The VLT-FLAMES survey of massive stars: atmospheric parameters and rotational velocity distributions for B-type stars in the Magellanic Clouds (vol 457, pg 265, 2006)

We correct the estimates of the dispersions in the rotational velocities for early-type stars in our Galaxy (Dufton et al. 2006, A&A, 457, 265) and the Magellanic Clouds (Hunter et al. 2008, A&A, 479, 541). The corrected values are pi(1/4) (i.e. approximately 33%) larger than those published in the original papers.

Turbulent diffusion and mixing in interstellar dark clouds with adsorption onto grains

This paper reports the results of models of dark cloud chemistry incorporating a depth dependent density distribution with diffusive mixing and adsorption onto grains. The model is based on the approach taken by Xie et al. (1995), with the addition of grain accretion effects. Without diffusion, the central regions of the cloud freeze out in less than 10(7) years. Freeze-out time is dependent on density, so the diffuse outer region of the cloud remains abundant in gas for about an order of magnitude longer. We find that fairly small amounts of diffusive mixing can delay freeze-out at the centre of the model cloud for a time up to an order of magnitude greater than without diffusion, due to material diffusing inward from the edges of the cloud. The gas-phase lifetime of the cloud core can thus be increased by up to an order of magnitude or more by this process. We have run three different grain models with various diffusion coefficients to investigate the effects of changing the sticking parameters.

Dissolved Argon Changes the Rate of Diffusion in Room Temperature Ionic Liquids: Effect of the Presence and Absence of Argon and Nitrogen on the Voltammetry of Ferrocene

This work explores the effects of argon and nitrogen, two electrochemically and chemically inert gases frequently used in sample preparation of room temperature ionic liquid (RTIL) solutions, on the eelectrochemical characterization of ferrocene (Fc) dissolved in the RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C(2)mim][NTf2]). Remarkably, chronoamperometrically determined diffusion coefficients of Fc in [C(2)mim][NTf2] are found to increase from 4.8 (+/- 0.2) x 10(-11) m(2) s(-1) under vacuum conditions to 6.6 (+/- 0.5) x 10(-11) m(2) s(-1) in an atmosphere of 1 atm Ar. In contrast, exposing a vacuum-purified sample to an atmosphere of 1 atm N-2 resulted in no significant change in the measured diffusion coefficient of Fc. The effect of dissolved argon on diffusion transport is unexpected and has implications in electrochemistry and elsewhere. Fc was found to volatilize under vacuum conditions. We propose, however, that evacuation of the cell by vacuum prior to electrochemical measurements being carried out is the only way to ensure that no contamination of the sample occurs, and use of an in situ method of determining the diffusion coefficient and concentration of Fc dispells,any ambiguity associated with Fc depletion by vacuum.

SO2 Saturation of the Room Temperature Ionic Liquid [C(2)mim][NTf2] Much Reduces the Activation Energy for Diffusion

The physical effect of high concentrations of reversibly dissolved SO2 on [C(2)mim][NTf2] was examined using cyclic voltammetry, chronoamperometry, and ESR spectroscopy. Cyclic voltammetry of the oxidation of solutions of ferrocene, N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), and chloride in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethanesufonyl)imide ([C(2)mim][NTf2]) reveals an increase in limiting current of each species corresponding to the addition of increasing concentrations of sulfur dioxide. Quantitative chronoamperometry reveals an increase in each species' diffusion coefficient with SO2 concentration. When chronoamperometric data were obtained for ferrocene in [C(2)mim][NTf2] at a range of temperatures, the translational diffusion activation energy (29.0 +/- 0.5 kJ mol(-1)) was found to be in good agreement with previous studies. Adding SO2 results in apparent near-activationless translational diffusion. A significant decrease in the activation energy of rotational diffusion with the SO2 saturation of a 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) solution in [C(2)mim][NTf2] (29.9 +/- 2.0 to 7.7 +/- 5.3 kJ mol(-1)) was observed using electron spin resonance (ESR) spectroscopy. The reversible physical absorption Of SO2 by [C(2)mim][NTf2] should have no adverse effect on the ability of that ionic liquid to be employed as a solvent in an electrochemical gas sensor, and it is possible that the SO2-mediated reduction of RTIL viscosity could have intrinsic utility.

