A comparative study on the reactivity of electrogenerated bromine with cyclohexene in acetonitrile and the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide

The reactivity of electrogenerated bromine with cyclohexene has been studied on a platinum microelectrode by linear sweep and cyclic voltammetry in both the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, and the conventional aprotic solvent, acetonitrile. Variation in the voltammetric response was observed in the two solvents, indicating that the bromination reaction proceeded via separate mechanisms. To identify the different products, electrolysis was conducted on the preparative scale and NMR spectroscopy confirmed that while bromination of the organic substrate in the ionic liquid yields trans-1,2-dibromocyclohexane, in acetonitrile, trans-1-(N-acetylamino)-2-bromocyclohexane is instead obtained as the major product. The reaction mechanism for bromination in acetonitrile has been modeled using digital simulation.

Electrochemical Oxidation of Hydrogen Sulfide at Platinum Electrodes in Room Temperature Ionic Liquids: Evidence for Significant Accumulation of H2S at the Pt/1-Butyl-3-methylimidazolium Trifluoromethylsulfonate Interface

Electrochemical oxidation of hydrogen sulfide gas (H2S) has been studied at a platinum microelectrode (10 mu m diameter) in five room temperature ionic liquids (RTILs): [C(4)mim][OTf], [C(4)dmim][NTf2], [C(4)mim][PF6],. [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP] (where [C-n mim](+) = 1-alkyl-3-methylimidazolium, [C(n)dmim](+) = 1-alkyl-2,3-dimethylimidazolium, [P-14,P-6,P-6,P-6](+) = tris(p-hexyl)-tetradecylphosphonium, [OTf](-) = trifluoromethlysulfonate, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [PF6](-) = hexafluorophosphate, and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate). In four of the RTILs ([C(4)dmim][NTf2], [C(4)mim][PF6], [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP]), no clear oxidative signal was observed. In [C(4)mim][OTf], a chemically irreversible oxidation peak was observed on the oxidative sweep with no signal seen on the reverse scan. The oxidative signal showed an adsorptive stripping peak type followed by near steady-state limiting current behavior. Potential step chronoamperometry was carried out on the reductive wave, giving a diffusion coefficient and solubility of 1.6 x 10(-11) m(2) s(-1) and 7 mM, respectively (at 25 degrees C). Using these data, we modeled the oxidation signal kinetically, assuming adsorption preceded oxidation and that adsorption was approximately Langmuirian. The oxidation step was described by an electrochemically fully irreversible Tafel law/Butler-Volmer formalism. Modeling indicated a substantial buildup of H2S in the double layer in excess of the coverage that would be expected for a monolayer of chemisorbed H2S, reflecting high solubility of the gas in [C(4)mim][OTf] and possible attractive interactions with the [OTf](-) anions accumulated at the electrode at potentials positive of the potential of zero charge. Solute enrichment of the double layer in the solution adjacent to the electrode appears a novel feature of RTIL electrochemistry.

Optomechanical to mechanical entanglement transformation

We present a scheme for generating entanglement between two mechanical oscillators that have never interacted with each other by using an entanglement-swapping protocol. The system under study consists of a Michelson-Morley interferometer comprising mechanical systems embodied by two cantilevers. Each of them is coupled to a field mode via the radiation pressure mechanism. Entanglement between the two mechanical systems is set by measuring the output modes of the interferometer. We also propose a control mechanism for the amount of entanglement based on path-length difference between the two arms.

Channel characterization for single- and multiple-antenna wearable systems used for indoor body-to-body communications

In this paper, an analysis of radio channel characteristics for single- and multiple-antenna bodyworn systems for use in body-to-body communications is presented. The work was based on an extensive measurement campaign conducted at 2.45 GHz representative of an indoor sweep and search scenario for fire and rescue personnel. Using maximum-likelihood estimation in conjunction with the Akaike information criterion (AIC), five candidate probability distributions were investigated and from these the kappa - mu distribution was found to best describe small-scale fading observed in the body-to-body channels. Additional channel parameters such as autocorrelation and the cross-correlation coefficient between fading signal envelopes were also analyzed. Low cross correlation and small differences in mean signal levels between potential dual-branch diversity receivers suggested that the prospect of successfully implementing diversity in this type application is extremely good. Moreover, using selection combination, maximal ratio, and equal gain combining, up to 8.69-dB diversity gain can be made available when four spatially separated antennas are used at the receiver. Additional improvements in the combined envelopes through lower level crossing rates and fade durations at low signal levels were also observed.

