27 research outputs found

    Efficiency Development in the German Pharmaceutical Market

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    Changes in Germany legislation since 2009 significantly limited the operation of German pharmacies. Since then, there has been a steady decline in the total number of pharmacies. This article deals with the efficiency change within the German retail and wholesale pharmaceutical sectors in the years 2009 to 2016. The efficiency calculation was based on the nonparametric data envelopment analysis method and the Malmquist index was used to evaluate changes. Two components of Malmquist index were also monitored separately, capturing changes in the area of technical efficiency and changes in the area of the production possibility set. The results point to the increasing efficiency which means that decreasing number of pharmacies is caused by concentration tendencies rather than by negative effects of government decisions.O

    Zur Gestaltung von orthographiedidaktischen Interventionstätigkeiten

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    Für die tertiäre Bildungsforschung ist das Thema Transfer von Wissenschaft in die Praxis – und zurück – ein grundlegendes. Zu spezifizieren ist dabei jedoch, um welche Art von Praxis es sich handelt, welches Begriffsverständnis dem Transfer unterliegt und unter welchen Bedingungen, Zielvorstellungen und Erfolgskriterien Transfer betrachtet wird. Dieser Band vereinigt verschiedene Beiträge zur Beschreibung von Gelingensbedingungen, Modellen und Nachhaltigkeit von Transfer im Bildungsbereich. Forscherinnen und Forscher aus Hochschuldidaktik, Lehreraus- und -weiterbildung und Schulentwicklung blicken jeweils aus ihren unterschiedlichen Perspektiven gemeinsam auf das Thema. Die Beiträge entstammen einer fachübergreifenden Tagung für Nachwuchswissenschaftlerinnen und -wissenschaftler zum Thema Praxistransfer in der tertiären Bildungsforschung an der Universität Hamburg im November 2017

    [3+2] cycloadditions of aziridines mechanistical studies

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    Gaebert C, Mattay J. [3+2] cycloadditions of aziridines mechanistical studies. JOURNAL OF INFORMATION RECORDING. 1996;23(1-2):3-6.The reaction of 1-butyl-2-phenyl aziridine with dimethyl acetylenedicarboxylate under PET conditions yields four products, two isomeric pyrrolidines and the corresponding pyrroles as oxidation products from the pyrrolidines. The reaction of the aziridine with dimethyl maleate and dimethyl fumarate respectively under PET conditions yields pyrroles with retained stereochemistry of the dipolarophiles. The addition of acrylonitrile to 1-butyl-trans-2,3-diphenyl aziridine under PET conditions leads to all four possible isomeric pyrrolidines whereas under direct photolysis only two pyrrolidines are formed. Based on these experimental data the mechanism involving a radical cation will be discussed

    [3+2] cycloadditions and nucleophilic additions of aziridines under C-C and C-N bond cleavage

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    Gaebert C, Mattay J. [3+2] cycloadditions and nucleophilic additions of aziridines under C-C and C-N bond cleavage. Tetrahedron. 1997;53(42):14297-14316.Under PET conditions (photoinduced electron transfer) aziridines react with dipolarophiles in a [3+2] cycloaddition to form five-membered heterocycles. In this study we, used mono- and disubstituted N-alkyl and N-arylaziridines. We noticed that the radical cation as intermediate reacts in a different manner to the classical azomethine ylide. Furthermore, under mild thermal conditions, aziridines react in acetonitrile in a formal [3+2] cycloaddition with activated acetylene derivatives under C-N bond cleavage. Using methanol as solvent, the intermediate is trapped leading to highly substituted enamines. A mechanism for this unexpected thermal reaction is proposed. (C) 1997 Elsevier Science Ltd

    Laser flash photolysis of some phenylaziridines

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    Siegner C, Gaebert C, Mattay J, Steenken S. Laser flash photolysis of some phenylaziridines. JOURNAL OF INFORMATION RECORDING. 1998;24(3-4):253-256.Laser flash photolysis (lambda(exc) = 248 nm) of the aziridines (E)-1-butyl-2,3-diphenylaziridine 1, (E)-2,3-diphenylaziridine 2, 1,2-diphenylaziridine 3 and 1-(p-methoxyphenyl)-2-phenylaziridine 4 were performed in acetonitrile. The reactive intermediates were identified as the corresponding azomethine ylides and spectroscopically and kinetically characterized

    Radical cations of phenyl-substituted aziridines: what are the conditions for ring opening?

