Kreislagerungen auf Flächen konstanter Krümmung

Ohne Zusammenfassung Vorgelegt von L. Fejes Tóth     

Enzyme stabilizer DTT catalyzes nitrilase analogue hydrolysis of nitriles

Amides are the dominating products in some nitrilase catalyzed conversions of alpha-activated nitriles, but unexpectedly this hydrolytic reaction is also catalyzed by 1,4-dithio-dl-threitol (DTT), a standard antioxidizing enzyme stabilizer.     

On the Green Function and Poisson Integrals of the Dunkl Laplacian

We prove the existence and study properties of the Green function of the unit ball for the Dunkl Laplacian △ _k in \(\mathbb {R}^{d}\). As applications we derive the Poisson-Jensen formula for △ _k -subharmonic functions and Hardy-Stein identities for the Poisson integrals of △ _k . We also obtain sharp estimates of the Newton potential kernel, Green function and Poisson kernel in the rank one case in \(\mathbb {R}^{d}\). These estimates contrast sharply with the well-known results in the potential theory of the classical Laplacian.     

Ab initio pseudopotential study of vacancies and self-interstitials in hcp titanium

By means of an ab initio plane-wave pseudopotential method, monovacancy, divacancy and self-interstitials in hcp titanium are investigated. The calculated monovacancy formation energy is 1.97 eV, which is in excellent agreement with other theoretical calculations, and agrees qualitatively with published experimental results. The relaxation of the atoms around a single vacancy is observed to be small. Two divacancy configurations, the in-plane and the off-plane, have also been shown to be equally stable. With regards to the interstitials, of the eight configurations studied, two (octahedral and basal octahedral) have relatively lower formation energies and are, thus, the most likely stable configurations. We find small energy differences between them, suggesting their possible co-existence. It is also observed that the tetrahedral configuration decays to a split dumbbell configuration, whereas both the basal tetrahedral and the basal pseudocrowdion interstitials decay to the basal octahedral configuration. Using the nudged elastic band method (NEB), we determine a possible minimum energy path (MEP) for the diffusion of self-interstitial titanium atoms from an octahedral site to the nearest octahedral site. The energy barrier for this migration mechanism is shown to be about 0.20 eV.     

Influence of Test Specimen Geometry and Water Soaking on the In Vitro Cytotoxicity of Orthocryl®, Orthocryl® LC,Loctite® EA 9483 and Polypropylene

Depending on their composition, plastics have a cytotoxic potential that needs to be evaluated before they are used in dentistry, e.g., as orthodontic removable appliances. Relevant guidelines set out requirements that a potential new resin in the medical field must meet, with a wide scope for experimental design. In the present study, test specimens of different geometries consisting of varying polymers (Orthocryl^®, Orthocryl^® LC, Loctite^® EA 9483, Polypropylene) were soaked for different periods of time, then transferred to cell culture medium for 24 h, which was subsequently used for 24-h cultivation of A549 cells, followed by cytotoxicity assays (WST-1, Annexin V-FITC-propidium iodide (PI) flow cytometry). In this context, a reduction in the cytotoxic effect of the eluates of test specimens prepared from Orthocryl^® LC and Loctite^® EA 9483 was particularly evident in the Annexin V-FITC-PI assay when the soaking time was extended to 48 h and 168 h, respectively. Consistent with this, a reduced release of potentially toxic monomers into the cell culture medium, as measured by gas chromatography-mass spectrometry, was observed when the prior soaking time of test specimens of all geometries was extended. Remarkably, a significant increase in cytotoxic effect was observed in the WST-1 assay, which was accompanied by a higher release of monomers when the thickness of the test sample was increased from 0.5 to 1.0 mm, although an elution volume adapted to the surface area was used. However, further increasing the thickness to 3.0 mm did not lead to an increase in the observed cytotoxicity or monomer release. Test specimens made of polypropylene showed no toxicity under all test specimen sizes and soaking time conditions. Overall, it is recommended to perform toxicity studies of test specimens using different geometries and soaking times. Thereby, the influence of the different specimen thicknesses should also be considered. Finally, an extension of the test protocols proposed in ISO 10993-5:2009 should be considered, e.g., by flow cytometry or monomer analysis as well as fixed soaking times.     

The use of APPLE II microcomputer as kinetic laboratory data acquisition system

A laboratory microcomputer system based on an APPLE II microcomputer is presented. Data transfer from a temperature jump equipment or a stopped flow apparatus can be performed via a serial interface, the data can be stored on a memory expansion card or on the disk drives. Data transfer to a central host computer can also be done. Application of the laboratory data system on kinetic and spectroscopic measurements are shown.Dedicated to Prof. Dr.K. L. Komarek on the occasion of his 60th birthday.     

Zur Reaktion von Derivaten des Thiosemicarbazids mit Bisimidchloriden der Oxalsäure

Summary Arylsubstituted oxalic bis-imidochlorides1 react with thiosemicarbazones of type5 as well as13 to give five-membered-ring heterocycles8,11, and16.¹³C-NMR spectroscopy, chemical methods and X-ray crystallography have been used to investigate the nature of the structures obtained. The¹³C-chemical shifts of13 and imidazolidines16 are correlated with Hammett _p constants and dual substituent parameters to evaluate the transmission of theX substitutent electronic effects via the side-chain iminyl carbon atom into the heterocyclic ring and its neighbouring phenyl groups.

     

Zur Ringumwandlung von 2-Amino-thiophen-3-carbonsäureestern: Pyridon- und Pyridazinon-Derivate

Whereas treatment of the ethyl 5-acetyl-2-amino-4-methyl-thiophene-3-carboxylate (1) with potassium hydroxide yields the 2-hydroxy-thiophene-3-carbonitrile4 its hydrazone2 is converted into the 1-amino-5-mercapto-2-pyridone derivative6. The transformation of the 2-amino-5-phenylazo-thiophene derivative9 by potassium hydroxide yields the substituted 3-mercapto-pyridazin-6(1H)one10, with sodium ethoxide the 5-phenylhydrazono-2-oxo-thiolen-3-carbonitrile11 is formed. From6 the 5-mercapto-2-pyridone derivatives7 d,e can be obtained.

     

Polarographic study of xylenol orange

In neutral medium the ring carbonyl group of xylenol orange is reduced in two one-electronsteps at a dropping mercury electrode. Step I is nearly reversible, but step II strongly irreversible. The half-wave potentials of both steps depend on pH, for the products of reduction, the dye radical formed in step I and the OH group produced in step II, behave as acids. From the E_1/2 vs. pH dependence, the pK of the dye radical is found to be 9.5, that of the hydroxy compound 5.6. On progressive acidification the height of step II continuously decreases, while that of step I increases. In solutions with pH<2, only a single (according to logarithmic analysis) one-electron, but overall (according to coulometry) two-electron step results. The ratio i^I/i^II for the two steps increases when larger amounts of alkali metal ions are added. The exaltation of the first wave at the expense of wave II is explained by an acid-dependent dismutation of the dye radical formed during the first one-electron step.