Farbeffekte in oxidischen and anderen Mn2+-Verbindungen – die Ligandenfeldspektren von MgO/MnO- und CaO/MnO-Mischkristallen sowie von MnAl2O4

Colour Effects in Oxidic and Other Mn²⁺ Compounds – the Ligand Field Spectra of Mixed Crystals MgO/MnO, CaO/MnO, and of MnAl₂O₄ The colour intensity and the shift of the hue is examined for mixed crystals Mg_1?xMn_x^IIO and Mn_1?y^IICa_yO in dependence of the Mn²⁺-concentration and interpreted in terms of Mn²⁺? Mn²⁺ pair interactions and variations of the Mn? O bond length, respectively. The experimental band positions (sextet-quartet transitions) could be fitted quantitatively – also in case of Mn²⁺ in tetrahedral (MnAl₂O₄) and dodecahedral oxygen coordination (Mn₃Al₂Ge₃O₁₂, MnY₂Mg₂Ge₃O₁₂) – by means of crystal field calculations. The obtained ligand field parameters are discussed in comparison with data for octahedral Mn²⁺ ions with H₂O, F^? and Cl^? as ligands.     

Isochorismate pyruvate lyase: a pericyclic reaction mechanism?

Isochorismate pyruvate lyase (IPL) catalyzes the cleavage of isochorismate to give salicylate and pyruvate, a key step in bacterial siderophore biosynthesis. We investigated the enzyme from Pseudomonas aeruginosa using isochorismate selectively deuterated at C2 as a substrate. Monitoring the reaction by 2H NMR spectroscopy revealed that the label is quantitatively transferred from C2 to C9, producing stoichiometric amounts of [3-2H]pyruvate as product. Moreover, the deuterium kinetic isotope effect of 2.34 +/- 0.08 on kcat indicates that C-H cleavage is significantly rate limiting. Consistent with these data, hybrid density functional theory (HDFT) calculations at the Becke3LYP/DZ+(2d,p) level of theory predict a concerted but highly asynchronous pericyclic transition structure, in which carbon-oxygen bond cleavage is more advanced than hydrogen atom transfer from C2 to C9; the calculated 2H isotope effect of 2.22 at C2 is in excellent accord with the experimental value. Together, these findings indicate that IPL should be added to the small set of proteins that are known to catalyze pericyclic reactions. They also raise the possibility that enzymes, such as chorismate pyruvate lyase, salicylate synthase, 4-amino-4-deoxychorismate lyase, and anthranilate synthase, which accelerate formally similar reaction steps, may also exploit pericyclic mechanisms.     

Abstract functions with continuous differences and Namioka spaces

Let be a semigroup and a topological space. Let be an Abelian topological group. The right differences of a function are defined by for . Let be continuous at the identity of for all in a neighbourhood of . We give conditions on or range under which is continuous for any topological space . We also seek conditions on under which we conclude that is continuous at for arbitrary . This led us to introduce new classes of semigroups containing all complete metric and locally countably compact quasitopological groups. In this paper we study these classes and explore their relation with Namioka spaces.

     

Synthese von endo- und exo-1,3-Dimethyl-2,9-dioxa-bicyclo[3.3.1]nonan

Synthesis of endo- and exo-1,3-dimethyl-2,9-dioxabicyclo[3.3.1]nonane The synthesis of a host-specific substance in norway spruce infested by Trypodendron lineatum OLIV . is described (cf. scheme 1 and 2). Alkylation of the acetyl-acetone di-anion (II) with 3-methyl-3-buten-1-yl-bromide (I) followed by sodium boro-hydride reduction yields erythro- and threo-8-methyl-8-nonen-2,4-diol (IV and V) which are separated by chromatography. Their configurations were established by converting them under equilibrium conditions into one (VI) or two (VII and VIII) benzal derivatives. Oxidative cleavage with ozone of the terminal double bond in the erythro diol IV produces a dihydroxy ketone IX which spontaneously cyclizes to endo-1,3-dimethyl-2,9-dioxa-bicyclo[3.3.1]nonane (X). The threo diol V is converted by the same reaction sequence exclusively into exo-1,3-dimethyl-2,9-dioxa-bicyclo-[3.3.1]nonane (XII). Comparison of the NMR. data of the two acetals X and XII with that of the natural product establishes the endo configuration of the latter. A second, more convenient, synthesis of a mixture of the acetals X and XII starting from the bromo-acetal XIII is also reported.     

