Pb/Bi)O₆ octahedron in the structure: this may support valence fluctuations and hence contribute to the mechanism of superconductivity in this particular compound.     

Observed difference between the probabilities of recoilless resonance absorptionf′ and reemissionf″ of gamma-quanta in single crystals of Na2[Fe(CN)5NO]·2 H2O

The recoilless absorption probability factor,f, and recoilless reemission,f, both measured on Na₂[Fe(CN)₅NO]·2 H₂O single crystals using the black filter technique, were found to be different. Unexpectedly, the results found weref>f. In the calculation off, selfabsorption in the scatterer, non-ideality of the black filter and the influence of non-resonant scattering processes have all been taken into account. By varying the scattering geometry for the incoming and outgoing -beam relative to the crystallographic axes only a change in the reemitted valuesf _a, f_b, f_c could be detected because of the long lifetime of the excited nucleus (10^–7 s) relative to the lattice vibration frequencies (10¹² Hz).     

Über die lokale Zetafunktion von Shimuravarietäten. Monodromiefiltration und verschwindende Zyklen in ungleicher Charakteristik

Ohne Zusammenfassung

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On the local zeta function of Shimura varieties. Monodromy filtration and vanishing cycles in unequal characteristic

     

The luminescence of Pr3+ in BaY4Si5O17

The cell constants of four new monoclinic compounds BaR₄X₅O₁₇ (R = Y, Gd; X = Si, Ge) are given. The luminescence of various RE activators in the silicates is reported. Pr³⁺-activated BaY₄Si₅O₁₇ shows efficient ultraviolet 5d → 4f emission and weak 4f → 4f emission (mainly red luminescence from the ¹D₂ level). The 5d → 4f emission is ascribed to Pr³⁺ on Y sites, the 4f → 4f emission to Pr³⁺ on Ba sites. Energy transfer from Pr³⁺ to Gd³⁺ has been observed. Gd³⁺ plays an intermediate role in the energy transfer from Pr³⁺ to Sm³⁺ and to Dy³⁺ in BaGd₄Si₅O₁₇. Upon activation with Tb³⁺ the silicates show characteristic green Tb³⁺ luminescence with a quantum efficiency of 75% for ultraviolet excitation.