Reaction pathways to dimer in polystyrene pyrolysis: A mechanistic modeling study

A detailed mechanistic model for polystyrene pyrolysis was created that built on a modeling framework developed in our previous work and was used to probe three competing pathways to dimer formation: benzyl radical addition, 1,3-hydrogen shift, and 7,3-hydrogen shift, based on recent literature reports. To incorporate the chemistry involved in the 7,3-hydrogen shift pathway, the 1,7- and 7,3-hydrogen shift reaction families were added to the model. The updated version of the model tracks 75 species and over 3500 reactions. Rate parameters for all families were specified based on our previous work, more recent literature reports, and regression against limited experimental data. The model was able to accurately predict the experimental results for polystyrene pyrolysis for different reactor configurations for a temperature range of 100 °C and two orders of magnitude of initial molecular weight for experimental data collected in our own lab and from Bouster and coworkers and Bockhorn and coworkers. The results from our model were studied using net rate analysis to gain insight into the competitiveness of the various reaction pathways to dimer formation. The net rate analysis demonstrated that 7,3-hydrogen shift is the dominant reaction pathway to dimer formation at the temperatures studied. Benzyl radical addition becomes a more competitive reaction pathway as the temperature increases, which is caused predominantly by an increase in the benzyl radical concentration with increasing temperature. Overall, it is quantitatively shown that both 7,3-hydrogen shift and benzyl radical addition are important pathways for dimer formation, with their relative competitiveness influenced by temperature.     

Geodesies in the Erez-Rosen space-time

We investigate null and time-like geodesics in the Erez-Rosen space-time, that is, in the exterior gravitational field of a mass with quadrupole moment. By using the weak-field approximation of the Erez-Rosen metric, we find the solution of the equation for equatorial time-like geodesics and determine how they differ from the corresponding Schwarzschild geodesies. For the exact form of the Erez-Rosen metric, we only draw some qualitative conclusions about the influence of the quadrupole moment on the path of test particles and on the motion of photons. We derive the relativistic contribution of the quadrupole moment to the perihelion shift and to the precession of the ascending node.     

The extended Higgs system in R-symmetric supersymmetry theories

The Higgs sector is extended in R  -symmetric supersymmetry theories by two iso-doublets R_d,u$R_{d,u}$ which complement the standard iso-doublets H_d,u$H_{d,u}$. We have analyzed masses and interactions of these novel states and describe their [non-standard] decay modes and their production channels at the LHC and e⁺e⁻$e^{+}{e}^{-}$ colliders.     

The effect of alternative scoring methods on the analysis of rank order categorical data

The purpose of this article is to examine the effects of five univariate scoring techniques for rank order categorical data and the results of analyses using each of the techniques for five‐ and ten‐point bi‐polar adjective scales. The effect of scoring method and scale length is assessed for the resultant distance to multivariate normality, inter‐item reliability, discriminant analysis, least squares regression and logistic regression. For these data, the strongest effect of scoring was on distance to multivariate normality and determination of significant variables.     

Chiral Single-Molecule Potentiometers Based on Stapled ortho- Oligo(phenylene)ethynylenes

We report on the chemical design of chiral molecular junctions with stress-dependent conductance, whose helicity is maintained during the stretching of a single molecule junction due to the stapling of both ends of the inner helix. In the reported compounds, different conductive pathways are observed, with clearly different conductance values and plateau-length distributions, attributed to different conformations of the helical structures. The large chiro-optical responses and the potential use of these molecules as unimolecular spin filters have been theoretically proved using state-of-the-art Density Functional Theory (DFT) calculations, including a fully ab-initio estimation of the CISS-originating spin polarization which is done, for the first time, for a realistic molecular system.     

On n-hamiltonian graphs

A graph G of order p ? 3 is called n-hamiltonian, 0 ? n ? p ? 3, if the removal of any m vertices, 0 ? m ? n, results in a hamiltonian graph. A graph G of order p ? 3 is defined to be n-hamiltonian, ?p ? n ? 1, if there exists ?n or fewer pairwise disjoint paths in G which collectively span G. Various conditions in terms of n and the degrees of the vertices of a graph are shown to be sufficient for the graph to be n-hamiltonian for all possible values of n. It is also shown that if G is a graph of order p ? 3 and $\text{K}\text{(G) ? β(G) + n (?p ? n ? p ? 3)}$, then G is n-hamiltonian.     

Microporous organic crystals: an unusual case for L-leucyl-L-serine

Cocrystallized acetonitrile solvent molecules located inside 5.2 A channels in the crystal structure of L-leucyl-L-serine have been replaced by I2 molecules with full retention of the peptide scaffold.     

Filtration with Multiple Species of Particles

Transport in Porous Media - Membrane filtration of feed containing multiple species of particles is a common process in the industrial setting. In this work, we propose a model for filtration of a...