Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Bis[3‐(trimethyl­silyl)prop­yl] ethyl­enebisphospho­nate,H2DTMSP[EBP]

The title compound (H₂DTMSP[EBP]), C₁₄H₃₆O₆P₂Si₂, was crystallized by the slow evaporation of a solution in a 20:1 mixture of pentane and acetone. The H₂DTMSP[EBP] mole­cule lies about an inversion center. In the solid state, the mol­ecule exists in an anti configuration, with the mol­ecular backbone C—C bond located on an inversion center. The compound exists in the solid state as hydrogen‐bonded infinite sheets in the ab plane, unlike the methyl­ene analogue, which exists as hydrogen‐bonded infinite chains, demonstrating an `even–odd' effect of the length of the backbone alkyl chain.     

Inclusive\bar K^{0*} (892) andK 0*(892) production on silicon by 200 GeVK − andπ −

The production of the neutralK ^? (892) resonances by 200 GeVK ^? andπ ^? has been studied over the kinematic range 0.0<x _f<1.0 andp _t ² <5.0 GeV². Longitudinal and transverse momentum distributions are presented. In addition the decay angular distributions inK ^? fragmentation to \(\bar K^{0*} \) have been investigated.     

Structure and properties of the ion pair charge-transfer complex of octacyanotungstate(IV) with the 2,2′-bipyridinium dication

The X-ray crystal structure of (bpyH2)2[W(CN)8]·4H2 O (bpyH2=2,2-bipyridinium) is described. The [W(CN)8]4– anion has an approximately square antiprismatic (D4d) conformation, seemingly imposed by strong anion–water–cation hydrogen-bonding interactions. Bond distances in the anion are: WC 2.150(5), 2.163(5); CN 1.128(6), 1.145(6)Å and the angles WCN are 177.6(5), 178.3(5)°. The dihydrate and the anhydrous salt are both intensely black solids, exhibiting ion-pair charge-transfer interaction between cation and anion. E.s.r. spectra indicate that 30% of the tungsten is present as WV in the solid state, but that in solution only the WIV complex is present. The electron withdrawing effect of the cation is discussed and compared with that in a series of salts with different bipyridinium cations.     

Solution-phase, triangular ag nanotriangles fabricated by nanosphere lithography

A novel method to produce solution-phase triangular silver nanoparticles is presented. Ag nanoparticles are prepared by nanosphere lithography and are subsequently released into solution. The resulting nanoparticles are asymmetrically functionalized to produce either single isolated nanoparticles or dimer pairs. The structural and optical properties of Ag nanoparticles have been characterized. Mie theory and the Discrete Dipole Approximation method (DDA) have been used to model and interpret the optical properties of the released Ag nanoparticles.     

The influence of ion pairing at the electrode/solution interface on the kinetics of heterogeneous electron transfer

A model is developed for the accelerating effect of non-reacting ions adsorbed on the inner Helmholtz plane on the kinetics of electron transfer to a reactant which is also situated on the same plane near the electrode. It is assumed that the charge density of non-reacting ions around the reacting ion can be described by a two dimensional distribution function analogous to that used by Fuoss to describe ion pairing in the bulk of the solution. Kinetic equations are presented in which the discreteness-of-charge terms are explicitly included and the magnitude of these terms is estimated on the basis of a simple model. The estimates show that the acceleration of hydrogen ion in the presence of adsorbed iodide ions can be attributed to the electrostatic effect of the surrounding ionic atmosphere.     

Thermal and mechanical properties of PE/organoclay nanocomposites

Polyethylene/montmorillonite clay nanocomposites were obtained via direct melt intercalation. The clay was organically modified with four different types of quaternary ammonium salts. The objective of this work is to study the use of montmorillonite clay in the production of nanocomposites by means on rheological, mechanical and crystallization properties of nanocomposites and to compare to the properties of the matrix and PE/unmodified clay nanocomposites. In general, the tensile test showed that the yield strength and modulus of the nanocomposites are close to the pure PE. Apparently, the mixture with Dodigen salt seems to be more stable than the pure PE and PE/unmodified clay.     

Predicting the shape and structure of face-centered cubic gold nanocrystals smaller than 3 nm.

Although a number of computational studies have examined the relative stability of icosahedral and decahedral gold clusters from 1 to 3 nm in size, few studies have focussed on the variety of face-centered cubic (fcc) nanoparticles in this size regime. In most cases small fcc gold particles are assumed to adopt the truncated octahedral shape, but in light of the fact that the shape and structure of gold nanoparticles is known to vary, the relative stability of fcc polyhedra may change with size. Presented here are results of first-principles calculations investigating the preferred shape of gold particles less than 3 nm in size. Our results indicate that the equilibrium shape of fcc gold nanoparticles less than 1 nm is the cuboctahedron, but this shape rapidly becomes energetically unstable with respect to the truncated octahedron, octahedron and truncated cube shapes as the size increases.