Aerobic intramolecular oxidative amination of alkenes catalyzed by NHC-coordinated palladium complexes

[reaction: see text] Palladium(II) complexes bearing a single N-heterocyclic carbene ligand serve as effective catalysts for the aerobic oxidative cyclization of alkenes with pendant sulfonamides. The use of carboxylic acid cocatalysts (AcOH and PhCO(2)H) often leads to significant improvements in catalyst stability and product yield and enables catalytic turnover to be achieved with air, rather than pure oxygen gas, as the source of O(2).     

Control of morphology in efficient photovoltaic diodes from discotic liquid crystals

We report on the role of morphology in photovoltaic diodes with blend active layers composed of perylene tetracarboxdiimide (EPPTC) and hexabenzocoronene (HBC) derivatives as electron and hole acceptors. Controlled annealing of HBC:EPPTC films while in conformal contact with a flat elastomeric stamp improves photovoltaic response, leading to an external quantum efficiency of 29.5% at 460 nm and an open-circuit voltage of 0.70 V. The improved performance is attributed in part to larger crystalline domains following annealing. The elastomeric stamp restricts the top surface of the thin film during annealing, leading to low surface roughness, while also allowing for greater vertical stratification of the components in the bulk. Blended HBC:EPPTC films also exhibit an unique optical absorption feature near 590 nm, which we attribute to an altered crystalline packing of EPPTC in the presence of HBC. The significance of the local structure at molecular heterojunctions in blended active layer photovoltaic diodes is discussed.     

Continuity versus nonexistence for a class of linear stochastic Cauchy problems driven by a Brownian motion

Let A = d/dθ denote the generator of the rotation group in the space C(Γ), where Γ denotes the unit circle. We show that the stochastic Cauchy problem

Fluorescence-quenching-based homogeneous caspase-3 activity assay using photon upconversion

Caspase proteases are key mediators in apoptosis and thus of great interest in pharmaceutical industry. Enzyme-activity assays are commonly employed in the screening of protease inhibitors that are potential drug candidates. Conventional homogeneous fluorescence-based assays are susceptible to autofluorescence originating from biological material. This background autofluorescence can be eliminated by using upconverting phosphors (UCPs) that emit visible light upon excitation at near-infrared. In the assay energy was transferred from a UCP-donor to a conventional fluorophore acceptor that resided at one end of a caspase-3-specific substrate peptide. Attached to the other end was a quencher molecule that was used to attenuate the acceptor emission through intramolecular energy transfer in an intact peptide. In non-inhibitory conditions the enzyme reaction separated the fluorophore from the quencher and the emission of the fluorophore was recovered. The method was applied for the detection and characterization of a known caspase-3 inhibitor Z-DEVD-FMK, and the assay gave IC₅₀ values of approximately 13 nM for this inhibitor. We have demonstrated the applicability of UCPs on a fluorescence-quenching-based homogeneous enzyme-activity assay for the detection of caspase-3 inhibitors. The use of near-infrared excitable UCPs enables inexpensive instrumentation and total elimination of autofluorescence, while the use of an internally quenched substrate molecule diminishes the background resulting from radiatively excited acceptor molecules. The reduction of autofluorescence and radiative background result in high signal-to-background ratios (ratios of approximately 100 were obtained). By further utilizing assay miniaturization and signal enhancement in a white microtitration plate, a significant reduction in the reagent consumption can be achieved rendering the assay applicable for high-throughput screening.     

The role of stimulus cross-splicing in an event-related potentials study. Misleading formant transitions hinder automatic phonological processing

The mental organization of linguistic knowledge and its involvement in speech processing can be investigated using the mismatch negativity (MMN) component of the auditory event-related potential. A contradiction arises, however, between the technical need for strict control of acoustic stimulus properties and the quest for naturalness and acoustic variability of the stimuli. Here, two methods of preparing speech stimulus material were compared. Focussing on the automatic processing of a phonotactic restriction in German, two corresponding sets of various vowel-fricative syllables were used as stimuli. The former syllables were naturally spoken while the latter ones were created by means of cross-splicing. Phonetically, natural and spliced syllables differed with respect to the appropriateness of coarticulatory information about the forthcoming fricative within the vowels. Spliced syllables containing clearly misleading phonetic information were found to elicit larger N2 responses compared to their natural counterparts. Furthermore, MMN results found for the natural syllables could not be replicated with these spliced stimuli. These findings indicate that the automatic processing of the stimuli was considerably affected by the stimulus preparation method. Thus, in spite of its unquestioned benefits for MMN experiments, the splicing technique may lead to interference effects on the linguistic factors under investigation.     

Influence of pH on the Molecular Weight of Poly-3-hydroxybutyric Acid (P3HB) Produced by Recombinant Escherichia coli

The production of ultrahigh molecular weight poly-3-hydroxybutyric acid (P3HB) from carbohydrates by recombinant Escherichia coli harboring genes from Ralstonia eutropha was evaluated. In shaken-flask experiments, E. coli XL1 Blue harboring plasmid pSK::phaCAB produced P3HB corresponding to 40 and 27 % of cell dry weight from glucose and xylose, respectively. Cultures in bioreactor using glucose as the sole carbon source at variable pH values (6.0, 6.5, or 7.0) allowed the production of P3HB with molecular weight varying between 2.0 and 2.5 MDa. These figures are significantly higher than the values often obtained by natural bacterial strains (0.5–1.0 MDa). Contrary to reports of other authors, no influence of pH was observed on the molecular weight of the polymer produced. Using xylose, P3HB with high molecular weight was also produced, indicating the possibility to produce these polymers from lignocellulosic materials.     

A stereospecific phosphonium ylide-salt coupling reaction

The stereospecific formation of a phosphonium ylide-salt via the stereospecific coupling of an allylic phosphonium ylide with the corresponding phosphonium salt is described.     

Aspects of organic analysis

Summary Kairoline (1-methyl-1,2,3,4-tetrahydroquinoline) is proposed as a powerful solvent in the Zerewitinoff determination of active hydrogen in highly insoluble organic compounds.

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Zusammenfassung Kairolin (1-Methyl-1,2,3,4-tetrahydrochinolin) wird als hervorragendes Lösungsmittel für die Bestimmung von aktivem Wasserstoff in sehr schwer löslichen organischen Substanzen nach Zerewitinoff vorgeschlagen.

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Résumé Les auteurs proposent la kairoline (methyl-1-tetrahydroquinoléine-1,2,3,4) comme solvant de haute efficacité pour les composés organiques particulièrement insolubles lors de la détermination de l'hydrogène actif par la méthode de Zerewitinoff.

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Part V: S. Afr. Industr. Chemist6, 274 (1952).