Chloration d'un polyethylene ramifie influence de la temperature et du solvant

The chlorination of branched high-pressure polyethylenes, promoted by u.v. at various temperatures in carbon tetrachloride and 1,1–2,2 tetrachloroethane, has been studied. It has been possible to elucidate the influence of the temperature and the nature of the solvent on the characteristics of the chlorinated polymers.The chlorination is more efficient in carbon tetrachloride, where the efficiency of the u.v. is not affected by the medium.At the same degree of chlorination, the chain-breaking mechanisms are more important in carbon tetrachloride than in tetrachloroethane; they increase when the temperature of the medium increases. The chlorine-saturated polyethylene obtained in carbon tetrachloride is richer in 1,2 dichloroethylene sequences.Below 60°, the yield of chlorinated polymer is the same in the two solvents. Chlorination at higher temperature in tetrachloroethane does not improve the structural regularity or the yield of the chlorine-saturated polyethylenes.     

Flash photolysis studies of the reaction of NH2 radicals with NO

The kinetics of the reaction NH₂ + NO → N₂ + H₂O were studied, using a conventional flash photolysis system. A value of k₁ = (1.1 ± 0.2) × 10¹⁰ & mole^?1 s^?1 was obtained at room temperature and in the pressure range 2–700 torr in the presence of nitrogen. A slight negative temperature coefficient was observed between 300 and 500 K, equivalent to a negative activation energy of 1.05 ± 0.2 kcal mole^?1.     

The RHIM of the Immune Adaptor Protein TRIF Forms Hybrid Amyloids with Other Necroptosis-Associated Proteins

TIR-domain-containing adapter-inducing interferon-β (TRIF) is an innate immune protein that serves as an adaptor for multiple cellular signalling outcomes in the context of infection. TRIF is activated via ligation of Toll-like receptors 3 and 4. One outcome of TRIF-directed signalling is the activation of the programmed cell death pathway necroptosis, which is governed by interactions between proteins that contain a RIP Homotypic Interaction Motif (RHIM). TRIF contains a RHIM sequence and can interact with receptor interacting protein kinases 1 (RIPK1) and 3 (RIPK3) to initiate necroptosis. Here, we demonstrate that the RHIM of TRIF is amyloidogenic and supports the formation of homomeric TRIF-containing fibrils. We show that the core tetrad sequence within the RHIM governs the supramolecular organisation of TRIF amyloid assemblies, although the stable amyloid core of TRIF amyloid fibrils comprises a much larger region than the conserved RHIM only. We provide evidence that RHIMs of TRIF, RIPK1 and RIPK3 interact directly to form heteromeric structures and that these TRIF-containing hetero-assemblies display altered and emergent properties that likely underlie necroptosis signalling in response to Toll-like receptor activation.     

Structural and Functional Analysis of the Pyridoxal Phosphate Homeostasis Protein YggS from Fusobacterium nucleatum

Pyridoxal 5′-phosphate (PLP) is the active form of vitamin B6, but it is highly reactive and poisonous in its free form. YggS is a PLP-binding protein found in bacteria and humans that mediates PLP homeostasis by delivering PLP to target enzymes or by performing a protective function. Several biochemical and structural studies of YggS have been reported, but the mechanism by which YggS recognizes PLP has not been fully elucidated. Here, we report a functional and structural analysis of YggS from Fusobacterium nucleatum (FnYggS). The PLP molecule could bind to native FnYggS, but no PLP binding was observed for selenomethionine (SeMet)-derivatized FnYggS. The crystal structure of FnYggS showed a type III TIM barrel fold, exhibiting structural homology with several other PLP-dependent enzymes. Although FnYggS exhibited low (<35%) amino acid sequence similarity with previously studied YggS proteins, its overall structure and PLP-binding site were highly conserved. In the PLP-binding site of FnYggS, the sulfate ion was coordinated by the conserved residues Ser201, Gly218, and Thr219, which were positioned to provide the binding moiety for the phosphate group of PLP. The mutagenesis study showed that the conserved Ser201 residue in FnYggS was the key residue for PLP binding. These results will expand the knowledge of the molecular properties and function of the YggS family.     