Diagnostic based modeling for determining absolute atomic oxygen densities in atmospheric pressure helium-oxygen plasmas

Absolute atomic oxygen ground state densities in a radio-frequency driven atmospheric pressure plasma jet, operated in a helium-oxygen mixture, are determined using diagnostic based modeling. One-dimensional numerical simulations of the electron dynamics are combined with time integrated optical emission spectroscopy. The population dynamics of the upper O 3p 3P (l=844 nm) atomic oxygen state is governed by direct electron impact excitation, dissociative excitation, radiation losses, and collisional induced quenching. Absolute values for atomic oxygen densities are obtained through comparison with the upper Ar 2p1 (l=750.4 nm) state. Results for spatial profiles and power variations are presented and show excellent quantitative agreement with independent two-photon laser-induced fluorescence measurements.

Silica grain labelling and EDX spectroscopy; evidence for inter-grain diffusion of Pt(NH3)(4)(2+) species during Pt/SiO2 catalyst preparation by ionic exchange

Labelling of silica grains and energy dispersive X-ray spectroscopy (EDX) in a TEM-FEG (field emission gun) were used to demonstrate the migration of Pt(NH3)(4)(2+) species from one grain to another during Pt/SiO2 catalyst preparation by the ion-exchange procedure.

Bimolecular rate constants for diffusion in ionic liquids

The temperature dependence of the bimolecular rate constants for a diffusion controlled reaction involving neutral reactants have been directly determined in five commonly used ionic liquids over the temperature range 5-70 degreesC.

The Y-procedure: How to extract the chemical transformation rate from reaction-diffusion data with no assumption on the kinetic model

The paper presents a new method to extract the chemical transformation rate from reaction–diffusion data with no assumption on the kinetic model (“kinetic model-free procedure”). It is a new non-steady-state kinetic characterization procedure for heterogeneous catalysts. The mathematical foundation of the Y-procedure is a Laplace-domain analysis of the two inert zones in a TZTR followed by transposition to the Fourier domain. When combined with time discretization and filtering the Y-procedure leads to an efficient practical method for reconstructing the concentration and reaction rate in the active zone. Using the Y-procedure the concentration and reaction rate of a non-steady state catalytic process can be determined without any pre-assumption regarding the type of kinetic dependence. The Y-procedure is the basis for advanced software for non-steady state kinetic data interpretation. The Y-procedure can be used to relate changes in the catalytic reaction rate and kinetic parameters to changes in the surface composition (storage) of a catalyst.

Diagnostic based modelling of radio-frequency driven atmospheric pressure plasmas

Diagnostic based modelling (DBM) actively combines complementary advantages of numerical plasma simulations and relatively simple optical emission spectroscopy (OES). DBM is employed to determine absolute atomic oxygen ground state densities in a helium–oxygen radio-frequency driven atmospheric pressure plasma jet. A comparatively simple one-dimensional simulation yields detailed information on electron properties governing the population dynamics of excited states. Important characteristics of the electron dynamics are found to be largely insensitive to details of the chemical composition and to be in very good agreement with space and phase-resolved OES. Benchmarking the time and space resolved simulation allows us to subsequently derive effective excitation rates as the basis for DBM with simple space and time integrated OES. The population dynamics of the upper O 3p 3P (? = 844 nm) atomic oxygen state is governed by direct electron impact excitation, dissociative excitation, radiation losses and collisional induced quenching. Absolute values for atomic oxygen densities are obtained through tracer comparison with the upper Ar 2p1 (? = 750.4 nm) state. The presented results for the atomic oxygen density show excellent quantitative agreement with independent two-photon laser-induced fluorescence measurements.

