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Sulfhydryl Groups, Methylmercury Containing Inactivator, Coenzyme Analogue Nicotinamide-(S-methylmercury-thioinosine) dinucleotide was formed by reaction of nicotin amide-(6-thiopurine) dinucleotide with methylmercury chloride. The compound exhibits coenzyme properties in the test with LDH (Km=1.5 × 10-4 м , Vmax=12500) and LADH (Km=1.7 × 10-4 м, Vmax=27) and inactivates YADH and GAPDH. From incubations with LDH and LADH the mercury containing coenzyme could be regained by column chromatography. The compound seems to be qualified for the X-ray structure analysis of the coenzyme-enzyme complex for some dehyrogenases based on the proportion of the heavy metal.
Photoelectron (PE) spectra of ethylene and vinylene carbonates and thiocarbonates as well as of methylene trithiocarbonate and some open-chain derivatives are reported.
The low energy bands, well separated in the unsaturated compounds, are assigned to lone pair and π type ionizations. The assignment is based on comparison of PE spectra, modified CNDO calculations, and sulfur Κβ emission spectra. The pronounced substituent effects due to which the first ionization potential varies from 8.4 eV to 11.1 eV are discussed.
Die mit dieser Arbeit einsetzende Rezeption der Rezeptionsgeschichte und Rezeptionsästhetik in der Literaturwissenschaft war – wie es scheint – durch folgende Erwartungen bestimmt:
1. Sie versprach, die "Kluft zwischen der historischen und der ästhetischen Betrachtung" zu schließen, formalistische und historisch-soziologische Betrachtungsweisen in ihrer Einseitigkeit zu überwinden und zu versöhnen und beiläufig die marxistische Literaturwissenschaft in die Wissenschaftspraxis zu integrieren.
2. Sie versprach, die Legitimationsfrage der Literaturwissenschaft zu lösen, indem die rezeptionsästhetische Methode die Literaturwissenschaftler in die Lage versetzen sollte, an der "Totalisierung des Vergangenen", will sagen an der Wiederaneignung von Werken der Vergangenheit und der Vermittlung vergangener Kunst und gegenwärtiger Kunsterfahrung teilzunehmen. Sie beanspruchte, für eine bewußt angestrebte neue Kanonbildung Kriterien bereitzustellen und damit die hoffnungslosen Aporien zu heilen, in welche der Historismus alle normativen Anstrengungen der Literaturwissenschaft gebracht hatte.
3. Sie stellte die Möglichkeit in Aussicht, die Wissenschaftsgeschichte insbesondere der Germanistik ohne allzu heftige Erschütterung zu beschreiben, indem sie erlaubte, in den literaturwissenschaftlichen Hervorbringungen der Vergangenheit ebenfalls die "sukzessive Entfaltung eines im Werk angelegten, in seinen historischen Rezeptionsstufen aktualisierten Sinnpotentials" zu sehen, ohne deswegen in den Verdacht zu kommen, einem Einrücken in diese Tradition oder einem Verzicht auf Kritik das Wort zu reden.
4. Schließlich erlaubten die vorgetragenen methodischen und theoretischen VorschIage durchaus unterschiedliche Folgerungen, vor allem aber eine Fülle von praktikablen neuen Projekten und Themenstellungen bei prinzipiell gleichbleibender Struktur der Lehr- und Forschungspraxis. Es zeigte sich, daß überall keineswegs voraussetzungslos begonnen werden mußte, daß insbesondere bei den von Jauß vorgeschlagenen Methoden der synchronen und diachronen Querschnittsanalysen, bei der Rekonstruktion von "Erwartungshorizonten" aus den Texten selbst und aus den Traditionen, in denen sie stehen, und auch bei der Rekonstruktion der "ereignishaften Geschichte der Literatur", in welcher sich Rezeption durch Kritiker und Autoren als Fundament neuer Produktionen darstellt, auf das ganze reiche Arsenal der eingeubten positivistischen Arbeitsweise der Gattungs-, Motiv- und Einflußgeschichte u. a. m. zurückgegriffen werden konnte.
The low temperature IR stretching vibrations of difluorodisulfane (FSSF) and thiothionylfluoride (SSF2), in the solid phase and in a cyclohexane matrix, of the mixtures FSSF -SSF2, FSSF-OSF2 and SSF, -OSF2, and of solid difluorotrisulfane (FS3F) have been investigated. While SSF, forms no distinct oligomers, a dimer with absorption bands at 635 and 682 cm-1 has been detected in the case of FSSF. These differences between FSSF and SSF, are rationalized by the different S-F bond lengths. A structure of the FSSF dimer similar to that of the sulfur tetrafluoride dimer is proposed. The low temperature spectrum of FS3F shows 3 bands in the frequency range between 460 and 1000 cm-1: 590, 605 and 680 cm-1, due to associated molecules. FS3F decomposes on warming. The main decomposition products containing fluorine are FSSF and SSF2. Mechanisms for the rearrangement and decomposition of the three compounds studied are discussed.
The mass spectra and the ion molecule reactions of methylphosphine, dimethylphosphine and dimethyldeuterophosphine have been studied by ion cyclotron resonance spectrometry. About 50 ion molecule reaction are observed for each compound. The product ions can be classified as ions with two phosphorus atoms: P2R5+, P2R3+, P2R2+ and P2R+ (R = CH3 or H), as phosphonium and phosphinium ions and ions resulting from collision dissociations and charge exchange reactions. Tertiary ions with three phosphorus atoms like CH3P3H2+ (from CH3PH2) and (CH3)4P3H2 (from (CH3)2PH) have also been detected. The mechanisms of the ion molecule reactions, rearrangements, P -H- and C-H-reactivities and product ion structures are discussed, using in the case of dimethylphosphine the results obtained with the deuterated compound. Rate constants of formation of the more abundant product ions from the molecular ion and the CH3P+ ion, both odd electron particles, have been determined. The reactions with dimethylphosphine have much smaller rate constants than the reactions with methylphosphine.
The rates of formation of three mono- and three dicarbenium ions of the triphenylmethyl type from the corresponding carbinols in trifluoro acetic acid - toluene mixtures were investigated using stopped flow techniques.
The reaction mechanisms are discussed in view of the obtained dependencies of the rate constants on acid concentration and temperature.
A model for the quantum yield of the coloration caused by UV-light in spiropyran layers is described. This model allows to calculate the sensitivity of layers having different compositions. The mechanism concerning the stability of the coloration is essentially clarified. Calculations of the stability for layers of different compositions are possible by a model describing the mechanism approximately.
Spectrophotometric investigation of the kinetics of the spontaneous reduction of the central metal ion in K2[Mn (IV)-2-α-hydroxyethyl-isochlorine e4] acetate in aqueous alkaline solution in the absence of any reducing agent reveals that it is a pseudo-first order reaction which is specifically hydroxide ion catalyzed. The pKα-value of the acid-base equilibrium has been estimated to be 14.4.
Electron transfer to the central metal ion is the rate limiting step. The measurements of its temperature dependence yields an activation enthalpy of ∆H‡ = 12 kcal/mol and an entropy of activation ∆S‡ = - 30 e.u. thus indicating that the electron transfer step is a bimolecular reaction. The most likely reactant is water. The reduction reaction does not take place with appreciable reaction rates at physiological pH. Thus, when bound to a suitable ligand of the chlorin type, Mn (IV)-compounds are sufficiently stable with respect to autoxidation to play some role in biological redox reactions as postulated recently for the photoreactivation process of the water splitting system in photosynthesis.