Ethylenically unsaturated polycarbosiloxanes for novel silicone hydrogels: synthesis,end‐group analysis,contact lens formulations,and structure–property correlations

A series of novel mono‐ethylenically unsaturated polycarbosiloxanes macromonomers as compatibilizer materials for soft silicon hydrogels were prepared from the anionic ring‐opening polymerization (AROP) of 2,2,5,5‐tetramethyl‐2,5‐disila‐1‐oxacyclopentane followed by methacrylation. The characterization was performed by end‐group analysis and included the determination of molecular weight, molecular weight distributions, end‐group functionality, and impurity profiles using gas chromatography‐mass spectrometry, gel permeation chromatography, nuclear magnetic resonance, and matrix‐assisted laser desorption/ionization time of flight mass spectrometry. The synthetic procedure was optimized to minimize the formation of any dimer that would have the potential to act as a low molecular weight cross linker. In addition, the novel di‐ethylenically unsaturated polycarbosiloxanes were synthesized by cationic polymerization. Use of these silicone derivatives was explored in the formulation of contact lenses, and the structure–property relationship was examined. When copoymerized with hydrophilic monomers, these were able to give transparent and wettable films with desired properties, particularly a low moduli for contact lenses. Contact lens with high modulus is often shown to impart a higher degree discomfort when worn upon the eye. It was clear from the structure–property relationship that the modulus and the tensile strength of the formulated material depend on the nature and length of the polycarbosiloxane used and may be tuned for the purpose as needed. Copyright © 2013 John Wiley & Sons, Ltd.     

Messung der Neutronenpolarisation bei der Reaktion12C(d,n 0)13N mit Hilfe der Mott-Schwinger-Streuung

The polarization of neutrons produced in the reaction¹²C(d, n ⁰)¹³N was measured. Deuterons from the Karlsruhe isochronous cyclotron were used to induce this reaction at 51,5 MeV laboratory energy. The degree of polarization was determined by using the special features of Mott-Schwinger scattering. With an uranium scatterer analysing efficiencies of up to 0.92 can be obtained at very small angles (0.23°). The analysing efficiency can be calculated if the differential cross section at 0° and the total cross section is known. These quantities were experimentally determined. The differential cross section for 49.4 MeV neutrons, scattered by uranium, was measured between 0.88° and 2.10°. By an extrapolation the value 43.4±2.6 b/sr was found for the nuclear differential cross section at zero degree. A total cross section ofσ _t=4.80±0.22 b was obtained. The neutron polarization was measured at a reaction angle of 24.5° and the result isP=?0.45±0.07. This value is fairly above the semiclassical 1/3 limit and can be only explained, if spin orbit forces are taken into account. For (d, n) reactions this is the first neutron-polarization measurement above an energy of 20 MeV.     

Aufschlu?verfahren zur Analyse der Alkylphenolkomponente in Alkylphenolpolyglykol?thern

Zusammenfassung Um die Polyglykolkette in oxalkylierten Alkylphenolen abzuspalten, werden diese in schmelzendem Kaliumhydroxid aufgeschlossen. Der Aufschluß entfernt die Polyglykolkette quantitativ, ohne die Alkylkette der Alkylphenole zu verändern. Die Alkylphenole werden isoliert und können nun mit den üblichen chromatographischen Methoden aufgetrennt werden. Ihre Strukturen lassen sich mit Hilfe von IR-, UV- und NMR-Spektren aufklären. Die Diskussion über die Spektren von Umsetzungsprodukten aus Butylphenol und Äthylenoxid sowie Propylenoxid belegt die Notwendigkeit einer solchen Abbaumethode.Herrn Prof. Dr. Werner Schultheis zum 70. Geburtstag gewidmet.     

Quenching problems in inorganic luminescent materials

Quenching problems were investigated on inorganic luminescent materials for fluorescent lamps. It could be shown that the decrease of luminescence intensity under the influence of short-wave UV radiation is not only a function of the irradiation time but also depends strongly on the activator concentration and a mechanical treatment. The photochemical luminescence quenching represented by the intensity loss as a function of the irradiation time can be expressed as a sum of three exponential terms, constants and exponents of which contain the concentration of virgin and UV induced lattice defects in both the bulk and the surface. To explain the complex quenching process the theory of radiationless energy transport was used.