Aminolaevulinic acid diffusion characteristics in 'in vitro' normal human skin and actinic keratosis: implications for topical photodynamic therapy

Background: The response rate of aminolaevulinic acid (ALA)-based photodynamic therapy (PDT) in certain subtypes of actinic keratosis (AK), such as hypertrophic and hyperkeratotic lesions, is variable, an effect attributable to a supposed lack of ALA penetration. A detailed and depth-related profile of spatial ALA permeation in AK following drug administration would lead to a greater understanding of concentrations achievable before protoporphyrin IX biosynthesis and subsequent PDT.

Nonlinear frequency coupling in dual radio-frequency driven atmospheric pressure plasmas

Plasma ionization, and associated mode transitions, in dual radio-frequency driven atmospheric pressure plasmas are governed through nonlinear frequency coupling in the dynamics of the plasma boundary sheath. Ionization in low-power mode is determined by the nonlinear coupling of electron heating and the momentary local plasma density. Ionization in high-power mode is driven by electron avalanches during phases of transient high electric fields within the boundary sheath. The transition between these distinctly different modes is controlled by the total voltage of both frequency components.

Diagnostic-based modeling on a micro-scale atmospheric-pressure plasma jet

Diagnostic-based modeling (DBM) actively combines complementary advantages of numerical plasma simulations and relatively simple optical emission spectroscopy (OES). DBM is applied to determine spatial absolute atomic oxygen ground-state density profiles in a micro atmospheric-pressure plasma jet operated in He–O2. A 1D fluid model with semi-kinetic treatment of the electrons yields detailed information on the electron dynamics and the corresponding spatio-temporal electron energy distribution function. Benchmarking this time- and space-resolved simulation with phase-resolved OES (PROES) allows subsequent derivation of effective excitation rates as the basis for DBM. The population dynamics of the upper O(3p3P) oxygen state (? = 844 nm) is governed by direct electron impact excitation, dissociative excitation, radiation losses, and collisional induced quenching. Absolute values for atomic oxygen densities are obtained through tracer comparison with the upper Ar(2p1) state (? = 750.4 nm). The resulting spatial profile for the absolute atomic oxygen density shows an excellent quantitative agreement to a density profile obtained by two-photon absorption laser-induced fluorescence spectroscopy.

Non-invasive VHF monitoring of low-temperature atmospheric pressure plasma

A real-time VHF swept frequency (20–300 MHz) reflectometry measurement for radio-frequency capacitive-coupled atmospheric pressure plasmas is described. The measurement is scalar, non-invasive and deployed on the main power line of the plasma chamber. The purpose of this VHF signal injection is to remotely interrogate in real-time the frequency reflection properties of plasma. The information obtained is used for remote monitoring of high-value atmospheric plasma processing. Measurements are performed under varying gas feed (helium mixed with 0–2% oxygen) and power conditions (0–40 W) on two contrasting reactors. The first is a classical parallel-plate chamber driven at 16 MHz with well-defined electrical grounding but limited optical access and the second is a cross-field plasma jet driven at 13.56 MHz with open optical access but with poor electrical shielding of the driven electrode. The electrical measurements are modelled using a lumped element electrical circuit to provide an estimate of power dissipated in the plasma as a function of gas and applied power. The performances of both reactors are evaluated against each other. The scalar measurements reveal that 0.1% oxygen admixture in helium plasma can be detected. The equivalent electrical model indicates that the current density between the parallel-plate reactor is of the order of 8–20 mA cm-2 . This value is in accord with 0.03 A cm-2 values reported by Park et al (2001 J. Appl. Phys. 89 20–8). The current density of the cross-field plasma jet electrodes is found to be 20 times higher. When the cross-field plasma jet unshielded electrode area is factored into the current density estimation, the resultant current density agrees with the parallel-plate reactor. This indicates that the unshielded reactor radiates electromagnetic energy into free space and so acts as a plasma antenna.