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    Gaebert C, Mattay J, Toubartz M, Steenken S, Muller B, Bally T. Radical cations of phenyl-substituted aziridines: what are the conditions for ring opening? CHEMISTRY-A EUROPEAN JOURNAL. 2005;11(4):1294-1304.Radical cations were generated from different phenyl-substituted aziridines by pulse radiolysis in aqueous solution containing T1OH(.+), N-3(.) or SO4.- as oxidants or in n-butyl chloride, by Co-60 gamma radiolysis in Freon matrices at 77 K, and in some cases by flash photolysis in aqueous solution. Depending on the substitution pattern of the aziridines, two different types of radical cations are formed: if the N atom carries a phenyl ring, the aziridine appears to retain its structure after oxidation and the resulting radical cation shows an intense band at 440-480 nm, similar to that of the radical cation of dimethylaniline. Conversely, if the N atom carries an alkyl substituent while a phenyl ring is attached to a C-atom of the aziridine, oxidation results in spontaneous ring opening to yield azomethine ylide radical cations which have broad absorptions in the 500-800 nm range. In aqueous solution the two types of radical cations are quenched by O-2 with different rates, whereas in n-butyl chloride, the ring-closed aziridine radical cations are not quenchable by O-2. The results of quantum chemical calculations confirm the assignment of these species and allow to rationalize the different effects that phenyl rings have if they are attached in different positions of aziridines. In the pulse radiolysis experiments in aqueous solution, the primary oxidants can also be observed, whereas in n-butyl chloride a transient at 325 nm remains unidentified. In the laser flash experiments, both types of radical cations were also observed

    Laser flash photolysis of aziridines. Spectroscopic and kinetic characterization of azomethine ylides. Their [3+2] cyclization with alkenes and protonation by water-alcohols to yield iminium ions

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    Gaebert C, Siegner C, Mattay J, Toubartz M, Steenken S. Laser flash photolysis of aziridines. Spectroscopic and kinetic characterization of azomethine ylides. Their [3+2] cyclization with alkenes and protonation by water-alcohols to yield iminium ions. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2. 1998;(12):2735-2740.The reactive intermediates generated by laser flash photolysis (lambda(exc) = 248 or 193 nm) of the aziridines (E)-1-butyl-2,3-diphenylaziridine 1, (E)-2,3-diphenylaziridine 2, 1,2-dliphenylaziridine 3, 1-(p-methoxyphenyl)-2-phenylaziridine 4 and 1-butyl-2-phenylaziridine 5 in acetonitrile and alcohols as solvents were identified as the corresponding azomethine ylides and spectroscopically and kinetically characterized. The rate constants for the [3 + 2] reaction of the ylides with electron-deficient alkenes to give pyrrolidines are between 10(6) and 10(9) M-1 s(-1). In the case of 1 and 2 iminium ions are produced by protonation (by H2O or ROH) of the ylides (also studied by time-resolved conductance). For this reaction, with MeOH as the proton donor, the kinetic isotope effect is k(MeO-H)/k(MeO-D) = 5-7, from which it is concluded that the transition state for protonation of the carbanionic site of the ylide is linear

    Formation of radical cations of aziridines generated by laser ash photolysis

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    Gaebert C, Siegner C, Mattay J, Toubartz M, Steenken S. Formation of radical cations of aziridines generated by laser ash photolysis. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES. 2004;3(11-12):990-991.The radical cations of 1-butyl-trans-2,3-diphenyl aziridine (1), 1-butyl-2-phenyl aziridine (2), 1,2-diphenyl aziridine (3) and 1-(p-methoxyphenyl)-2-phenyl aziridine (4) were generated upon laser flash photolysis in aqueous and aqueous acetonitrile solutions by direct photoionisation as indicated by the broad absorption band of the solvated electron above 550 nm as well
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