Voltammetric characterization of the ferrocene vertical bar ferrocenium and cobaltocenium vertical bar cobaltocene redox couples in RTILs

Ferrocene, Fc, and cobaltocenium hexafluorophosphate, CcPF(6), have been recommended for use as internal reference redox couples in room-temperature ionic liquids (RTILs), as well as in more conventional aprotic solvents. In this study, the electrochemical behavior of Fc and CcPF(6) is reported in eight commonly used RTILs; [C(2)mim][NTf2], [C(4)mim][NTf2], [C(4)mim][BF4], [C(4)mim][PF6], [C(4)mim][OTf], [C(4)mim][NO3], [C(4)mpyrr][NTf2], and [P-14,P-6.6,P-6][FAP], where [C(n)mim](+) = 1-butyl-3-methylimidazolium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [BF4](-) = tetrafluoroborate, [PF6](-) = hexafluorophosphate, [OTf](-) = trifluoromethylsulfonate, [NO3](-) = nitrate, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [P-14,P-6,P-6,P-6](+) = tris(ri-hexyl)-tetradecylphosphonium and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate, over a range of concentrations and temperatures. Solubilities and diffusion coefficients, D, of both the charged and neutral species were determined using double potential-step chronoamperometry, and CcPF(6) (36.5-450.0 mM) was found to be Much more Soluble than Fc (27.5-101.8 mM). It was observed that classical Stokes-Einstein diffusional behavior applies for Fc and CcPF(6) in all eight RTILs. Diffusion coefficients of Fc and CcPF(6) were calculated at a range of temperatures, and activation energies calculated. It was also determined that D for Fc and CcPF(6) does not change significantly with concentration. This supports the use of both Fe and CcPF(6) to provide a well-characterized and model redox couple for use as a voltammetric internal potential reference in RTILs contrary to previous literature reports in the former case.

Electrochemical kinetics of Ag vertical bar Ag+ and TMPD vertical bar TMPD+center dot in the room-temperature ionic liquid [C(4)mpyrr][NTf2]; toward optimizing reference electrodes for voltammetry in RTILs

The voltammetry and kinetics of the Ag vertical bar Ag+ system (commonly used as a reference electrode material in both protic/aprotic and RTIL solvents) was studied in the room-temperature ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C(4)mpyrr][NTf2] on a 10 mu m diameter Pt electrode. For the three silver salts investigated (AgOTf, AgNTf2, and AgNO3, where OTf- = trifluoromethanesulfonate, NTf2- = bis(trifluoromethylsulfonyl)imide, and NO3- = nitrate), the voltammetry gave rise to a redox couple characteristic of a

Investigating the Mechanism and Electrode Kinetics of the Oxygen vertical bar Superoxide (O-2 vertical bar O-2(center dot-)) Couple in Various Room-Temperature Ionic Liquids at Gold and Platinum Electrodes in the Temperature Range 298-318 K

The reduction of oxygen was studied over a range of temperatures (298-318 K) in n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2], and 1-butyl-2,3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [C(4)dmim][NTf2] on both gold and platinum microdisk electrodes, and the mechanism and electrode kinetics of the reaction investigated. Three different models were used to simulate the CVs, based on a simple electron transfer ('E'), an electron transfer coupled with a reversible homogeneous chemical step ('ECrev') and an electron transfer followed by adsorption of the reduction product ('EC(ads)'), and where appropriate, best fit parameters deduced, including the heterogeneous rate constant, formal electrode potential, transfer coefficient, and homogeneous rate constants for the ECrev mechanism, and adsorption/desorption rate constants for the EC(ads) mechanism. It was concluded from the good simulation fits on gold that a simple E process operates for the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2], and an ECrev process for [C(4)dmim][NTf2], with the chemical step involving the reversible formation of the O-2(center dot-)center dot center dot center dot [C(4)dmim](+) ion-pair. The E mechanism was found to loosely describe the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2] on platinum as the simulation fits were reasonable although not perfect, especially for the reverse wave. The electrochemical kinetics are slower on Pt, and observed broadening of the oxidation peak is likely due to the adsorption of superoxide on the electrode surface in a process more complex than simple Langmuirian. In [C(4)dmim][NTf2] the O-2(center dot-) predominantly ion-pairs with the solvent rather than adsorbs on the surface, and an ECrev quantitatively describes the reduction of oxygen on Pt also.

Subwavelength resolution for horizontal and vertical polarization by coupled arrays of oblate nanoellipsoids

A structure comprising a coupled pair of two-dimensional arrays of oblate plasmonic nanoellipsoids in a dielectric host medium is proposed as a superlens in the optical domain for both horizontal and vertical polarizations. By means of simulations it is demonstrated that a structure formed by silver nanoellipsoids is capable of restoring subwavelength features of the object for both polarizations at distances larger than half wavelength. The bandwidth of subwavelength resolution is in all cases very large (above 13%). (C) 2009 Optical Society of America

Computer simulations of seasonal outbreak and diurnal vertical migration of cyanobacteria

