An Investigation of the N-Arylsulfonylation of 2-Azetidinones

N-Arylsulfonylation of 2-azetidinones can lead to the diastereoselective formation of oligomerization products. However, a simple increase of arylsulfonyl chloride concentration minimized oligomerization and allowed preparation of 1-arylsulfonyl-2-azetidinones in good yield.     

Simultaneous determination of various cardiac glycosides by liquid chromatography–hybrid mass spectrometry for the purity assessment of the therapeutic monitored drug digoxin

A high performance liquid chromatography–hybrid tandem mass spectrometry (LC–MSⁿ) method utilising electrospray ionisation has been developed and implemented for the simultaneous determination of several cardiac glycosides (CGs) as well as their corresponding aglycones formed by and extracted from herbaceous plants of the genus Digitalis. The method has been validated in-house and its performance characteristics (linearity, repeatability, limits of detection, etc.) were assessed for use in the quantification of CGs and their corresponding aglycones. LODs from 38 to 936 pg g⁻¹ in solution, corresponding to mass fraction impurity levels from 0.0009 (or 0.00008%) to 0.019 mg g⁻¹ (or 0.0019%) detectable in the pure materials have been realized. Moreover, the method was used to characterize and to determine the inherent CG impurities in batches of the therapeutic monitored drug digoxin which served as candidate reference material for an organic purity assessment inter-laboratory study (CCQM-P20.f) organised by the BIPM Chemistry Section and carried out within the framework of the Organic Analysis Working Group (OAWG) of the Consultative Committee for Amount of Substance – Metrology in Chemistry (CCQM). Digoxin was selected from materials required for the establishment of reference measurement systems for clinical chemistry and laboratory medicine.     

ALDH2 Mediates 5-Nitrofuran Activity in Multiple Species

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Highlights? Zebrafish provide a viable assay for the biological toxicity of 5-nitrofurans ? ALDH2 inhibitors prevent 5-nitrofuran toxicity in zebrafish and yeast ? Genetic dependence on ALDH2 for 5-nitrofuran toxicity in zebrafish and yeast systems ? 5-Nitrofurans bind to and are substrates of human ALDH2     

Application of the copper catalysed N-arylation of amidines in the synthesis of analogues of the chemical tool, blebbistatin

A robust protocol for the CuI-catalysed arylation of amidines is presented. Whilst the initially identified conditions were useful for benzamidine-derived substrates, difficulties were encountered with more complex substrates. This problem was overcome following a change in ligand type, enabling the synthesis of analogues of the chemical tool, blebbistatin.     

Asymmetric catalytic oxidative cleavage of polycyclic systems: the synthesis of atropisomeric diazonanes and diazecanes

Oxidative cleavage of internal double bonds in polycyclic systems can give access to compounds containing medium- to large-sized rings. In this example, the nine- and ten-membered ring containing compounds that resulted from the mCPBA-mediated (mCPBA=meta-chloroperoxybenzoic acid) oxidative cleavage reaction were shown to exhibit atropisomerism. The reaction of the polycyclic system with catalytic amounts of ruthenium tetraoxide followed by diol cleavage achieved the same synthetic goal. Use of the Nishiyama-Beller ruthenium-based catalysts enabled the synthesis of optically-enriched samples, providing the first example of an atropselective oxidative cleavage reaction.     

Using Fractionation and Diffusion Ordered Spectroscopy to Study Lignin Molecular Weight.

Recent reports demonstrate that applications of the biopolymer lignin can be helped by the use of a fraction of the lignin which has an optimal molecular weight range. Unfortunately, the current methods used to determine lignin's molecular weight are inconsistent or not widely accessible. Here, an approach that relies on 2D DOSY NMR analysis is described that provides a measure of lignin's molecular weight. Consistent results were obtained using this well-established NMR technique across a range of lignins.     

Generalization of the rotated parabolic equation to variable slopes

The rotated parabolic equation [J. Acoust. Soc. Am. 87, 1035-1037 (1990)] is generalized to problems involving ocean-sediment interfaces of variable slope. The approach is based on approximating a variable slope in terms of a series of constant slope regions. The original rotated parabolic equation algorithm is used to march the field through each region. An interpolation-extrapolation approach is used to generate a starting field at the beginning of each region beyond the one containing the source. For the elastic case, a series of operators is applied to rotate the dependent variable vector along with the coordinate system. The variable rotated parabolic equation should provide accurate solutions to a large class of range-dependent seismo-acoustics problems. For the fluid case, the accuracy of the approach is confirmed through comparisons with reference solutions. For the elastic case, variable rotated parabolic equation solutions are compared with energy-conserving and mapping solutions.     

The effect of the earth's magnetic field on auger analysis

Semi-quantitative analyses of thin films or surfaces are commonly obtained from the peak intensities in the differentiated Auger spectrum. To reduce effects of surface roughness, beam focus and electron current, ratios of peak heights are used rather than absolute values. In performing analysis of CdSe single crystal and thin film samples in a commercial Auger analyzer fitted with a cylindrical mirror analyzer (CMA), the ratio of the Cd(376 eV) to Se(1315 eV) peaks was found to vary by as much as 15% when the diameter of the incident electron beam was increased from 5 to 60 μm. The effect was found to be due to an energy-dependent shift of the electron beam caused by the earth's magnetic field. The electron transmission of the CMA was measured as a function of the primary electron beam spot position on the sample. The transmission decreases rapidly once the spot falls outside an area with a radius ～25 μm. Due to this response, the relative shift in position caused by the magnetic field produces variations in peak ratios when the spot size is changed. This effect will produce inaccurate analysis if the Auger peaks differ significantly in energy and the primary electron beam spot size is large, and accounts for the observed 15% variation in $\text{Cd}\text{Se}$ ratio.