Influence of ethanol oxidation rate on the lactate/pyruvate ratio and phosphorylation state of the liver in fed rats.

The effect of the ethanol oxidation rate on the interaction between the phosphorylation state (the [ATP]/[ADP] X [HPO4]2- ratio) and the redox state (the free [NAD+]/[NADH] ratio) of the liver cytosol was studied in intact fed rats. The rate of ethanol oxidation was inhibited to different degrees with pyrazole. The ethanol oxidation rate had no influence on the liver lactate level but correlated significantly with the pyruvate level. Accordingly, a significant correlation was also found between the ethanol oxidation rate and the lactate/pyruvate ratio. The rate of ethanol oxidation correlated significantly with the liver 3-phosphoglycerate level. No change in the glyceraldehyde-3-phosphate level was found. No correlation was found between the ethanol oxidation rate and the glyceraldehyde-3-phosphate/3-phosphoglycerate redox couple. Ethanol administration slightly increased the liver ATP level, but the simultaneous administration of pyrazole eliminated this effect. Other adenine nucleotides and HPO4 2- were not changed. The changes in the rate of ethanol oxidation had no effect on the phosphorylation state in the fed liver. It is assumed that in the fed liver the phosphorylation state is so well stabilized that the redox level has no influence.     

R?ntgenspektrometrische Elementbestimmung in Abwasser: Probenvorbereitung und Matrixkorrekturverfahren

Zusammenfassung Für Elementbestimmungen in Abwasser wird ein Röntgenfluorescenzverfahren beschrieben. Zur Probenvorbereitung werden die Elemente durch Gefriertrocknung auf einem inerten Träger angereichert. Diese Anreicherung ist nicht selektiv und erfaßt praktisch alle in Abwasser gelösten und suspendierten Verunreinigungen. Für die Berechnung der Elementkonzentrationen aus den gemessenen Fluorescenzintensitäten wird ein Matrixkorrekturverfahren angegeben, welches dem unterschiedlichen Absorptionsverhalten der Probenmatrix Rechnung trägt. Die Massenabsorptionskoeffizienten werden durch Messung der diffus gestreuten Bremsstrahlung bzw. der Comptonstreustrahlung ermittelt. Die Selbstabsorption des zu bestimmenden Elementes wird rechnerisch berücksichtigt. Das Korrekturverfahren kann auf alle mit Röntgenfluorescenzanalyse bestimmbaren Elemente angewendet werden.

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Determination of elements in waste water by x-ray fluorescence analysis: Sample preparation and matrix correction method

Summary For sample preparation the elements are enriched upon an inert carrier by freeze-drying. This enriching procedure is not selective and collects all dissolved and suspended contaminations from the waste water. In order to calculate the element concentrations from the measured fluorescence intensities a matrix correction method is given which considers the different absorption behaviour of the matrix. The mass absorption coefficients are obtained by measuring the scattered X-ray tube spectrum or a Compton scattered X-ray tube line, respectively. The self-absorption of the element to be determined is taken into account. The correction method is applicable to all elements detectable by X-ray fluorescence.

Herrn Dr. H. Wagner danken wir für das stete Interesse, die zahlreichen konstruktiven Diskussionen und die Hilfe beim Abfassen des Manuskripts.     

Mass spectrometric study of 4-azafluorenes

The dissociative ionization of 4-azafluorene and its methyl and phenyl derivatives was investigated. The relative intensity of the [M — CH₃]⁺ ion peak depends on the position of the CH₃ group in the 4-azafluorene ring. It was established that the loss of an RCN particle (R=H, CH₃, and C₆H₅) for unsubstituted 4-azafluorene takes place from the M⁺ and [M — H]⁺ ion, exclusively from the [M — H]⁺ ion for the methyl-substituted compounds, and from the [M — H]⁺ and [H — 2H]⁺ fragments for the phenyl-substituted derivatives. Randomization of the deuterium ions in the 9,9-d₂-4-azafluorene molecular ion was observed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 246–250, February, 1978.     

Zur Magnetochemie des zweiwertigen Silbers Neue Fluoroargentate(II): Cs2AgF4, Rb2AgF4 und K2AgF4

Magnetochemistry of Divalent Silver. New Fluoroargentates(II): Cs₂AgF₄, Rb₂AgF₄, and K₂AgF₄ Hitherto unknown blue compounds Rb₂AgF₄ and Cs₂AgF₄ are prepared. Guinier patterns show, that Cs₂AgF₄ cristallise in the K₂NiF₄ structure (a = 4.58₁, c = 14.19₂ Å). The structure of the Rb-compound is still unknown. The magnetic behaviour of K₂AgF₄, Rb₂AgF₄, and Cs₂AgF₄ is discussed.     

The kinetics of oxidation of selenosemicarbazide by oxygen in the presence of cupric ions

In acidic medium selenosemicarbazide undergoes oxidation by oxygen, dissolved in water, in the presence of copper(II) as a catalyst. The oxidation product exhibits an activating effect. The kinetics of the reaction have been investigated and the kinetic equations deduced both for small and high concentrations of the oxidation product. The constants involved in the kinetic equations deduced have been calculated. The proposed mechanism of the reaction agrees with the experimental results. The oxidation product is supposed to be the bis-selenosemicarbazidinium cation. The postulation of formation of this cation is based on the electronic structure and reactivity of selenosemicarbazide. The reaction can be used for copper determination.     

Reactions of copper acetylides. Structure of (π-C5H5)Ru(PPh3)2 (CCPh)CuCl,and new syntheses of transition metal cluster compounds

In contrast to a related iron—copper compound, the complex (π-C₅H₅)Ru(PPh₃)₂(C₂Ph)CuCl is shown to be monomeric, and contains linear dicoordinate copper(I); the reactions of this and similar complexes with metal carbonyls are sources of new mixed-metal clusters, such as (π-C₅H₅)Fe₂ Ru(C₂Ph)(CO)₆ (PPh₃).     

The thermodynamics of proton dissociation of adenine

The thermodynamic quantities associated with ionization of the N₁ and N₉ protons of adenine have been calorimetrically determined as a function of temperature. The H values for proton dissociation of these groups, with pK values of 4.19 and 9.92, were found to be 5.1 and 9.1 kcal/mole, respectively, at 25°C, =0.025. The C _p values for proton dissociation of these groups were estimated to be –11 and –17 cal/mole-deg. These results indicate that the large heat capacity changes observed during conformational transitions of polynucleotides are not the result of ionization of the bases.     

Variable electronegativity SCF-MO calculations on the electronic structure and spectra of some substituted benzenes I. Monosubstitutions

π-electron SCF-MO theory in its variable electronegativity formalism has been applied to some monosubstituted benzenes. Calculated charge densities and bond orders for the ground and the first excited electronic states are correlated with chemical reactivity and the changes in molecular geometry on electronic excitation. The calculated results for spectra are compared with those obtained using the PPP method and also with the available experimental data.     

Steroid Total Synthesis,Part II; (−)-17β-Hydroxy-des-A-androst-9-en-5-one

Based on the results obtained in the racemic series (part I), (—)-17β-hydroxy-des-A-androst-9-en-5-one has been synthesized, starting with (S)-(—)-5-heptanolide. The key step, viz. the condensation of (S)-(—)-7-hydroxy-1-nonen-3-one (or its amine adduct) with 2-methyl-cyclopentane-1, 3-dione involves an asymmetric induction. Model experiments with (R)-(+)-5-decanolide leading to the enantiomeric homolog of the BCD-tricyclic compound are also described.