1-Ethyl-1,4-dihydro-4-oxo-7-(pyridinyl)-3-quinolinecarboxylic acids. I. Synthesis of 3- and 4-(3-aminophenyl)pyridine intermediates

A series of substituted 3- and 4-(3-aminophenyl)pyridines has been prepared as intermediates for the synthesis of some 1-alkyl-1,4-dihydro-4-oxo-7-pyridinyl-3-quinolinecarboxylic acids. The Hantzsch, Hauser and other pyridine syntheses were used. 4-(3-Aminophenyl)pyridine was prepared via 3-(4-pyridinyl)-2-cyclohexen-1-one using the Semmler-Wolff reaction.     

The electronic structure of molecules by a many-body approach

The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C₃H₆ the ordering of the ionization potentials is 2e(), 1e(), 2a₁(), 1a₂(), 1e(). The assignment of the 2a₁ and the 1a₂ ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C₂H₄O the ordering of the ionization potentials is 2b ₁(), 4a ₁, 1a ₂(), 2b ₂,3a ₁, 1b ₁(), 1b ₂, 2a ₁ and for C₂H₅N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory.     

Coordination Chemistry of Acrylamide 4. Crystal Structures and IR Spectroscopic Properties of Acrylamide Complexes with CoII,NiII, and ZnII nitrates

Acrylamide complexes of metal nitrates: [M(O‐OC(NH₂)CHCH₂)_n(H₂O)_m][NO₃]₂ (M = Co( 1 ), Ni( 2 ) (n = 6 and m = 0) and Zn( 3 ) (n = 4 and m = 2)) have been determined by using single crystal X‐ray diffraction analysis. All complexes crystallize in the triclinic space group . The structures of 1 and 2 represent octahedral species [M(AAm)₆]²⁺ (AAm = O‐OC(NH₂)CHCH₂ and M = Co or Ni) and uncoordinated nitrate ions. The structure of 3 involves the octahedral cation [Zn(AAm)₄(H₂O)₂]²⁺ in which the Zn²⁺ environment includes oxygen atoms of four acrylamide and two water molecules that are stabilized using ionic nitrate ions. The observations of the solid‐state IR spectroscopic vibrational frequencies of these acrylamide complexes are in agreement with the crystal structures.     

Growth and characterization of Mn- and Co-doped ZnO nanowires

A flow injection chemiluminescence method is proposed for the determination of cobalt, based on the strong catalytic effect of Cobalt(II) (1,10-phenanthroline)₃ complex on the lucigenin-periodate reaction in alkaline medium. Under the optimum experimental conditions, the chemiluminescence signal responded linearly to the concentration of cobalt(II) in the 1.0 × 10⁻⁹–3.0 × 10⁻⁷ g mL⁻¹ range with a detection limit of 4.4 × 10⁻¹⁰ g mL⁻¹ cobalt(II). The relative standard deviation for the determination of 5.0 × 10⁻⁸ g mL⁻¹ of cobalt was 2.3% in eleven replicated measurements. The method was successfully applied to the determination of cobalt(II) in pharmaceutical preparations.     

Electron correlation as the driving force for charge transfer: charge migration following ionization in N-methyl acetamide

A hole charge created in a molecule, for instance, by ionization, can migrate through the system solely driven by electron correlation. The migration of a hole charge following ionization in N-methyl acetamide (a molecular system containing a peptide bond) is investigated. The initial hole charge is localized at one specific site of the molecule. Ab initio calculations show that nearly 90% of the hole migrates to a remote site of the molecule in 4.2 fs. This migration of charge is highly efficient and ultrafast. The underlying mechanism for this migration of a hole charge is identified and compared with a simple model.     

Fluorometric assay of histamine in tissues and body fluids: Choice of the purification procedure and identification in the nanogram range

Summary Several procedures for the isolation of histamine from tissues and body fluids were examined. For the fluorometric assay of histamine concentrations higher than 1 g/g tissue or ml blood the extraction into n-butanol as well as the cation-exchange chromatography on Dowex 50W-X8 proved suitable. The determination of histamine in whole blood of dogs gave valid results only after chromatography on Dowex 50, in human plasma and gastric juice only after the combined application of both purification methods. Histamine was identified by thin-layer chromatography on cellulose, by inactivation in the presence of purified diamine oxidase from pig kidney and purified histamine methyltransferase from guinea-pig brain, by the biological activities and by the fluorescence spectra of the condensation product between histamine and o-phthaldialdehyde. Histamine concentrations in tissues and body fluids of man and some laboratory animals are reported.

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Fluorimetrische Bestimmung von Histamin in Geweben und Körperflüssigkeiten: Wahl eines geeigneten Reinigungsverfahrens und Identifizierung im ng-Bereich

Zusammenfassung Verschiedene Isolierungsverfahren für Histamin zur fluorimetrischen Bestimmung wurden geprüft. Für Histamingehalte von mehr als 1 g/g Gewebe oder Milliliter Vollblut eignet sich sowohl die Butanolextraktion als auch die Ionenaustausch-Chromatographie an Dowex 50W-X8, für Vollblut des Hundes nur das letztere Verfahren, für Plasma und Magensaft des Menschen nur die Kombination der beiden Isolierungsmethoden. Histamin wurde identifiziert durch Dünnschicht-Chromatographie auf Cellulose, Umsatz durch angereicherte Diaminoxydase und Histaminmethyltransferase, durch die Fluorescenzspektren nach Kondensation mit o-Phthaldialdehyd und durch seine biologische Aktivität. Die Histamingehalte in Geweben und Körperflüssigkeiten des Menschen und einiger Versuchstiere werden mitgeteilt.

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Members of SFB 37 (Restitution und Substitution innerer Organe of Deutsche Forschungsgemeinschaft).     

Uniaxial deformation and orientation of ethylene–tetrafluoroethylene films

This study concerns the thermal and mechanical response of several commercial grades of ethylene – tetrafluoroethylene copolymer films. Differential scanning calorimetry was used to show that, although films have similar degrees of crystallinity and melting temperature, the melting endotherms and crystallisation exotherms differ between materials, suggesting small changes in composition between manufacturers. Films were deformed in tension at a range of temperatures and rates. Selected films were unloaded immediately after stretching, and measurement of the elastic recovery highlighted further differences between materials. Batches of films were pre-drawn uniaxially above the glass transition and immediately quenched. When these materials were subsequently re-drawn below the glass transition temperature, most of them exhibited much improved yield stress, modulus and tensile strength (improving by factors of 5, 5 and 4, respectively at a draw ratio of 3), but a reduced strain to failure. In most of the films, the pre-drawing, as well as the initial orientation of the films, is accounted for by a simple shift in the true strain axis. This is indicative of a material response dominated by entropic network stretch. It also suggests that, in the cases where strain superposition does not work, a different arrangement of crystalline lamellae may be present, limiting the extent to which improved properties can be achieved in some materials.