A new class of macrocyclic complexes formed via nickel-promoted macrocyclisation of dioxime with dinitrile

o-Phthalonitrile couples with chelating dioxime on nickel(II), with formation of a dinuclear nickel(II) macrocyclic complex--the first representative of a new class of imine-appended macrocycles.     

Speckle detection for 3D ultrasound

Positioning accuracy of 3D ultrasound slice planes can be enhanced by speckle decorrelation of the B-scans. A suitable method requires accurate identification of zones of non-specular reflection in the image, a feature of parenchymal tissue. This has traditionally been achieved with statistics such as signal-to-noise ratios and measures of autocorrelation curves. Co-occurrence matrices and structural approaches have also been applied to ultrasound images. In this paper we assess the performance of these methods when only B-scan display data is available. We also report improved results with in vivo images using a proposed structural algorithm that detects speckle kernels. All detection algorithms yielded detection error rates between 28% and 38%, suggesting that user intervention may be required for clinically useful performance.     

Intrinsic aging and effective viscosity in the slow dynamics of a soft glass with tunable elasticity

We investigate by rheology and light scattering the influence of the elastic modulus, G0, on the slow dynamics and the aging of a soft glass. We show that the slow dynamics and the aging can be entirely described by the evolution of an effective viscosity, eta(eff), defined as the characteristic time measured in a stress relaxation experiment times G0. At all times, eta(eff) is found to be independent of G0, of elastic perturbations, and of the rate at which the sample is quenched in the glassy phase. We propose a simple model that links eta(eff) to the internal stress built up at the fluid-to-solid transition.     

Synthesis of (Ca,Ce,Ce)2Ti2O7: a pyrochlore with mixed-valence cerium

Pyrochlore with mixed-valence Ce was synthesized by firing and annealing Ce(NO₃)₄, TiO₂, and Ca(OH)₂ with a stoichiometry of CaCeTi₂O₇ at 1300 °C. The product contains Ce-pyrochlore, Ce-rich perovskite, CeO₂ (cerianite), and minor CaO. Electron energy-loss spectroscopy (EELS) revealed both Ce⁴⁺ and Ce³⁺ in the Ce-pyrochlore with a Ce⁴⁺ to total Ce (Ce⁴⁺/ΣCe) of 0.80 giving . Cerium in the perovskite and cerianite is dominated by Ce³⁺ and Ce⁴⁺, respectively. High-resolution transmission electron microscope (HRTEM) images show that the boundary between Ce-pyrochlore and Ce-rich perovskite is semi-coherently bonded. The orientational relationship between the neighboring Ce-pyrochlore and Ce-rich perovskite is not random. Ce-pyrochlore (CaCeTi₂O₇) is a chemical analogue for CaPuTi₂O₇, which is a proposed ceramic waste form for deposition of excess weapons-usable Pu in geological repositories. It is postulated, based on the presence of Ce³⁺ in the Ce-pyrochlore, that neutron poisons such as Gd can be incorporated into the CaPuTi₂O₇ phase.     

Flow linear dichroism to probe binding of aromatic molecules and DNA to single-walled carbon nanotubes

Structures of carbon nanotube/ligand complexes were studied by flow linear dichroism (the differential absorption of light polarized parallel and perpendicular to the flow orientation direction) with the aim of establishing linear dichroism as a technique to study such systems. Anthracene, naphthalene, and DNA were chosen as ligands, and the potential for flow linear dichroism to probe ligands noncovalently (as well as covalently) bound to single-walled nanotubes is reported. Linear dichroism enables the determination of approximate orientations of the ligands on the carbon nanotubes.     

Use of electron density critical points as chemical function-based reduced representations of pharmacological ligands

In this paper, we propose a reduced representation of molecules of pharmacological interest based on their chemical functions. The proposed representations of the molecules are obtained by a topological analysis of their electron density maps at medium resolution, leading to graphs of critical points. The distribution of the different types of critical points are compared at various levels of resolution for a training set of 22 molecules in order to define the optimal resolution level leading to the best representation of the various chemical functions. The reduced representations can in the future be used for molecular similarity research and pharmacophore proposals.     

Concentration of sodium ion as the determining factor for the association of dansyl amino acids with the teicoplanin molecule in reversed-phase liquid chromatography

The mechanism of the binding of D,L dansyl amino acids to teicoplanin was investigated. Na+ was used as an indicator of the interactions between the solutes and teicoplanin. The number (n) of sodium ions, Na+, excluded from the solute-teicoplanin interface when analyte transfer occurred was determined. A thermodynamic study and enthalpy-entropy compensation were performed to further explore the interaction mechanism. From these results, it was shown that teicoplanin was balanced between 2 conformational states characterized by distinct enantioselective properties. This approach indicates that liquid chromatography (LC) is a useful tool to extract physicochemical and molecular information from retention data. Thus, LC can be used as a complementary technique with the conventional techniques of molecular interaction analysis.     

