Interacting kinetics of neutral and ionic species in an atmospheric-pressure helium-oxygen plasma with humid air impurities

We unravel the complex chemistry in both the neutral and ionic systems of a radio-frequency-driven atmospheric-pressure plasma in a helium-oxygen mixture (He-0.5% O) with air impurity levels from 0 to 500 ppm of relative humidity from 0% to 100% using a zero-dimensional, time-dependent global model. Effects of humid air impurity on absolute densities and the dominant production and destruction pathways of biologically relevant reactive neutral species are clarified. A few hundred ppm of air impurity crucially changes the plasma from a simple oxygen-dependent plasma to a complex oxygen-nitrogen-hydrogen plasma. The density of reactive oxygen species decreases from 10 to 10 cm, which in turn results in a decrease in the overall chemical reactivity. Reactive nitrogen species (10 cm ), atomic hydrogen and hydroxyl radicals (10-10 cm) are generated in the plasma. With 500 ppm of humid air impurity, the densities of positively charged ions and negatively charged ions slightly increase and the electron density slightly decreases (to the order of 10 cm). The electronegativity increases up to 2.3 compared with 1.5 without air admixture. Atomic hydrogen, hydroxyl radicals and oxygen ions significantly contribute to the production and destruction of reactive oxygen and reactive nitrogen species. © 2013 IOP Publishing Ltd.

Chemical kinetics and reactive species in atmospheric pressure helium-oxygen plasmas with humid-air impurities

In most applications helium-based plasma jets operate in an open-air environment. The presence of humid air in the plasma jet will influence the plasma chemistry and can lead to the production of a broader range of reactive species. We explore the influence of humid air on the reactive species in radio frequency (rf)-driven atmospheric-pressure helium-oxygen mixture plasmas (He-O, helium with 5000 ppm admixture of oxygen) for wide air impurity levels of 0-500 ppm with relative humidities of from 0% to 100% using a zero-dimensional, time-dependent global model. Comparisons are made with experimental measurements in an rf-driven micro-scale atmospheric pressure plasma jet and with one-dimensional semi-kinetic simulations of the same plasma jet. These suggest that the plausible air impurity level is not more than hundreds of ppm in such systems. The evolution of species concentration is described for reactive oxygen species, metastable species, radical species and positively and negatively charged ions (and their clusters). Effects of the air impurity containing water humidity on electronegativity and overall plasma reactivity are clarified with particular emphasis on reactive oxygen species. © 2013 IOP Publishing Ltd.

Release kinetics of oleyl alcohol from a self-lubricating silicone biomaterial

The development of self-lubricating silicone elastomeric biomaterials, prepared using the novel crosslinking agent tetra( oleyloxy) silane and having very low coefficients of friction, has recently been reported. In this study, the in vitro release characteristics of lubricious oleyl alcohol produced during the silicone curing reaction have been quantitatively evaluated for a range of tetra( propoxy) silane/tetra(oleyloxy) silane crosslinker compositions using a novel evaporative light scattering detection method in combination with high performance liquid chromatography. The mechanism of oleyl alcohol release was seen to deviate from a simple, matrix-controlled diffusion process and instead obeyed an anomalous transport mechanism. An explanation for the observed release behaviour has been proposed based on competitive reaction kinetics between the tetra( oleyloxy) silane and tetra( propoxy) silane substituents of the silicone crosslinking agents.

Thin Ta films: growth, stability, and diffusion studied by molecular-dynamics simulations

We report results of classical molecular-dynamics simulations of bcc and beta-Ta thin films. Thermal PVD film growth, surface roughness, argon ion bombardment, phase stability and transformation, vacancy and adatom diffusion, and thermal relaxation kinetics are discussed. Distinct differences between the two structures are observed, including a complex vacancy diffusion mechanism in beta-Ta. Embedded atom method potentials, which were fitted to bcc properties, have been used to model the Ta-Ta interactions. In order to verify the application of these potentials to the more complex beta-Ta structure, we have also performed density functional theory calculations. Results and implications of these calculations are discussed.

