New aspects of the Hunsdiecker-Barton halodecarboxylation—syntheses of phospha-shikimic acid and derivatives

We report an efficient synthetic approach to phospha-isosteres of important intermediates of the shikimic acid pathway by the application of the Hunsdiecker-Barton halodecarboxylation to cyclohexenylcarboxylic acids. As examples, phospha-shikimic acid, its 3-dehydro derivative and the respective monomethyl esters were synthesized. The approach has proven equally useful in the synthesis of isosteres of the antiviral agent oseltamivir.     

ATMOS (ATM optical switching)—system perspective

The expected traffic growth from new broadband services will require network capacities that can be beneficially provided by optical WDM transport networks. Optical packet techniques are essential for large networks to provide flexibility and granularity. A layered network architecture with a transparent optical layer and optical packet layers has been elaborated. Four switching concept options for large optical ATM switch fabrics in the public network and small access nodes are presented. The technology for the related key functions of space and wavelength switching was developed in the RACE ATMOS project and the feasibility of concepts and technologies was verified in four system demonstrators.     

Homogeneous turbulence subjected to rotation-dominated plane distortion

A new configuration of distorted homogeneous turbulence is investigated in the domain of rotation-dominated elliptical flows. The experimental results are compared with exact numerical solutions obtained in Fourier space for the linear part of the problem. The inherently periodic character of the flow results in typical oscillatory variations of the anisotropy and the pressure-strain correlations. A new two-point closure approach of the EDQNM type is proposed for the nonlinear problem; it is based on a representation of the spectral tensor by scalar functions expanded in terms of spherical harmonics.     

α‐Peptide–Oligourea Chimeras: Stabilization of Short α‐Helices by Non‐Peptide Helical Foldamers

Short α‐peptides with less than 10 residues generally display a low propensity to nucleate stable helical conformations. While various strategies to stabilize peptide helices have been previously reported, the ability of non‐peptide helical foldamers to stabilize α‐helices when fused to short α‐peptide segments has not been investigated. Towards this end, structural investigations into a series of chimeric oligomers obtained by joining aliphatic oligoureas to the C‐ or N‐termini of α‐peptides are described. All chimeras were found to be fully helical, with as few as 2 (or 3) urea units sufficient to propagate an α‐helical conformation in the fused peptide segment. The remarkable compatibility of α‐peptides with oligoureas described here, along with the simplicity of the approach, highlights the potential of interfacing natural and non‐peptide backbones as a means to further control the behavior of α‐peptides.     

Acid‐Labile Thermoresponsive Copolymers That Combine Fast pH‐Triggered Hydrolysis and High Stability under Neutral Conditions

Biodegradable polymeric materials are intensively used in biomedical applications. Of particular interest for drug‐delivery applications are polymers that are stable at pH 7.4, that is, in the blood stream, but rapidly hydrolyze under acidic conditions, such as those encountered in the endo/lysosome or the tumor microenvironment. However, an increase in the acidic‐degradation rate of acid‐labile groups goes hand in hand with higher instability of the polymer at pH 7.4 or during storage, thus posing an intrinsic limitation on fast degradation under acidic conditions. Herein, we report that a combination of acid‐labile dimethyldioxolane side chains and hydroxyethyl side chains leads to acid‐degradable thermoresponsive polymers that are quickly hydrolyzed under slightly acidic conditions but stable at pH 7.4 or during storage. We ascribe these properties to high hydration of the hydroxy‐containing collapsed polymer globules in conjunction with autocatalytic acceleration of the hydrolysis reactions by the hydroxy groups.     

Liquid chromatography–high-resolution mass spectrometry for identifying aqueous chlordecone hydrate dechlorinated transformation products formed by reaction with zero-valent iron

Chlordecone (CLD) is a persistent toxic chlorinated pesticide which contaminates different ecosystems in French West Indies. A soil remediation process including zero-valent iron (ZVI) has produced promising results but failed to completely degrade CLD, and the analytical procedures used yielded little information on the transformation products. To fill these gaps, dechlorination of aqueous CLD by micrometric particles of ZVI has been investigated. Aliquots of water with 25% (v/v) of acetone spiked with 100 ppm CLD were taken at different times during a 30-day ZVI treatment and directly analysed by ultra-high-performance liquid chromatography in negative electrospray ionisation mode. CLD has been totally transformed after 14 days into 14 dechlorinated degradation products, including 9 isomeric compounds. The maximum chloride concentrations appearing in the medium represent 44% of that which would result from total dechlorination of CLD. The CLD transformation products identified by accurate mass measurements on an ultra-high-resolution Q-TOF mass spectrometer (Q-TOF-MS) were C₁₀H₃Cl₉O₂, C₁₀H₄Cl₈O₂, C₁₀H₅Cl₇O₂, C₁₀H₆Cl₆O₂ and C₁₀H₇Cl₅O₂. The results show the interest of LC-Q-TOF-MS for identifying transformation products of organic contaminants, and the effectiveness of micrometric ZVI particles to totally transform CLD into less chlorinated products.     

On a boundary layer problem for the nonlinear Boltzmann equation

This article deals with a boundary-layer problem arising in the kinetic theory of gases when the mean free path of molecules tends to zero. The model considered here is the stationary, nonlinear Boltzmann equation in one dimension with a slightly perturbed reflection boundary condition. We restrict our attention to the case of hard spheres collisions, with Grad's cutoff assumption. Existence, uniqueness and asymptotic behavior are derived by means of energy estimates.