Algal blooms caused by cyanobacteria are characterized by two features with different time scales: one is seasonal outbreak and collapse of a bloom and the other is diurnal vertical migration. Our two-component mathematical model can simulate both phenomena, in which the state variables are nutrients and cyanobacteria. The model is a set of one-dimensional reaction-advection-diffusion equations, and temporal changes of these two variables are regulated by the following five factors: (1) annual variation of light intensity, (2) diurnal variation of light intensity, (3) annual variation of water temperature, (4) thermal stratification within a water column and (5) the buoyancy regulation mechanism. The seasonal change of cyanobacteria biomass is mainly controlled by factors, (1), (3) and (4), among which annual variations of light intensity and water temperature directly affect the maximum growth rate of cyanobacteria. The latter also contributes to formation of the thermocline during the summer season. Thermal stratification causes a reduction in vertical diffusion and largely prevents mixing of both nutrients and cyanobacteria between the epilimnion and the hypolimnion. Meanwhile, the other two factors, (2) and (5), play a significant role in diurnal vertical migration of cyanobacteria. A key mechanism of vertical migration is buoyancy regulation due to gas-vesicle synthesis and ballast formation, by which a quick reversal between floating and sinking becomes possible within a water column. The mechanism of bloom formation controlled by these five factors is integrated into the one-dimensional model consisting of two reaction-advection-diffusion equations.

Observation of stable phase jump lines in convection of a twisted nematic liquid crystal

We report observations of stable, localized, linelike structures in the spatially periodic pattern formed by nematic electroconvection, along which the phase of the pattern jumps by pi. With increasing electric voltage, these lines form a gridlike structure that goes over into a structure indistinguishable from the well-known grid pattern. We present theoretical arguments that suggest that the twisted cell geometry we are using is indirectly stabilizing the phase jump lines, and that the phase jump lines lattice is caused by an interaction of phase jump lines and a zig-zag instability of the surrounding pattern.

Weakly nonlinear vertical dust grain oscillations in dusty plasma crystals in the presence of a magnetic field

The weakly nonlinear regime of transverse paramagnetic dust grain oscillations in dusty (complex) plasma crystals is discussed. The nonlinearity, which is related to the sheath electric/magnetic field(s) and to the intergrain (electrostatic/magnetic dipole) interactions, is shown to lead to the generation of phase harmonics and, in the case of propagating transverse dust-lattice modes, to the modulational instability of the carrier wave due to self-interaction. The stability profile depends explicitly on the form of the electric and magnetic fields in the plasma sheath. The long term evolution of the modulated wave packet, which is described by a nonlinear Schrodinger-type equation, may lead to propagating localized envelope structures whose exact forms are presented and discussed. Explicit suggestions for experimental investigations are put forward. (C) 2004 American Institute of Physics.

Discrete breather modes associated with vertical dust grain oscillations in dusty plasma crystals

Accounting for the lattice discreteness and the sheath electric field nonlinearity in dusty plasma crystals, it is demonstrated that highly localized structures (discrete breathers) involving vertical (transverse, off-plane) oscillations of charged dust grains may exist in a dust lattice. These structures correspond to either extremely localized bright breather excitations (pulses) or dark excitations composed of dips/voids. Explicit criteria for selecting different breather modes are presented. (C) 2005 American Institute of Physics.

Prospective study of workplace social capital and depression: are vertical and horizontal components equally important?

Background Recent studies have emphasised the multidimensional nature of the social capital concept, but it is not known whether the health effects of social capital vary by dimension. The objective of this study was to examine the vertical component (ie, respectful and trusting relationships across power differentials at work) and the horizontal component of workplace social capital (trust and reciprocity between employees at the same hierarchical level) as risk factors for subsequent depression.

Measuring party organization: The vertical dimension of the multilevel organization of statewide parties in Spain and the UK

Over the past few years, attention to the role of state-wide political parties in multi-level polities has increased in recognition of their linkage function between levels of government, as these parties compete in both state-wide and regional elections across their countries. This article presents a coding scheme designed to describe the relationship between central and regional levels of state-wide parties. It evaluates the involvement of the regional branches in central decision-making and their degree of autonomy in the management of regional party affairs. This coding scheme is applied to state-wide parties in Spain (the socialist PSOE and the conservative Partido Popular) and in the UK (Labour, the Conservatives and the Liberal Democrats). It is an additional tool with which to analyse party organization and it facilitates the comparison of parties across regions and in different countries.

Granular anchors under vertical loading - axial pull

Granular anchors are a relatively new concept in ground engineering with relatively little known regarding their load–displacement behaviour, failure modes, ultimate pullout capacity and also potential applications. A granular anchor consists of three main components: a base plate; tendon and compacted granular backfill. The tendon is used to transmit the applied load to the base plate which compresses the granular material to form the anchor. A study of the load–displacement response and ultimate pullout capacity of granular anchors constructed in intact lodgement till and made ground deposits is reported in this paper. Parallel tests were also performed on cast insitu concrete anchors which are traditionally used for anchoring purposes. A new method of analysis for the determination of the ultimate pullout capacity of granular anchors is presented and verified experimentally, with the dominant mode of failure controlled by the column length to diameter ratio. Granular anchors with L/D > 7 principally failed on bulging whereas short granular anchors failed on shaft resistance, with the latter mobilising similar pullout capacities as conventional concrete anchors.