Experimental and theoretical study of the reaction of the ethynyl radical with nitrous oxide, C2H + N2O

We investigated the rate constants and reaction mechanism of the gas phase reaction between the ethynyl radical and nitrous oxide (C(2)H + N(2)O) using both experimental methods and electronic structure calculations. A pulsed-laser photolysis/chemiluminescence technique was used to determine the absolute rate coefficient over the temperature range 570 K to 836 K. In this experimental temperature range, the measured temperature dependence of the overall rate constants can be expressed as: k(T) (C(2)H + N(2)O) = 2.93 × 10(-11) exp((-4000 ± 1100) K/T) cm(3) s(-1) (95% statistical confidence). Portions of the C(2)H + N(2)O potential energy surface (PES), containing low-energy pathways, were constructed using the composite G3B3 method. A multi-step reaction route leading to the products HCCO + N(2) is clearly preferred. The high selectivity between product channels favouring N(2) formation occurs very early. The pathway corresponds to the addition of the terminal C atom of C(2)H to the terminal N atom of N(2)O. Refined calculations using the coupled-cluster theory whose electronic energies were extrapolated to the complete basis set limit CCSD(T)/CBS led to an energy barrier of 6.0 kcal mol(-1) for the entrance channel. The overall rate constant was also determined by application of transition-state theory and Rice-Ramsperger-Kassel-Marcus (RRKM) statistical analyses to the PES. The computed rate constants have similar temperature dependence to the experimental values, though were somewhat lower.     

The maximum order of adjacency matrices of graphs with a given rank

We look for the maximum order m(r) of the adjacency matrix A of a graph G with a fixed rank r, provided A has no repeated rows or all-zero row. Akbari, Cameron and Khosrovshahi conjecture that m(r)?=?2^(r+2)/2 ? 2 if r is even, and m(r)?=?5 · 2^(r?3)/2 ? 2 if r is odd. We prove the conjecture and characterize G in the case that G contains an induced subgraph ${\frac{r}{2}K_2}$ or ${\frac{r-3}{2}K_2+K_3}$ .     

The electronic properties of graphene and graphene ribbons under simple shear strain

A tight-binding model is used to study the energy band of graphene and graphene ribbon under simple shear strain. The ribbon consists of lines of carbon atoms in an armchair or zigzag orientation where a simple shear strain is applied in the x-direction keeping the atomic distances in the y-direction unchanged. Such modification in the lattice gives an energy band that differs in several aspects from the one without any shear and with pure shear. The changes in the spectrum depend on the line displacement of the ribbon, and also on the modified hopping parameter. It is also shown that this simple shear strain tunes the electronic properties of both graphene and graphene ribbon, opening and closing energy gaps for different displacements of the system. The modified density of states is also shown.     

Quantum cascades in nano-engineered superconductors: geometrical, thermal and paramagnetic effects

The effect of a parallel magnetic field on the orbital motion of electrons in high-quality superconducting nanowires resulting in a superconductor-to-normal transition which occurs through a cascade of jumps in the order parameter as a function of the magnetic field. Such cascades originate from the transverse size quantization that splits the conduction band into a series of subbands. Here, based on a numerical solution of the Bogoliubov-de Gennes equations for a hollow nanocylinder, we investigate how the quantum-size cascades depend on the confining geometry, i.e., by changing the cylinder radius R and its thickness d we cover the range from the nanowire-like to the nanofilm-like regime. The cascades are shown to become much less pronounced when increasing R/d, i.e., when the nanofilm-like regime is approached. When the temperature is non-zero they are thermally smoothed. This includes the spin-magnetic-field interaction which reduces the critical (depairing) parallel magnetic field H(c,//) but does not have any qualitative effect on the quantum cascades. From our calculations it is seen that the paramagnetic limiting field H(par) significantly exceeds H(c,//) even in extremely narrow nanocylinders, i.e., when R,d are down to a few nanometers, and H(c,//) is only about 10% larger when switching-off the spin-magnetic-field interaction in this case. Both characteristic fields, H(c,//) and H(par), exhibit pronounced quantum-size oscillations. We demonstrate that the quantum cascades and the quantum-size oscillations survive in the presence of surface roughness.     

(R)-4-phenyloxazolidin-2-thione: an efficient chiral auxiliary for [4+2] cycloaddition of 1-aminodiene and activated phosphonodienophiles

A theoretical model for the facial selectivity of N-dienyl oxazolidin-2-(thi)one and thiazolidin-2-thione 2a-c is presented. Our analysis provides a clear understanding of factors controlling stereoselectivity in reaction of these dienes, and allows predictions of high diastereoselectivity in the case of oxazolidin-2-thionyl diene (2b). The application of this diene to the synthesis of β- and γ-aminophosphonic derivatives is then investigated. Under classical conditions or under microwave activation, the D-A reaction of diene 2b leads to aminophosphonic chirons with high regio- and stereoselectivities.     

Novel commensurability effects in superconducting films with antidot arrays

Vortex configurations in superconducting films with regular arrays of antidots (holes) are calculated within the nonlinear Ginzburg-Landau theory. In addition to the well-established matching phenomena, we predict (i) the nucleation of giant-vortex states between the antidots, (ii) the combination of giant- and multivortices at rational matching fields, and (iii) for particular values of the vorticity, symmetry imposed creation of vortex-antivortex configurations.     

HPLC-DAD-qTOF Compositional Analysis of the Phenolic Compounds Present in Crude Tomato Protein Extracts Derived from Food Processing

The conversion of raw fruits and vegetables, including tomatoes into processed food products creates side streams of residues that can place a burden on the environment. However, these processed residues are still rich in bioactive compounds and in an effort to valorize these materials in tomato by-product streams, the main aim of this study is to extract proteins and identify the main phenolic compounds present in tomato pomace (TP), peel and skins (TPS) by HPLC-DAD-ESI-QTOF. Forty different phenolic compounds were identified in the different tomato extracts, encompassing different groups of phenolic compounds, including derivatives of simple phenolic acid derivatives, hydroxycinnamoylquinic acid, flavones, flavonones, flavonol, and dihydrochalcone. In the crude protein extract (TPE) derived from tomatoes, most of these compounds were still present, confirming that valuable phenolic compounds were not degraded during food processing of these co-product streams. Moreover, phenolic compounds present in the tomato protein crude extract could provide a valuable contribution to the required daily intake of phenolics that are usually supplied by consuming fresh vegetables and fruits.     

Orthogonal representations over finite fields and the chromatic number of graphs

We study the relationship between the minimum dimension of an orthogonal representation of a graph over a finite field and the chromatic number of its complement. It turns out that for some classes of matrices defined by a graph the 3-colorability problem is equivalent to deciding whether the class defined by the graph contains a matrix of rank 3 or not. This implies the NP-hardness of determining the minimum rank of a matrix in such a class. Finally we give for any class of matrices defined by a graph that is interesting in this respect a reduction of the 3-colorability problem to the problem of deciding whether or not this class contains a matrix of rank equal to three.The author is financially supported by the Cooperation Centre Tilburg and Eindhoven Universities.