Synthesis ofo-thiatelluraphenylenezirconocenes. X-ray crystal structure of

o-Thiatelluraphenylenezirconocene complexes were obtained in good yield by reaction of dilithiumo-benzenthiatelluride with zirconocene dichlorides. These compounds represent the first examples of heterodichalcogenaphenylene bent metallocences. They were characterized by spectroscopic methods and the effect on the n.m.r. results of stepwise substitution of one and two Te atoms for S is discussed. X-ray crystal structure analysis was performed for one representative complex. The structure is very similar to that previously reported for a diselenaphenylene complex, but the disorder observed for chalcogen atoms prevents an accurate comparison of the geometrical parameters with other related compounds.     

Chemical triple-mutant boxes for quantifying cooperativity in intermolecular interactions

Chemical double-mutant cycles have been used to quantify intermolecular functional-group interactions in H-bonded zipper complexes in chloroform. If the same interaction is measured in zippers of different overall stability, the double-mutant cycles can be combined to produce a triple-mutant box. This construct quantifies cooperativity between the functional group interaction of interest and the other interactions that are used to change the overall stability of the complexes. The sum of two edge-to-face aromatic interactions (-2.9 +/- 0.5 kJ mol-1) is shown to be insensitive to changes of up to 13.7 +/- 0.2 kJ mol-1 in the overall stability of the complex. In principle, enthalpic cooperative effects caused by entropy-enthalpy compensation could perturb the measurement of intermolecular interactions when using the double-mutant cycle approach, but these experiments show that, for this system, the magnitude of the effect lies within the error of the measurements.     

Peroxynitrite decomposition catalyst prevents apoptotic cell death in a human astrocytoma cell line incubated with supernatants of HIV-infected macrophages

Background  

Oxidative stress has shown to contribute in the mechanisms underlying apoptotic cell death occuring in AIDS-dementia complex. Here we investigated the role of peroxynitrite in apoptosis occurring in astroglial cells incubated with supernatants of HIV-infected human primary macrophages (M/M).     

Energy-filtered electron microscopy for imaging core–shell nanostructures

CuAg core–shell nanoparticles are synthesized by ultra-high vacuum thermal evaporation. We show on this system how the Energy-Filtered Transmission Electron Microscopy (EFTEM) technique allows one to improve the characterization by precisely pointing out the formation of core–shell arrangements in bimetallic nanoparticle assemblies. A criterion to measure the shell thickness from EFTEM images on unique core–shell nanoparticles is defined, that can be used for core–shell nanoparticles of any sizes, with shell thicknesses over 1 nm. It is based on the intensity variation along a line drawn across a core–shell nanoparticle on a EFTEM image. This criterion has been validated by a close comparison of the shell thickness measurements performed in this work and the ones obtained by acoustic micro-Raman spectroscopy. Using this criterion, we report a strong correlation between the size of the Cu cores and the formation of the core–shell arrangements in the nanoparticle assembly studied in this work. The influence of the Cu core shape is also evidenced. The characterisation of such systems using High Resolution TEM (HRTEM) is also discussed.     

A general route for the stereoselective synthesis of (E)-(1-propenyl)phenyl esters by catalytic CC bond isomerization

A general and efficient procedure for the stereoselective synthesis of (E)-(1-propenyl)phenyl esters from readily accessible allylphenols has been developed. The process involves a two-step sequence consisting of the initial acylation of the allylphenols with an acid chloride, followed by catalytic CC bond isomerization in the resulting allylphenyl esters. The latter step was performed in methanol at 80 °C using catalytic amounts (0.5 mol %) of the commercially available bis(allyl)-ruthenium(IV) dimer [{RuCl(μ-Cl)(η³:η³-C₁₀H₁₆)}₂] (C₁₀H₁₆=2,7-dimethylocta-2,6-diene-1,8-diyl). Reactions proceeded in high yields (68–93%) and short times (4–9 h) with complete E-selectivity.     

A colloid perspective of hair cell cilia: a selective literature review

Cilia of hair cells are structurally similar to unilaminar phospholipid vesicles. The close juxtaposition of adjacent cilia is similar to the intervesicle distances found in groups of vesicles. Both cilia and vesicles operate in similar ionic environments. By comparing the cross section of cilia, which are cylinders with the cross section of vesicles, which are spherical, we can see how colloid theory can be applied to both cilia and vesicles. While vesicles have been studied as colloid particles, thus far colloid theory has not been applied to hair cell cilia. This paper presents a basic explanation of colloid theory in a simple graphic form that facilitates a colloid perspective of hair cell cilia behavior. A review of relevant hair cell cilia behavior supports the hypothesis that colloid knowledge is applicable to the problem of understanding cilia functionality in the hair cell. The electromagnetic nature of colloid forces allows for their involvement in the relatively high speed operation required of hair cells which are dealing with signals of up to 2×10⁵ Hz. A fresh look at the biophysics of the hair cell from a colloid perspective may lower the barrier to a closer understanding of active mechanical sensory transduction, amplification and adaptation, and suggest a new domain for the application of colloid theory.     

Regioselective epoxide ring opening. Steroselective synthesis of a tetrahydropyran ring

The stereoselective synthesis of a 2-substituted tetrahydropyran with adjacent alkoxy-bearing stereogenic centre is described. The key steps of this synthesis were the stereoselective epoxidation of an allylic alcohol and the regioselective epoxide ring opening by lithium aluminum hydride. The regio and stereoselective synthesis of a trihydroxyselenide and a trihydroxysulfide is also described. The latter compounds are not suitable for cyclization to tetrahydrofuran ring.     

Characterization of the Core Oligosaccharide and the O‐Antigen Biological Repeating Unit from Halomonas stevensii Lipopolysaccharide: The First Case of O‐Antigen Linked to the Inner Core

A novel core structure among bacterial lipopolysaccharides (LPS) that belong to the genus Halomonas has been characterized. H. stevensii is a moderately halophilic microorganism, as are the majority of the Halomonadaceae. It brought to light the pathogenic potential of this genus. On account of their role in immune system elicitation, elucidation of LPS structure is the mandatory starting point for a deeper understanding of the interaction mechanisms between host and pathogen. In this paper we report the structure of the complete saccharidic portion of the LPS from H. stevensii. In contrast to the finding that the O‐antigen is usually covalently linked to the outer core oligosaccharide, we could demonstrate that the O‐polysaccharide of H. stevensii is linked to the inner core of an LPS. By means of high‐performance anion‐exchange chromatography with pulsed amperometric detection we were able to isolate the core decasaccharide as well as a tridecasaccharide constituted by the core region plus one O‐repeating unit after alkaline degradation of the LPS. The structure was elucidated by one‐ and two‐dimensional NMR spectroscopy, ESI Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry, and chemical analysis.