Synthesis and characterization of thermally crosslinkable hole‐transporting polymers for PLEDs

Two new thermally crosslinkable hole‐transporting polymers, X‐PTPA and X‐PCz, were synthesized via Yamamoto coupling reactions. The number‐averaged molecular weights (M_n) of X‐PTPA and X‐PCz were found to be 45,000 and 48,000, respectively, and therewith, polydispersity indices were of 1.8 and 1.7, respectively. Thermally crosslinked X‐PTPA and X‐PCz exhibit excellent solvent resistance and stable optoelectronic properties. The UV–visible maximum absorption peaks of X‐PTPA and X‐PCz in the thin film state are at 389 and 322 nm, respectively. The HOMO levels of X‐PTPA and X‐PCz are estimated to be ?5.27 and ?5.39 eV, respectively. Multilayered devices (ITO/crosslinked X‐PTPA or X‐PCz/SY‐PPV/LiF/Al) were fabricated with SY (SuperYellow) as the emitting layer. The maximum efficiency of the multilayered device with a crosslinked X‐PTPA layer is approximately three times higher than that of the device without a crosslinked X‐PTPA layer and much higher than that of the crosslinked X‐PCz device. This result can be explained by the observations that crosslinked X‐PTPA produces increased electron accumulation within the emitter, SY, and also efficient exciton formation due to improved charge balance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5111–5117     

Ozonolysis of dipterocarpol and its derivatives

Oxidation of dipterocarpol and its derivatives with ozone gave compounds containing lactone, lactol, alkoxytetrahydrofuran, aldehyde, and methyl ketone fragments in the side chain, as well as 1,2,4-trioxolane fragment in the A ring. The molecular and crystalline structures of dipterocarpol were determined by X-ray analysis.     

Contribution of the triangle graphs to the neutron electric dipole moment

In the Kobayashi-Maskawa model we compute a new contribution to the neutron electric dipole moment induced byCP violating flavour-changing transitions of the typess→d+gluon+γ through heavy quark loops. This contribution, essentially given by the triangle anomaly graph, is by itself gauge invariant. We obtain from this mechanismD _n /e=3.10^?32 cm, one order of magnitude below our previous estimate from usual penguin diagram contributions.     

Sidewall-insert compound based on ZnO-treated aramid pulp fibers for run-flat tires

Abstract

To improve the endurance performance of run-flat tires by preventing the sidewall from folding at zero air pressure, a master batch of natural rubber and ZnO-treated aramid pulp (AP) is applied to the rubber sidewall-insert-layer compound. The mechanical, viscoelastic, and fatigue properties of the compounds are investigated by varying the AP content, and the endurance performance of actual run-flat tires is assessed. The results indicate that the mechanical properties are improved and the hysteresis is reduced as the AP content increased. The overall trend of the endurance times of the run-flat tires is consistent with the results of the DeMattia tests, constant-strain fatigue tests, and high-temperature tensile tests. The run-flat endurance time of the tire containing one part per hundred rubber (phr) of AP is superior to that of the tire containing 3 phr of AP because of the enhanced dispersion of the AP fibers.     

Improvement of ultrasound speckle image velocimetry using image enhancement techniques

Ultrasound-based techniques have been developed and widely used in noninvasive measurement of blood velocity. Speckle image velocimetry (SIV), which applies a cross-correlation algorithm to consecutive B-mode images of blood flow has often been employed owing to its better spatial resolution compared with conventional Doppler-based measurement techniques. The SIV technique utilizes speckles backscattered from red blood cell (RBC) aggregates as flow tracers. Hence, the intensity and size of such speckles are highly dependent on hemodynamic conditions. The grayscale intensity of speckle images varies along the radial direction of blood vessels because of the shear rate dependence of RBC aggregation. This inhomogeneous distribution of echo speckles decreases the signal-to-noise ratio (SNR) of a cross-correlation analysis and produces spurious results. In the present study, image-enhancement techniques such as contrast-limited adaptive histogram equalization (CLAHE), min/max technique, and subtraction of background image (SB) method were applied to speckle images to achieve a more accurate SIV measurement. A mechanical sector ultrasound scanner was used to obtain ultrasound speckle images from rat blood under steady and pulsatile flows. The effects of the image-enhancement techniques on SIV analysis were evaluated by comparing image intensities, velocities, and cross-correlation maps. The velocity profiles and wall shear rate (WSR) obtained from RBC suspension images were compared with the analytical solution for validation. In addition, the image-enhancement techniques were applied to in vivo measurement of blood flow in human vein. The experimental results of both in vitro and in vivo SIV measurements show that the intensity gradient in heterogeneous speckles has substantial influence on the cross-correlation analysis. The image-enhancement techniques used in this study can minimize errors encountered in ultrasound SIV measurement in which RBCs are used as flow tracers instead of exogenous contrast agents.