The effect of low concentrations of a polyatomic gas in argon on erosion on copper cathodes in a magnetically rotated arc

Experimental results are presented for electrode erosion on copper cathodes in magnetically rotated arcs in argon, dry air, nitrogen, ammonia, and carbon monoxide as well mixtures of the above with argon. Water-saturated argon was also used. Erosion rates were determined by weight loss after chemical cleaning, and the runs were sufficiently long (between 5 to 60 min) to represent steady-state operation. Arc currents of 100 A and gas pressures of 1.1 atm. were used. Pure argon gave the highest erosion rates and the lowest arc velocities. Small concentrations of any of the diatomic gases in argon greatly increased the arc velocity and decreased the erosion rates. The results suggest that erosion is primarily a thermal phenomenon but that the surface chemistry can greatly influence erosion rates by modifying arc behavior.     

Equilibrium and structural characterization of ofloxacin–cyclodextrin complexation

The enantiomer-specific characterization of ofloxacin–cyclodextrin complexes was carried out by a set of complementary analytical techniques. The apparent stability constants of the ofloxacin enantiomers with 20 different cyclodextrins at two different pH values were determined to achieve good resolution capillary electrophoresis enantioseparation either to establish enantioselective drug analysis assay, or to interpret and design improved host–guest interactions at the molecular level. The cyclodextrins studied differed in the nature of substituents, degree of substitution (DS), charge and purity, allowing a systematic test of these properties on the complexation. The seven-membered beta-cyclodextrin and its derivatives were found to be the most suitable hosts. Highest stability and best enantioseparation were observed for the carboxymethylated-beta-cyclodextrin (DS ~ 3.5). The effect of substitution pattern (SP) was investigated by molecular modeling, verifying that SP greatly affects the complex stability. Induced circular dichroism was observed and found especially significant on carboxymethylated-beta-cyclodextrin. The complex stoichiometry and the geometry of the inclusion complexes were determined by ¹H NMR spectroscopy, including 2D ROESY techniques. Irrespective of the kind of cyclodextrin, the complexation ratio was found to be 1:1. The alfa-cyclodextrin cavity can accommodate the oxazine ring only, whereas the whole tricyclic moiety can enter the beta- and gamma-cyclodextrin cavities. These equilibrium and structural information offer molecular basis for improved drug formulation.     

Synthese stereoisomerer Pinanthromboxane und Evaluation der Verbindungen als Plättchenaggregationsinhibitoren

Synthesis of Stereisomeric Pinanthromboxane Derivatives and Evaluation of the Compounds as Platelet Aggregation Inhibitors Starting from the two enantiomeric myrtenols ((?)- 1 and (+)- 1 ; cf. Scheme 1), the synthesis of twelve stereoisomeric pinanthromboxane derivatives ((+)- and (?)- 10, -11, -14, -15, -21 and -22 ) is described (cf. Schemes 1–4). Biological data from the evaluation as platelet aggregation inhibitors (cf. Table 6 and 7), thromboxane synthetase inhibitors (cf. Table 8) and from the assessment as antagonists of leukotriene E₄ induced bronchoconstriction (cf. Table 9) are presented.     

Stabilization and Solubilization of Lipophilic Natural Colorants with Cyclodextrins

The paper provides data on the practical utilization of the benefits of the molecular encapsulation of natural colorants by cyclodextrins. Experimental results on the stability of cyclodextrin complexed curcumin, curcuma oleoresin, -carotene and carotenoid oleoresins against light-, heat- and oxygen prove the benefits of molecular encapsulation of colorants. The parent -cyclodextrin stabilized most effectively the curcumines, while the stability of carotenoids was most effectively achieved by -cyclodextrin complexation. Methylated -cyclodextrin was found to be the most potent solubilizing agent for both carotenoids and curcuminoids.     