Gas-phase reactivity of silver and copper coordinated monosaccharide cations studied by electrospray ionization and tandem mass spectrometry

The analytical distinction of the most common isomeric underivatized hexoses was investigated by means of mass spectrometry experiments. Electrospray ionization and tandem mass spectrometry were used in the analysis of silver and copper-coordinated monosaccharides (D-glucose, D-galactose, D-fructose, O-methyl-alpha-D-glucose and O-methyl-beta-D-glucose). The results show that cationization by Ag(+) allows the differentiation of the three first monosaccharides while the complexes formed by association of Cu(+) with these three monosacharides display a similar reactivity that prevents stereoisomer distinction. Unlike copper, silver adduct-ions of both alpha and beta anomeric O-methyl-D-glucoses exhibit specific decomposition patterns (i.e. a loss of methanol for the alpha-anomer and a loss of silver hydride for the beta-anomer), which allow an easy characterization. A theoretical survey of selected complexes, based on the use of DFT calculations were carried out on both anomers in order to rationalize the experimental findings.     

Unified semi‐analytical wall boundary conditions for inviscid,laminar or turbulent flows in the meshless SPH method

Wall boundary conditions in smoothed particle hydrodynamics (SPH) is a key issue to perform accurate simulations. We propose here a new approach based on a renormalising factor for writing all boundary terms. This factor depends on the local shape of a wall and on the position of a particle relative to the wall, which is described by segments (in two‐dimensions), instead of the cumbersome fictitious or ghost particles used in most existing SPH models. By solving a dynamic equation for the renormalising factor, we significantly improve traditional wall treatment in SPH, for pressure forces, wall friction and turbulent conditions. The new model is demonstrated for cases including hydrostatic conditions for still water in a tank of complex geometry and a dam break over triangular bed profile with sharp angle where significant improved behaviour is obtained in comparison with the conventional boundary techniques. The latter case is also compared with a finite volume and volume‐of‐fluid scheme. The performance of the model for a two‐dimensional laminar flow in a channel is demonstrated where the profiles of velocity are in agreement with the theoretical ones, demonstrating that the derived wall shear stress balances the pressure gradient. Finally, the performance of the model is demonstrated for flow in a schematic fish pass where both the velocity field and turbulent viscosity fields are satisfactorily reproduced compared with mesh‐based codes. Copyright © 2012 John Wiley & Sons, Ltd.     

Linear Synthesis of The Methyl Glycosides of Tri-, Tetra-, and Pentasaccharide Fragments of The Shigella Flexneri Serotype 5A O-Antigen

ABSTRACT

The stepwise synthesis of methyl α-D-glucopyranosyl-(1→3)-α-L-rhamnopyranosyl-(1→3)-α-L-rhamnopyranoside (EBC-OMe, 1), methyl α-L-rhamnopyranosyl-(1→2)-[α-D-glucopyranosyl-(1→3)]-α-L-rhamnopyranosyl-(1→3)-α-L-rhamnopyranoside (A(E)BC-OMe, 2), and methyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→2)-α-L-rhamnopyranosyl-(1→2)-[α-D-glucopyranosyl-(1→3)]-α-L-rhamnopyranosyl-(1→3)-α-L-rhamnopyranoside (DA(E)BC-OMe, 3) is described. Compounds 1, 2 and 3 constitute the methyl glycosides of fragments of the O-specific polysaccharide of Shigella flexneri serotype 5a. Methyl 2,4-di-O-benzoyl-α-L-rhamnopyranosyl-(1→3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside was an appropriate BC precursor for the synthesis of 1. For the synthesis of the branched targets 2 and 3, a benzyl group was best suited at position 2 of rhamnose C. Thus, methyl 4-O-benzyl-α-L-rhamnopyranosyl-(1→3)-2,4-di-O-benzyl-α-L-rhamnopyranoside was the key intermediate to the BC portion. In all cases, 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl fluoride was a convenient E precursor, when used in combination with titanium tetrafluoride. All along, attention was paid to steric hindrance as a factor of major impact on the condensation steps outcome. Therefore, based on previous experience, 2-O-acetyl-3,4-di-O-allyl-α-L-rhamnopyranosyl trichloroacetimidate and 3,4,6-tri-O-acetyl-2-deoxy-2-trichloroacetamido-α-D-glucopyranosyl trichloroacetimidate were used as donors. Both suited all requirements when used as key precursors for residues A and D in the synthesis of 3, respectively.