Extraction of electrode kinetic parameters from microdisc voltammetric data measured under transport conditions intermediate between steady-state convergent and transient linear diffusion as typically applies to room temperature ionic liquids

The extraction of electrode kinetic parameters for electrochemical couples in room-temperature ionic liquids (RTILs) is currently an area of considerable interest. Electrochemists typically measure electrode kinetics in the limits of either transient planar or steady-state convergent diffusion for which the voltammetic response is well understood. In this paper we develop a general method allowing the extraction of this kinetic data in the region where the diffusion is intermediate between the planar and convergent limits, such as is often encountered in RTILs using microelectrode voltammetry. A general working surface is derived, allowing the inference of Butler-Volmer standard electrochemical rate constants for the peak-to-peak potential separation in a cyclic voltammogram as a function of voltage scan rate. The method is applied to the case of the ferrocene/ferrocenium couple in [C(2)mim][N(Tf)(2)] and [C(4)mim][N(Tf)(2)].

EFFECT OF ULTRASOUND ON THE KINETICS OF REDUCTION OF HEXACYANOFERRATE(III) BY THIOSULFATE IONS MEDIATED BY RUTHENIUM DIOXIDE HYDRATE

Ultrasound promotes the reduction of hexacyanoferrate(III) by thiosulfate ions mediated by RuO2 . xH(2)O under diffusion-controlled conditions. There is a strong correlation between the measured first-order rate constant and the absorbance of the dispersion, which, in turn, is closely related to the specific surface area of the catalyst. The enhancement in rate with ultrasonic irradiation appears to be largely associated with the dispersive action of the ultrasound on the aggregated particles of RuO2 . xH(2)O. The rate of reaction increases with increasing %duty cycle and ultrasonic intensity. The measured overall activation energies for the reaction with and without ultrasound, i.e. 18 +/- 1 and 20 +/- 1 kJ mol(-1), respectively, are very similar to those expected for a diffusion-controlled reaction. The homogeneous reaction is not promoted by ultrasound.

KINETICS OF REDUCTION OF HEXACYANOFERRATE(III) BY THIOSULFATE IONS MEDIATED BY RUTHENIUM DIOXIDE HYDRATE

The kinetics of reduction of hexacyanoferrate(III) by excess thiosulfate, mediated by RuO2.xH2O, are investigated. At high concentrations of S2O32- (0.1 mol dm-3) the kinetics of Fe(CN)63- reduction are first order with respect to [Fe(CN)63-] and [RuO2.xH2O] and independent of [Fe(CN)64-], [S2O32-] and [S4O62-]. At relatively low concentrations Of S2O32- (0.01 mol dm-3) and in the presence of appreciable concentrations of Fe(CN)64- and S4O62- (0.01 mol dm-3) the kinetics depend directly upon [Fe(CN)63-] and [RuO2.xH2O] and inversely upon [Fe(CN)64-]. Both sets of kinetics can be rationalised using an electrochemical model of redox catalysts in which a reversible reduction reaction [Fe(CN)63- + e- --> Fe(CN)64-] is coupled to an irreversible oxidation reaction (s2O32- - e- --> 1/2S4O62-), by a dispersion of RuO2.xH2O microelectrodes. At high concentrations Of S2O32- this model predicts that the kinetics of Fe(CN)63- reduction are controlled by the rate of diffusion of the Fe(CN)63- ions to the RuO2.xH2O particles. The kinetics observed at low concentrations of S2O32- are predicted by the electrochemical model, assuming that the Tafel slope for the oxidation Of S2O32- to S4O62- on the RuO2.xH2O particles is 56.4 mV decade-1.

