Palladium-catalysed 5-endo-trig allylic (hetero)arylation

A palladium-catalysed intramolecular allylic (hetero)arylation strategy for the synthesis of fused cyclopentenes incorporated with all-carbon quaternary and spiro centres is described. The method is straightforward, shows broad scope, proceeds in synthetically useful yields, and provides a rare means to construct complex cyclopentanoids. The reaction is believed to involve a kinetically unfavourable 5-endo-trig carbocyclisation of the tethered (π-allyl)palladium system. Further, this method was successfully applied as the key step in the total synthesis of diterpene natural products taiwaniaquinone H and dichroanone.

A palladium-catalysed intramolecular allylic (hetero)arylation strategy for the synthesis of fused cyclopentenes incorporated with all-carbon quaternary and spiro centres is described.     

Dual-label autoradiographic analysis of human skin fibroblast and myoblast proteins by two-dimensional polyacrylamide gel electrophoresis using immobilised pH gradients in the first dimension

Horizontal two-dimensional polyacrylamide gel electrophoresis with immobilised pH gradients in the first dimension has been applied to the analysis of human skin fibroblast and muscle myoblast total cell proteins. Excellent two-dimensional separations of skin fibroblast proteins were obtained using pH 4-10 immobilised pH gradient gels with a long interelectrode distance (16 cm), but resolution was degraded, particularly of the more acidic proteins, by the use of shorter (10 cm) gels. Improved resolution of acidic and basic proteins was obtained using separate pH 4-7 and pH 7-10 immobilised pH gradient gels respectively in the first dimension. Two-dimensional protein maps of skin fibroblast proteins were visualised both by silver staining and by autoradiography of samples labelled synthetically with [35S]methionine. Horizontal two-dimensional electrophoresis, using pH 4-7 and pH 7-10 immobilised pH gradient gels in the first dimension, was applied to the analysis of protein samples from skin fibroblasts and muscle myoblasts dual-labelled synthetically with [35S]methionine and [75Se]selenomethionine in an attempt to identify sets of proteins specific to each cell type. In addition, two-dimensional maps or protein samples derived from normal individuals and patients with Duchenne muscular dystrophy were compared to search for protein changes associated with the disease state. Although sets of qualitative protein spot differences were observed by visual inspection of the two-dimensional gels, more rigorous qualitative and quantitative analysis of the patterns using a computerised analysis system will be required to obtain the maximum amount of information from these data.     

HPTLC Method for Quantification of Apigenin in the Dried Root Powder of Gmelina arborea Linn.

JPC – Journal of Planar Chromatography – Modern TLC - A sensitive high-performance thin-layer chromatographic method has been established for quantification of apigenin in dried root...     

Synthesis and Biological Activity of 3-[4H-(1,2,4)-Triazolyl]-2,6-diaryl-1,3,5-oxadiazine-4-thione

4-Amino-1,2,4-triazole (1) undergoes facile condensation with aromatic aldehydes to afford the corresponding 4-(arylidene-amino)-4H-[1,2,4]-triazole (2a–h) in good yield. Rearrangement of compounds (2a–h) with benzoyl isothiocyanate/4-chloro-benzoyl isothiocyanate/2,4-dichloro-benzoyl isothiocyanate yields corresponding 1,3,5-oxadiazine derivatives (3). Structural elucidation of these compounds was based on elementary analysis and spectral data studies. The newly synthesized compounds were evaluated for their antibacterial activities.     

Validated LC–MS/MS method for quantification of agomelatine in human plasma and its application in a pharmacokinetic study

An analytical method based on liquid–liquid extraction has been developed and validated for analysis of agomelatine in human plasma. Fluoxetine was used as an internal standard for agomelatine. A Betasil C18 (4.0 × 100 mm, 5 µm) column provided chromatographic separation of analytes followed by detection with mass spectrometry. The method involves simple isocratic chromatographic conditions and mass spectrometric detection in the positive ionization mode using an API‐4000 system. The proposed method has been validated with linear range of 0.050–8.000 ng/ml for agomelatine. The intra‐run and inter‐run precision values are within 12.12% and 9.01%, respectively, for agomelatine at the lower limit of quantification level. The overall recovery for agomelatine and fluoxetine was 67.10% and 72.96%, respectively. This validated method was used successfully for analysis of plasma samples from a pharmacokinetic study. Copyright © 2012 John Wiley & Sons, Ltd.     

On levels in arrangements and voronoi diagrams

This paper gives efficient, randomized algorithms for the following problems: (1) construction of levels of order 1 tok in an arrangement of hyperplanes in any dimension and (2) construction of higher-order Voronoi diagrams of order 1 tok in any dimension. A new combinatorial tool in the form of a mathematical series, called a θ series, is associated with an arrangement of hyperplanes inR ^d . It is used to study the combinatorial as well as algorithmic complexity of the geometric problems under consideration.     

A generalization of dehn-sommerville relations to simple stratified spaces

We generalize the classical Dehn-Sommerville relations for simple, convex polytopes to compact, transverse intersections of arbitrary smooth manifolds with boundaries.This research was supported by NSF Grant CCR 8906799 and a Packard fellowship.     

Control and modeling of the dielectrophoretic assembly of on-chip nanoparticle wires

Suspensions of metallic nanoparticles in water were assembled via the action of an alternating electric field (dielectrophoresis) into wires of micrometer thickness. Two modes of microwire assembly, one through the bulk of the suspension and one as half-cylinders on the glass surface between the electrodes, were identified. The operating conditions responsible for the two assembly modes were recognized. The control of the process parameters allows making, for example, straight single connectors or massively parallel arrays of microwires on the surface of the chip, which can be extracted in dry form. The microwire assembly process was modeled using finite element electrostatic calculations. The direction of growth can be guided by introducing conductive islands or particles in the suspension. The experiments, supported by electrostatic calculations, show that the wires grow in the direction of highest field intensity, "automatically" making electrical connections to the objects between the electrodes. The results point the way to controlled dielectrophoretic assembly of nanoparticles into on-chip electrical connectors, switches, and networks.