Dendrochronology and Deer Park Farms

This chapter examines some aspects of the environmental
context for the constructional activity observed at Deer
Park Farms (DPF). This can be done at several levels by
observing what dendrochronology suggests in terms of
environment and environmental change across the period
from around AD 500 to 1000. Looking at the broad sweep
of tree growth across the period, something not previously
attempted, we can make comparisons between tree
growth in Ireland and elsewhere in Europe. We can study
abrupt events in the records and draw on information
from other sources in an attempt to paint a picture of the
period against which to view the constructional activity
on the site itself. It is worth remarking that there is no
blueprint for this work. Most of the information used has
only recently been produced and it is largely independent
of conventional history.

Sex, drugs and STDs: Preliminary findings from the Belfast Youth Development Study

Young people's participation in sexual risk behaviours is commonly linked with participation in a range of other risky behaviours, and in particular with substance use behaviours. This cross-sectional analysis of the sixth sweep of the Belfast Youth Development Study aimed to examine associations between substance use and sexual activity and related risks among 17-19-year olds in Northern Ireland. Being sexual activity and participating in sexual risk behaviours was associated with the use of a range of licit and illicit substances particularly alcohol and ecstasy. Additionally, females were more likely to have been tested for a sexually transmitted disease (STD). The findings add to the existing research body suggesting that substance misuse and sexual risk behaviours tend to co-occur in adolescence and highlight a need to develop appropriate interventions and initiatives for school aged young people.

A frequency measure robust to linear filtering

It is noted that the determination of an oscillation frequency by used of the power spectrum of measured time series is susceptible to filtering of the signal. Similarly, frequency measurements made by period counting can yield different, results depending on how the signal is filtered for noise reduction. In an attempt to eliminate these ambiguities, a new measure of frequency, based on an approximate reconstruction of the phase-space trajectory of the oscillator from the signal, is introduced. This measure is shown to be invariant under linear filtering. For this reason, it is also inaccessible by spectral methods. The effect of filtering on frequency for weakly nonlinear, noisy oscillators, to which this definition applies only imperfectly, is quantified. This work provides the theoretical basis for frequency measurements employing MIRVA filtering.

Phase synchronization from noisy univariate signals

We present methods for detecting phase synchronization of two unidirectionally coupled, self-sustained noisy oscillators from a signal of the driven oscillator alone. One method detects soft phase locking; another hard phase locking. Both are applied to the problem of detecting phase synchronization in von Karman vortex flow meters.

Spontaneous nucleation of structural defects in inhomogeneous ion chains

Structural defects in ion crystals can be formed during a linear quench of the transverse trapping frequency across the mechanical instability from a linear chain to a zigzag structure. The density of defects after the sweep can be conveniently described by the Kibble-Zurek mechanism (KZM). In particular, the number of kinks in the zigzag ordering can be derived from a time-dependent Ginzburg-Landau equation for the order parameter, here the zigzag transverse size, under the assumption that the ions are continuously laser cooled. In a linear Paul trap, the transition becomes inhomogeneous, since the charge density is larger in the center and more rarefied at the edges. During the linear quench, the mechanical instability is first crossed in the center of the chain, and a front, at which the mechanical instability is crossed during the quench, is identified that propagates along the chain from the center to the edges. If the velocity of this front is smaller than the sound velocity, the dynamics become adiabatic even in the thermodynamic limit and no defect is produced. Otherwise, the nucleation of kinks is reduced with respect to the case in which the charges are homogeneously distributed, leading to a new scaling of the density of kinks with the quenching rate. The analytical predictions are verified numerically by integrating the Langevin equations of motion of the ions, in the presence of a time-dependent transverse confinement. We argue that the non-equilibrium dynamics of an ion chain in a Paul trap constitutes an ideal scenario to test the inhomogeneous extension of the KZM, which lacks experimental evidence to date.

Berry phase in open quantum systems: a quantum Langevin equation approach

The evolution of a two level system with a slowly varying Hamiltonian, modeled as a spin 1/2 in a slowly varying magnetic field, and interacting with a quantum environment, modeled as a bath of harmonic oscillators is analyzed using a quantum Langevin approach. This allows to easily obtain the dissipation time and the correction to the Berry phase in the case of an adiabatic cyclic evolution.

Managing Island Life:Social, Economic and Political Dimensions of Formality and Informality in Island Life

"Managing Island Life: Social, Economic and Political Dimensions of Formality and Informality in Island Life" is a significant and timely contribution to the study of islands and island life. Wide-ranging in terms of both geographical and theoretical sweep, contributions consider the conceptualisation of the island as well as social, economic and political dimensions of island life and living. Showcasing the current state of island research, contributors cover diverse areas of island life such as: informal economies in the West Indies; the effects of natural convservation policies in the Highlands and Islands of Scotland; the role of internet sites in British Isles heritage tourism, and the impact of multicultural policies in the Indian Ocean. This volume will appeal to undergraduate social scientists as well as professional anthropologists, sociologists and geographers, policy makers and islands and regional specialists.

