Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

An efficient sonochemical oxidation of benzyl alcohols into benzaldehydes by FeCl3/HNO3 in acetone

Sonochemical oxidation of benzyl alcohols into corresponding aldehydes by FeCl(3)/HNO(3) in acetone at room temperature has been reported. All substrates give good yield of the products within 10-25 min. The reaction of selected substrates were also studied under reflux and at the room temperature. Further, various Lewis acids were used to evaluate their catalytic efficacy.     

233Pa(2nth, f ) cross-section determination using a fission track technique

The νp process is a primary nucleosynthesis process which occurs in core-collapse supernovae. An essential role in this process is being played by electron antineutrinos. They generate, by absorption on protons, a supply of neutrons which, by (n, p) reactions, allow to overcome waiting point nuclei with rather long beta-decay and proton-capture lifetimes. The synthesis of heavy elements by the νp process depends sensitively on the $\bar \nu _e$ luminosity and spectrum. As has been shown recently, the latter are affected by collective neutrino flavor oscillations which can swap the $\bar \nu _e$ and $\bar \nu _{\mu ,\tau }$ spectra above a certain split energy. Assuming such a swap scenario, we have studied the impact of collective neutrino flavor oscillations on the νp-process nucleosynthesis. Our results show that the production of light p-nuclei up to mass number A = 108 is very sensitive to collective neutrino oscillations.     

Study of the K shell photoelectric parameters of Dy,Yb and W atoms using low energy bremsstrahlung radiation

Low energy external bremsstrahlung (EB) photons were used to estimate the K shell photoelectric parameters; the K shell photoelectric cross section at the K edge, the K shell binding energy, the K shell jump ratio, the K shell jump factors, the Davisson-Kirchner ratio and the K shell oscillator strength for dysprosium (Dy), ytterbium (Yb) and tungsten (W) atoms. The EB photons are produced in the nickel (Ni) target by using the beta particles from a weak beta source of ⁹⁰Sr–⁹⁰Y. These photons are made to fall on these elemental targets of our interest and the transmitted spectrum is measured using GMX 10P HPGe detector coupled to an 8K multichannel analyzer. The sharp decrease at the K edge in the measured spectrum is used to determine the K shell photoelectric parameters of these elements. The experimental results are in good agreement with the theoretical values.     

Effect of metallic and hyperbolic metamaterial surfaces on electric and magnetic dipole emission transitions

Spontaneous emission patterns of electric and magnetic dipoles on different metallic surfaces and a hyperbolic metamaterial (HMM) surface were simulated using the dyadic Green’s function technique. The theoretical approach was verified by experimental results obtained by measuring angular-dependent emission spectra of europium ions on top of different films. The results show the modified behavior of electric and magnetic dipoles on metallic and HMM surfaces. The results of numerical calculations agree well with experimental data.     

Frequency down-conversion using cascading arrays of coupled nonlinear oscillators

A novel coupling scheme using M≥2 arrays of coupled nonlinear elements arranged in a specific configuration can produce multifrequency patterns or a frequency down-converting effect on an external (input) signal. In such a configuration, each array contains N≥3 nonlinear elements with similar dynamics and each element is coupled unidirectionally within the array. The subsequent arrays in the cascade are coupled in a similar fashion except that the coupling direction is arranged in the opposite direction with respect to that of the preceding array. Previous theoretical work and numerical results have already been reported in [P. Longhini, A. Palacios, V. In, J. Neff, A. Kho, A. Bulsara, Exploiting dynamical symmetry in coupled nonlinear elements for efficient frequency down-conversion, Phys. Rev. E 76 (2007) 026201]. This paper is focused on results of experiments implemented on two distinct systems: the first system is fabricated using discrete component circuits to approximate an overdamped bistable Duffing oscillator described by a quartic potential system, and the second system is built in a microcircuit, where the nonlinearity is described by a hyperbolic tangent function, with the option of applying an external signal to investigate resonant effects. In particular, the circuit implementations for each case use M=2 arrays, but their voltage oscillations already demonstrate that the frequency relations between each of the successive arrays decrease by a rational factor, conforming to earlier theoretical and numerical results for the general case containing M arrays. This behavior is important for efficient frequency down-converting applications which are essential in many communication systems where heterodyning is typically used and it involves multi-step processes with complicated circuitry.     

Efficient implementation of the proper outlet flow conditions in blood flow simulations through asymmetric arterial bifurcations

We present an efficient implementation of the proper (in vivo) outlet boundary conditions in detailed, three‐dimensional (3D) and time‐periodic simulations of blood flow through arteries. This is achieved through the intermediate use of an approximate ‘simulant’ model of the outlet pressure/flow relationship corresponding to the full 3D and time‐dependent numerical simulation. This model allows us to efficiently couple the 3D outlet pressure/flow conditions to the equivalent relations due to the downstream arterial network, as obtained from a one‐dimensional approximate model in the form of Fourier frequency impedance coefficients. An adjustable time‐periodic function correction term in the simulant model requires input from the full 3D model that has to run iteratively until convergence. The advantage of the proposed numerical scheme is that it decouples the upstream detailed simulation from the downstream approximate network model offering exceptional versatility. This approach is demonstrated here in a series of detailed 3D simulations of blood flow, performed using the commercial software FLUENT?, through an asymmetric arterial bifurcation. Two cases are considered: first a healthy system patterned after the left main coronary arterial bifurcation, and second a diseased case where an occlusion has developed in one of the daughter vessels, resulting in strengthening the asymmetry of the bifurcation. Rapid convergence of the iterative process was achieved in both cases. Subtle changes occur in the shear patterns of the daughter vessels, whereas the flow distribution is quite different. In the presence of a stenosis additional regions of low shear develop due to inertial effects. Copyright © 2010 John Wiley & Sons, Ltd.     

Performance analysis of nitride alternative plasmonic materials for localized surface plasmon applications

We consider methods to define the performance metrics for different plasmonic materials to be used in localized surface plasmon applications. Optical efficiencies are shown to be better indicators of performance as compared to approximations in the quasistatic regime. The near-field intensity efficiency, which is a generalized form of the well-known scattering efficiency, is a more flexible and useful metric for local-field enhancement applications. We also examine the evolution of the field enhancement from a particle surface to the far-field regime for spherical nanoparticles with varying radii. Titanium nitride and zirconium nitride, which were recently suggested as alternative plasmonic materials in the visible and near-infrared ranges, are compared to the performance of gold. In contrast to the results from quasistatic methods, both nitride materials are very good alternatives to the usual plasmonic materials.