Chlorinated polyethylene nanocomposites using PCL/clay nanohybrid masterbatches

Exfoliated nanocomposites were prepared by dispersion of poly(ε-caprolactone) (PCL) grafted montmorillonite nanohybrids used as masterbatches in chlorinated polyethylene (CPE). The PCL-grafted clay nanohybrids with high inorganic content were synthesized by in situ intercalative polymerization of ε-caprolactone between silicate layers organo-modified by alkylammonium cations bearing two hydroxyl functions. The polymerization was initiated by tin alcoholate species derived from the exchange reaction of tin(II) bis(2-ethylhexanoate) with the hydroxyl groups borne by the ammonium cations that organomodified the clay. These highly filled PCL nanocomposites (25 wt% in inorganics) were dispersed as masterbatches in commercial chlorinated polyethylene by melt blending. CPE-based nanocomposites containing 3-5 wt% of inorganics have been prepared. The formation of exfoliated nanocomposites was assessed both by wide-angle X-ray diffraction and transmission electron microscopy. The thermal and thermo-mechanical properties were studied as a function of the filler content, by differential scanning calorimetry and dynamic mechanical analysis, respectively. The mechanical properties were also assessed by tensile tests. The Young’s modulus of CPE is increased by a decade when a PCL-grafted clay masterbatch is exfoliated to reach 5 wt% of clay in the resulting nanocomposite. The influence of PCL-grafting on the properties of these nanocomposites was investigated by comparison with materials obtained with ungrafted-PCL.     

Bonding mode of a bifunctional P approximately Si-H ligand in the ruthenium complex "Ru(PPh2CH2OSiMe2H)3"

The phosphinosilane compound PPh 2CH 2OSiMe 2H is potentially a bifunctional P approximately Si-H ligand. By treatment with the Ru (II) precursor RuH 2(H 2) 2(PCy 3) 2, the complex Ru(PPh 2CH 2OSiMe 2H) 3 ( 2), resulting from the coordination of three ligands and the displacement of two PCy 3 and two dihydrogen ligands, was formed. The different bonding modes for each of the three bifunctional P approximately Si-H ligands are discussed on the basis of multinuclear NMR, X-ray diffraction, and density functional theory studies. One ligand acts as a monodentate phosphine ligand with a pendant Si-H group, whereas the two others act as bidentate ligands with different Si-H bond activations. Indeed, an intermediate structure between two arrested forms 2a and 2b can be proposed: a dihydrido(disilyl)ruthenium(IV) species (form 2a) resulting from two Si-H oxidative additions or a hydrido(silyl)ruthenium(II) species (form 2b) presenting an agostic Si-H bond and only one oxidative addition.     

An engineered protein tag for multiprotein labeling in living cells

The visualization of complex cellular processes involving multiple proteins requires the use of spectroscopically distinguishable fluorescent reporters. We have previously introduced the SNAP-tag as a general tool for the specific labeling of SNAP-tag fusion proteins in living cells. The SNAP-tag is derived from the human DNA repair protein O6-alkylguanine-DNA alkyltransferase (AGT) and can be covalently labeled in living cells using O6-benzylguanine derivatives bearing a chemical probe. Here we report the generation of an AGT-based tag, named CLIP-tag, which reacts specifically with O2-benzylcytosine derivatives. Because SNAP-tag and CLIP-tag possess orthogonal substrate specificities, SNAP and CLIP fusion proteins can be labeled simultaneously and specifically with different molecular probes in living cells. We furthermore show simultaneous pulse-chase experiments to visualize different generations of two different proteins in one sample.     

Porous BCN nanotubular fibers: growth and spatially resolved cathodoluminescence

Porous boron carbonitride nanotubular fibers with BCN stoichiometry and homogeneous B, C, and N species distribution were fabricated via the CVD method. Spatially resolved cathodoluminescence measurements on individual nanostructures revealed intense ultraviolet emission centered at 319 nm, suggesting the characteristics of a semiconductor with a band gap of 3.89 eV. It is believed that the present nanostructures may have a variety of applications in ultraviolet optical devices, hydrogen storage systems, and field emission apparatus.     

Total synthesis of (+/-)-mycothiazole and formal enantioselective approach

[Reaction: see text] A total synthesis of (+/-)-mycothiazole and a formal enantioselective approach have been achieved from 2,4-dibromothiazole. A chain extension of a homoallylic alcohol proceeding through an unsaturated sultone intermediate, generated by ring-closing metathesis, was used as a key step for the elaboration of the conjugated (Z)-dienol moiety.     

Stabilized Galerkin approximation of convection-diffusion-reaction equations: discrete maximum principle and convergence

We analyze a nonlinear shock-capturing scheme for -conform- ing, piecewise-affine finite element approximations of linear elliptic problems. The meshes are assumed to satisfy two standard conditions: a local quasi-uniformity property and the Xu-Zikatanov condition ensuring that the stiffness matrix associated with the Poisson equation is an -matrix. A discrete maximum principle is rigorously established in any space dimension for convection-diffusion-reaction problems. We prove that the shock-capturing finite element solution converges to that without shock-capturing if the cell Péclet numbers are sufficiently small. Moreover, in the diffusion-dominated regime, the difference between the two finite element solutions super-converges with respect to the actual approximation error. Numerical experiments on test problems with stiff layers confirm the sharpness of the a priori error estimates.

     

Photomagnetic nanorods of the Mo(CN)8Cu2 coordination network

Nanorods of the photomagnetic coordination network Mo(CN)8Cu2 coated with polyvinylpyrrolidone were prepared and exhibit an enhanced effect upon irradiation when compared to the bulk.     

Time evolution of second-order nonlinear profiles induced within thermally poled silica samples

The second-order nonlinear profile induced within thermally poled Infrasil silica samples is characterized as a function of the duration of the poling process. For poling durations shorter than 5 min the spatial distribution of the chi(2) susceptibility exhibits a triangular shape. This observation, as well as the maximum value of the electric field recorded during poling (1.9 x 10(9) V/m), is in excellent agreement with charge migration models that involve a single charge carrier. It is shown that for higher poling durations the nonlinear profiles tend to flatten; in that case the charge injection mechanisms cannot be neglected. For another point of view, the experimental method introduced herein has allowed us to determine the mobility of the rapid charge carrier involved in the poling process: micro = 1.5 x 10(-15) m2 V(-1) s(-1) at 250 degrees C.