Strong Coupling and Long-Range Collective Interactions in Optomechanical Arrays

We investigate the collective optomechanics of an ensemble of scatterers inside a Fabry-Pérot resonator and identify an optimized configuration where the ensemble is transmissive, in contrast to the usual reflective optomechanics approach. In this configuration, the optomechanical coupling of a specific collective mechanical mode can be several orders of magnitude larger than the single-element case, and long-range interactions can be generated between the different elements since light permeates throughout the array. This new regime should realistically allow for achieving strong single-photon optomechanical coupling with massive resonators, realizing hybrid quantum interfaces, and exploiting collective long-range interactions in arrays of atoms or mechanical oscillators.

The role of Na surface species on oxygen charge transfer in the Pt/YSZ system

The role of sodium surface species in the modification of a platinum (Pt) catalyst film supported on 8 mol% yttria-stabilised-zirconia (YSZ) was investigated under a flow of 20 kPa oxygen at 400 °C. Cyclic and linear sweep voltammetry were used to investigate the kinetics of the oxygen charge transfer reaction. The Pt/YSZ systems of both ‘clean’ and variable-coverage sodium-modified catalyst surfaces were also characterised using SEM, XPS and work function measurements using the Kelvin probe technique.

Samples with sodium coverage from 0.5 to 100% were used. It was found that sodium addition modifies the binding energy of oxygen onto the catalyst surface. Cyclic voltammetry experiments showed that higher overpotentials were required for oxygen reduction with increasing sodium coverage. In addition, sodium was found to modify oxygen storage and/or adsorption and diffusion increasing current densities at higher cathodic overpotential. Ex situ XPS measurements showed the presence of sodium hydroxide, carbonate and/or oxide species on the catalyst surface, while the Kelvin probe technique showed a decrease of approximately 250 meV in the work function of samples with more than 50% sodium coverage (compared to a nominally ‘clean’ sample).

Selectable linear or quadratic coupling in an optomechanical system

There has been much interest recently in the analysis of optomechanical systems incorporating dielectric nano- or microspheres inside a cavity field. We analyse here the situation when one of the mirrors of the cavity itself is also allowed to move. We reveal that the interplay between the two oscillators yields a cross-coupling that results in, e.g., appreciable cooling and squeezing of the motion of the sphere, despite its nominal quadratic coupling. We also discuss a simple modification that would allow this cross-coupling to be removed at will, thereby yielding a purely quadratic coupling for the sphere.

Comparative performances of birnessite and cryptomelane MnO as electrode material in neutral aqueous lithium salt for supercapacitor application

Na-doped Birnessite-type manganese oxide (d-MnO) has been synthesized using the chemical method and characterized through X-ray diffraction and SEM, showing the lamellar structure and high crystal structure. A comparative study of the electrochemical performances of this material with those of the commercial Cryptomelane-type MnO has then been undertaken in ten neutral aqueous electrolytes for supercapacitor applications. Aqueous electrolytes, containing a lithium salt, LiX (where X = SO , NO, CHCO , CHSO, ClO , CHCO, TFSI, Beti, BOB, or Lact), have been first prepared under neutral pH conditions to reach the salt concentration, providing the maximum in conductivity. Their transport properties are then investigated through conductivities, viscosities, and self-diffusion coefficient measurements. Second, the thermal behaviors of these electrolytic aqueous solutions are then evaluated by using a differential scanning calorimeter from (213.15 to 473.15) K in order to access their liquid range temperatures. Cyclic voltammograms (CV) in three electrode configurations are thereafter investigated using Na Birnessite and Cryptomelane as working electrode material from (-0.05 to 1.5) V versus Ag/AgCl at various sweep rates from (2 to 100) mV·s. According to anion nature/structure and manganese oxide material type, different CV responses are observed, presenting a pure capacitive profile for Beti or CH CO and an additional pseudocapacitive signal for the smallest anions, such as ClO and NO . The capacitances, energies, and efficiencies are finally calculated. These results indicate clearly that electrolytes based on a mineral lithium salt under neutral pH condition and high salt concentration (up to 5 mol·L) have better electrochemical performances than organic ones, up to 1.4 V with good material stability and capacity retention. The relationship between transport properties, electrostatic and steric hindrance considerations of hydrated ions, and their electrochemical performances is discussed in order to understand further the lithium intercalation-deintercalation processes in the lamellar or tunnel structure of investigated MnO. © 2013 American Chemical Society.