Reaction of acetylenes with transition metals: VIII. π-allylpalladium complexes from acetylenes and alkenes

Coupling of diarylacetylenes with alkenes in the presence of dichlorobis(benzonitrile)palladium gives chloro(syn-1-chloro-anti-1-aryl-syn-3-alkyl)-π-allylpalladium complexes.     

1,2,3-Thiadiazole derivatives with a nearly linear N-S…O grouping. X-ray crystal structure analysis of four methylated products of 4-phenyl-1,2,3-thiadiazole-5-carbaldoxime

The title oxime 6 was methylated under different conditions and yielded four monomethylated products 7-10 and two bismethylated products 11 and 12 which were easily distinguished by their ¹³C nmr spectra. In view of the potential thiapentalene character of 8, 9, 10 and 11 , their X-ray crystal structures were determined. The structural properties of the nitroso compound 9 are in accordance with a thiapentalene structure, whereas those of the other compounds deviate in the order 10 < 11 < < 8 .     

Inorganic-organic interpenetrating frameworks: 4,4'-bipyridine N,N'-dioxide as a bridging hydrogen-bond acceptor

4,4'-Bipyridine N,N'-dioxide (L) acts as a hydrogen-bond acceptor in the compounds ([M(NO3)2(H2O)4].L2) (M = Co, Ni) to form doubly-interpenetrated framework materials with sixfold topological connectivity.     

High-performance thin-layer chromatography assay for epoxide hydrolase activity and the determination of phenoxypropane-1,2-diols

A simple, rapid and sensitive high-performance thin-layer chromatographic assay for the determination of epoxide hydrolase activity in rat liver homogenates is described. It is extended to the determination of a series of phenoxypropane-1,2-diols. The hydrolase assay has the advantages of using a readily available substrate, 2,3-epoxypropyl 4-methoxyphenyl ether, of multiple sample application, and of the simultaneous determination of reaction product (diol) as well as unchanged substrate (epoxide). The use of an internal standard, 4-nitroanisole, results in high sensitivity and good reproducibility of the proposed method. The limit of diol detection is 20 pmol.     

Application of high-field NMR and cryogenic probe technologies in the structural elucidation of poecillastrin a,a new antitumor macrolide lactam from the sponge poecillastra species

Poecillastrin A (1), a new polyketide-derived macrolide lactam, was isolated from a deep-water collection of the marine sponge Poecillastra species. The structure of poecillastrin A (1) was assigned using NMR data acquired at 500 MHz with an inverse-detection cryogenic probe and at 800 MHz with a room-temperature probe.     

Temperature measurements by H2-CARS in the reactive zone of a plasma test reactor for hydrocarbon synthesis

The application of coherent anti-Stokes Raman spectroscopy (CARS) to an electric are test reactor is described in which acetylene synthesis in analogy to the large-scale industrial process is .studied. We report on spatially resolved measurements of H₂-CARS spectra, the comparison with calculated spectra, and the determination of temperatures in the reaction zone.Dedicated to Prof. Rudolf Wienecke on the occasion of his 65 birthday.     

Characterisation of Sugar Cane Combustion Particles in the Araraquara Region, Southeast Brazil

Biomass burning is an important primary and secondary source of aerosol particles. The presence of carbonaceous particles in the respirable size range makes the study of this fraction important in view of possible health and climatic effects. The annual burning of sugar cane plantations causes emission of huge amounts of pyrogenic particles. Aerosol samples were collected in Araraquara city, São Paulo state, Brazil, during the harvest season for fine and coarse particles and bulk; they were analysed by electron-probe microanalysis, including facilities for low-Z element determination (low-Z EPMA) and by energy-dispersive X-ray fluorescence (EDXRF), in order to investigate the elemental composition of individual particles and bulk samples, respectively. Numerical analysis of the EPMA results by hierarchical clustering shows high contributions of carbonaceous particles that can be distinguished mainly in two different types: biogenic and carbon-rich. Additionally, two significant contributions of aluminosilicate particles were identified: as rather pure aluminosilicates or mixed with carbonaceous species. The EDXRF results are compatible with those of aerosol particles in Amazon, which is nowadays one of the main sources of biogenic particles in the world.     

Purification of S1 nuclease from Aspergillus oryzae by recycling isoelectric focusing

We describe the purification of a single-strand nuclease from Aspergillus oryzae using the first commercial prototype of an instrument (RF3TM) designed by Milan Bier et al. for preparative-scale isoelectric focusing. Protein separation takes place entirely in solution, with shear-stabilized laminar flow counteracting convective disturbances generated by the electric field. Conditions for isoelectric focusing were determined by focusing fractions with nuclease activity, following chromatography on DEAE-Sepharose, in analytical gels containing carrier ampholytes. The separation was then scaled up to process larger quantities of protein in the RF3. When partially-purified protein (250 mg, 6700 U/mg) was focused in pH 3-4 carrier ampholytes. 67% of the activity was recovered in pooled peak fractions with a specific activity of 54,000 U/mg protein. Overall, 82% of the activity loaded on the RF3 was recovered. Eliminating two steps prior to isoelectric focusing, and increasing the protein load from 250 mg to 1.2 g, produced an enzyme with a nearly four-fold increase in specific activity (from 4000 U/mg protein to 15,000 U/mg protein) but with unacceptable color. Our results indicate that a high quality enzyme can be prepared in quantity when heat denaturation and ammonium sulfate precipitation are included prior to isoelectric focusing.     

Thermal Properties of Hot-Stage Extrudates of Itraconazole and Eudragit E100. Phase separation and polymorphism

Solid dispersions of itraconazole and eudragit E100 were prepared by hot-stage extrusion. Analysis of the physical structure revealed the existence of different phases, depending on the manufacturing condition. Extrudates prepared at 453 K existed as a molecular dispersion of itraconazole in eudragit E100 when the drug concentration did not exceed ca. 13% mass/mass. At higher concentrations, a second phase consisting of pure glassy itraconazole emerged. In other dispersions prepared at 413 K, the second phase consisted of pure crystalline itraconazole. The difference can be attributed to the relation of the process-temperature to the melting point. Heating of both dispersions induced cold crystallization. Extrudates prepared at 453 K showed comparable behavior before and after milling, with the exception that unmilled dispersions with a drug load of ≥60% mass/mass recrystallized upon heating into a polymorphic modification of itraconazole (T _m=431 K). Upon further heating the polymorph recrystallized to the stable crystalline form (T _m=441 K). This revised version was published online in August 2006 with corrections to the Cover Date.     

A potentiometric study of the water-soluble silver(I) complexes of n,n'-bis(2-hydroxyethyl)dithiooxamide : Part III. Determination of the different species

Silver(I) and N,N'-bis(2-hydroxyethyl)dithiooxamide (H₂X) in acidic solutions, form a series of water-soluble polynuclear complexes. These complexes can be represented by two general formulae: H_2qAg_pX_q and H_2q-1Ag_pX_q with q=1,2,3 and p=q, q-1.