A rationalization of the solvent effect on the Diels-Alder reaction in ionic liquids using multiparameter linear solvation energy relationships

The Diels-Alder reaction between cyclopentadiene and three dienophiles (acrolein, methyl acrylate and acrylonitrile) having different hydrogen bond acceptor abilities has been carried out in several ionic liquids and molecular solvents in order to obtain information about the factors affecting reactivity and selectivity. The solvent effects on these reactions are examined using multiparameter linear solvation energy relationships. The collected data provide evidence that the solvent effects are a function of both the solvent and the solute. For a solvent effect to be seen, the solute must have a complimentary character; selectivities and rates are determined by the solvent hydrogen bond donation ability (alpha) in the reactions of acrolein and methyl acrylate, but not of acrylonitrile.     

Pressure-induced polymerization in solid ethylene

Ethylene is the simplest organic molecule containing a double bond and is the starting monomeric unit in the synthesis of polyethylene, one of the most largely produced polymers. Here we report a high pressure infrared study of ethylene at room temperature. A polymerization reaction is observed when the crystalline phase I is compressed above 3.0 GPa. The reaction kinetics was investigated at two different pressures, 3.6 and 5.4 GPa. The recovered product was identified in both cases as polyethylene, but while a conformationally disordered and branched low-density polymer is obtained at the highest pressure, a high-density crystalline polymer is obtained at 3.6 GPa. A reaction mechanism was proposed on the basis of the kinetic data and the structural information.     

High energy proton emission in reactions induced by 315 MeV 16O ions

Inclusive proton spectra have been measured for the reaction ¹⁹⁷Au(¹⁶O, p)X at 315 MeV. The data, which are consistent with emission from a moving source, are compared with the fireball model and with models preequilibrium emission.     

A calibration procedure for center of rotation estimation in ultrasound tomography without position sensor

Experimental Techniques -     

Light‐Induced Catalyst and Solvent‐Free High Pressure Synthesis of High Density Polyethylene at Ambient Temperature

The combined effect of high pressure and electronic photo‐excitation has been proven to be very efficient in activating extremely selective polymerisations of small unsaturated hydrocarbons in diamond anvil cells (DAC). Here we report an ambient temperature, large volume synthesis of high density polyethylene based only on high pressure (0.4–0.5 GPa) and photo‐excitation (~350 nm), without any solvent, catalyst or radical initiator. The reaction conditions are accessible to the current industrial technology and the laboratory scale pilot reactor can be scaled up to much larger dimensions for practical applications. FTIR and Raman spectroscopy, and X‐ray diffraction, indicate that the synthesised material is of comparable quality with respect to the outstanding crystalline material obtained in the DAC. The polydispersity index is comparable to that of IV generation Ziegler‐Natta catalysts. Moreover the crystalline quality of the synthesised material can be further enhanced by a thermal annealing at 373 K and ambient pressure.

     

On the rational cohomology of moduli spaces of curves with level structures

We investigate low degree rational cohomology groups of smooth compactifications of moduli spaces of curves with level structures. In particular, we determine H^k([`(S)]<sub>g</sub>, \mathbb Q){H^k\left({\bar S}_{g}, {\mathbb Q}\right)} for g ≥ 2 and k ≤ 3, where [`(S)]_g{{\bar S}_{g}} denotes the moduli space of spin curves of genus g.     

Particle scattering by a test fluid on a Schwarzschild spacetime: the equation of state matters

The motion of a massive test particle in a Schwarzschild spacetime surrounded by a perfect fluid with equation of state p ₀=wρ ₀ is investigated. Deviations from geodesic motion are analyzed as a function of the parameter w, ranging from w=1, which corresponds to the case of massive free scalar fields, down into the so-called “phantom” energy, with w<−1. It is found that the interaction with the fluid leads to capture (escape) of the particle trajectory in the case 1+w>0 (<0), respectively. Based on this result, it is argued that inspection of the trajectories of test particles in the vicinity of a Schwarzschild black hole with matter around may offer a new means of gaining insights into the nature of cosmic matter.     

Solution of Maxwell’s equations on a de Sitter background

The Maxwell equations for the electromagnetic potential, supplemented by the Lorenz gauge condition, are decoupled and solved exactly in de Sitter space–time studied in static spherical coordinates. There is no source besides the background. One component of the vector field is expressed, in its radial part, through the solution of a fourth-order ordinary differential equation obeying given initial conditions. The other components of the vector field are then found by acting with lower-order differential operators on the solution of the fourth-order equation (while the transverse part is decoupled and solved exactly from the beginning). The whole four-vector potential is eventually expressed through hypergeometric functions and spherical harmonics. Its radial part is plotted for given choices of initial conditions. We have thus completely succeeded in solving the homogeneous vector wave equation for Maxwell theory in the Lorenz gauge when a de Sitter space–time is considered, which is relevant both for inflationary cosmology and gravitational wave theory. The decoupling technique and analytic formulae and plots are completely original. This is an important step towards solving exactly the tensor wave equation in de Sitter space–time, which has important applications to the theory of gravitational waves about curved backgrounds.     

A-Codes from Rational Functions over Galois Rings

In this paper, we describe authentication codes via (generalized) Gray images of suitable codes over Galois rings. Exponential sums over these rings help determine—or bound—the parameters of such codes.     

Jahn-Teller transition in Al doped LiMn2O4 spinel

Al-doped lithium manganese spinels, with starting composition Li_1.02Al_xMn_1.98−xO₄ (0.00<x≤0.06), are investigated to determine the influence of the Al³⁺ doping on the Jahn-Teller (J-T) cooperative transition temperature T_J-T. X-ray powder diffraction (XRPD), nuclear magnetic resonance, electron paramagnetic resonance, conductivity and magnetic susceptibility data are put into relation with the tetrahedral and octahedral occupancy fraction of the spinel sites and with the homogeneous distribution of the Al³⁺ ions in the spinel phase. It is observed that Al³⁺ may distribute between the two cationic sublattices. The J-T distortion, associated with a drop of conductivity near room temperature in the undoped sample, is shifted towards lower temperature by very low substitution. However, for x>0.04 T_J-T it increases with increasing x, as clearly evidenced in low temperature XRPD observations. A charge distribution model in the cationic sublattice, for Al substitution, is proposed to explain this peculiar behavior.