Mucoadhesive, syringeable drug delivery systems for controlled application of metronidazole to the periodontal pocket: In vitro release kinetics, syringeability, mechanical and mucoadhesive properties

Novel mucoadhesive formulations containing hydroxyethylcellulose (HEC; 3 and 5%, w/w) or Carbopol (3 and 5%, w/w), polycarbophil (PC; 1 and 3%, w/w) and metronidazole (5%, w/w) at pH 6.8 were designed for the treatment of periodontal diseases. Each formulation was characterised in terms of hardness, compressibility, adhesiveness and cohesiveness (using Texture Profile Analysis), drug release, adhesion to a mucin disc (measured as a detachment force using the texture analyser in tensile mode) and, finally, syringeability (using the texture analyser in compression mode). Drug release from all formulations was non-diffusion controlled. Drug release was significantly decreased as the concentration of each polymeric component was increased, due to both the concomitant increased viscosity of the formulations and, additionally, the swelling kinetics of PC following contact with dissolution fluid. Increasing the concentrations of each polymeric component significantly increased formulation hardness, compressibility, adhesiveness, mucoadhesion and syringeability, yet decreased cohesiveness. Increased product hardness, compressibility and syringeability were due to polymeric effects on formulation viscosity. The effects on cohesiveness may be explained both by increased viscosity and also by the increasing semi-solid nature of products containing 5% HEC or Carbopol and PC (1 or 3%). The observations concerning formulation adhesiveness/mucoadhesion illustrate the adhesive nature of each polymeric component. Greatest adhesion was noted in formulations where neutralisation of PC was maximally suppressed. For the most part, increased time of contact between formulation and mucin significantly increased the required force of detachment, due to the greater extent of mucin polymer hydration and interpenetration with the formulations. Significant statistical interactions were observed between the effects of each polymer on drug release and mechanical/mucoadhesive properties. These interactions may be explained by formulatory effects on the extent of swelling of PC. In conclusion, the formulations described offered a wide range of mechanical and drug release characteristics. Formulations containing HEC exhibited superior physical characteristics for improved drug delivery to the periodontal pocket and are now the subject of long-term clinical investigations. (C) 1997 Elsevier Science B.V.

Characterization of physio-chemical processes and hydration kinetics in concretes containing supplementary cementitious materials using electrical property measurements

The current study monitors both the short- and long-term hydration characteristics of concrete using discretized conductivity measurements from initial gauging, through setting and hardening, the latter comprising both the curing and post-curing periods. In particular, attention is directed to the near-surface concrete as it is this zone which protects the steel from the external environment and has a major influence on durability, performance and service-life. A wide range of concrete mixes is studied comprising both plain Portland cement concretes and concretes containing fly-ash and ground granulated blast furnace slag. The parameter normalised conductivity was used to identify four distinct stages in the hydration process and highlight the influence of supplementary cementitious materials (SCM) on hydration and hydration kinetics. A relationship has been presented to account for the temporal decrease in conductivity, post 10-days hydration. The testing procedure and methodology presented lend itself to in-situ monitoring of reinforced concrete structures. (c) 2013 Elsevier Ltd. All rights reserved.

Nanoscale mapping of oxygen vacancy kinetics in nanocrystalline Samarium doped ceria thin films

The position-dependent oxygen vacancy dynamics induced by a biased scanning probe microscopy tip in Samarium doped ceria thin films grown on MgO (100) substrates is investigated. The granularity of the samples gives rise to spatially dependent local electrochemical activity, as explored by electrochemical strain microscopy. The kinetics of the oxygen vacancy relaxation process is investigated separately for grain boundaries and grains. Higher oxygen vacancy concentration variation and slower diffusion are observed in the grain boundary regions as compared to the grains.

Plasmid DNA damage following exposure to atmospheric pressure non-thermal plasma: kinetics and influence of oxygen admixture

The nature and kinetics of plasmid DNA damage after DNA exposure to a kHz-driven atmospheric pressure nonthermal plasma jet has been investigated. Both single-strand break (SSB) and double-strand break (DSB) processes are reported here. While SSB had a higher rate constant, DSB is recognized to be more significant in living systems, often resulting in loss of viability. In a helium-operated plasma jet, adding oxygen to the feed gas resulted in higher rates of DNA DSB, which increased linearly with increasing oxygen content, up to an optimum level of 0.75% oxygen, after which the DSB rate decreased slightly, indicating an essential role for reactive oxygen species in the rapid degradation of DNA.