Cathode erosion in inert gases: The importance of electrode contamination

Experimental results are presented for electrode erosion on copper electrodes in magnetically rotated arcs in argon and helium. Measurements were also made of the arc voltage and velocity. The effects due to the contamination of the electrode surface by either a native contaminant layer (copper oxide and carbon traces) or the continuous injection of very small amounts of various diatomic gases (nitrogen, oxygen, chlorine, and carbon monoxide) into the inert plasma gases were determined. The erosion rates for pure argon were significantly higher than those for pure helium (13.5 g/C for argon and 1 g/C for helium) and with both gases, very high arc velocities were measured initially (>60 m/s for argon and >160 m/s for helium) when a natural contaminant layer was still present on the cathode. The removal of this layer resulted in lower velocities (2m/s for argon and 20m/s for helium) and higher erosion rates. The removal of the layer was much faster with argon, due possibly to higher electrode surface current densities for argon arcs.     

Cyclodextrin knowledgebase a web-based service managing CD-ligand complexation data

Cyclodextrins are cyclic oligosaccharides that are able to form water-soluble inclusion complexes with small molecules. Because of their complexing ability, they are widely applied in food, pharmaceutical and chemical industries. In this paper we describe the development of a free web-service, Cyclodextrin KnowledgeBase: (http://www.cyclodextrin.net). The database contains four modules: the Publication, Interaction, Chirality and Analysis Modules. In the Publication Module, almost 50,000 publication details are collected that can be retrieved by text search. In the Interaction and Chirality Modules relevant literature data on cyclodextrin complexation and chiral recognition are collected that can be retrieved by both text and structural searches. Moreover, in the Analysis Module, the geometries of small molecule-cyclodextrin complexes can be predicted using molecular docking tools in order to explore the structures and interaction energies of the inclusion complexes. Complex geometry prediction is made possible by the built-in database of 95 cyclodextrin derivatives, where the 3D structures as well as the partial charges are calculated and stored for further utilization. The use of the database is demonstrated by several examples.     

Dimethyl ether oxidation at elevated temperatures (295-600 K)

Dimethyl ether (DME) has been proposed for use as an alternative fuel or additive in diesel engines and as a potential fuel in solid oxide fuel cells. The oxidation chemistry of DME is a key element in understanding its role in these applications. The reaction between methoxymethyl radicals and O(2) has been examined over the temperature range 295-600 K and at pressures of 20-200 Torr. This reaction has two product pathways. The first produces methoxymethyl peroxy radicals, while the second produces OH radicals and formaldehyde molecules. Real-time kinetic measurements are made by transient infrared spectroscopy to monitor the yield of three main products-formaldehyde, methyl formate, and formic acid-to determine the branching ratio for the CH(3)OCH(2) + O(2) reaction pathways. The temperature and pressure dependence of this reaction is described by a Lindemann and Arrhenius mechanism. The branching ratio is described by f = 1/(1 + A(T)[M]), where A(T) = (1.6(+2.4)(-1.0) x 10(-20)) exp((1800 +/- 400)/T) cm(3) molecule(-1). The temperature dependent rate constant of the methoxymethyl peroxy radical self-reaction is calculated from the kinetics of the formaldehyde and methyl formate product yields, k(4) = (3.0 +/- 2.1) x 10(-13) exp((700 +/- 250)/T) cm(3) molecule(-1) s(-1). The experimental and kinetics modeling results support a strong preference for the thermal decomposition of alkoxy radicals versus their reaction with O(2) under our laboratory conditions. These characteristics of DME oxidation with respect to temperature and pressure might provide insight into optimizing solid oxide fuel cell operating conditions with DME in the presence of O(2) to maximize power outputs.     

Enhanced structure determination of beta-pyrrole and N-substituted porphyrins by desorption chemical ionization mass spectrometry.

The extensive macrocycle—but minimal substituent—fragmentation occurring in the chemical ionization mass spectra of porphyrins when ammonia, rather than hydrogen, is the reagent gas leads to more detailed structure determinations.