Fluorescence-based thin plastic film ion-pair sensors for oxygen

A general method of preparation of thin-film sensors for O-2, incorporating the dye ion-pair tris(4,7-diphenyl-1,10-phenanthroline) rutheninm(II) ditetraphenylborate, in a variety of different thin film polymer/plasticizer matrices is described, The sensitivity of the sensor depends upon the nature of the polymer matrix and plasticizer, A detailed study of one of these systems utilising the polymer poly(methyl methacrylate), PMMA, is reported. The sensitivity of this O-2 sensor depends markedly upon the plasticizer concentration and is largely independent of temperature (24,5-52.5 degrees C) and age (up to 30 d), When exposed to an alternating atmosphere of O-2 and N-2, a typical oxygen film sensor in PMMA exhibits a 0-90% response and recovery time of 0.4 and 4.5 s, respectively.

Transport Properties Investigation of Aqueous Protic Ionic Liquid Solutions through Conductivity, Viscosity, and NMR Self-Diffusion Measurements

We present a study on the transport properties through conductivity (s), viscosity (?), and self-diffusion coefficient (D) measurements of two pure protic ionic liquids—pyrrolidinium hydrogen sulfate, [Pyrr][HSO4], and pyrrolidinium trifluoroacetate, [Pyrr][CF3COO]—and their mixtures with water over the whole composition range at 298.15 K and atmospheric pressure. Based on these experimental results, transport mobilities of ions have been then investigated in each case through the Stokes–Einstein equation. From this, the proton conduction in these PILs follows a combination of Grotthuss and vehicle-type mechanisms, which depends also on the water composition in solution. In each case, the displacement of the NMR peak attributed to the labile proton on the pyrrolidinium cation with the PILs concentration in aqueous solution indicates that this proton is located between the cation and the anion for a water weight fraction lower than 8%. In other words, for such compositions, it appears that this labile proton is not solvated by water molecules. However, for higher water content, the labile protons are in solution as H3O+. This water weight fraction appears to be the solvation limit of the H+ ions by water molecules in these two PILs solutions. However, [Pyrr][HSO4] and [Pyrr][CF3COO] PILs present opposed comportment in aqueous solution. In the case of [Pyrr][CF3COO], ?, s, D, and the attractive potential, Epot, between ions indicate clearly that the diffusion of each ion is similar. In other words, these ions are tightly bound together as ion pairs, reflecting in fact the importance of the hydrophobicity of the trifluoroacetate anion, whereas, in the case of the [Pyrr][HSO4], the strong H-bond between the HSO4– anion and water promotes a drastic change in the viscosity of the aqueous solution, as well as on the conductivity which is up to 187 mS·cm–1 for water weight fraction close to 60% at 298 K.

Rates for repair of pBR 322 DNA radicals by thiols as measured by the gas explosion technique: evidence that counter-ion condensation and co-ion depletion are significant at physiological ionic strength.

Rates of rapair of pBR 322 plasmid DNA radicals by thiols of varying net charge (Z) at pH 7 and physiological ionic strength were measured using the oxygen explosion technique. The extent of conversion of supercoiled to relaxed circular plasmid was measured by HPLC as a function of the time of oxygen exposure before or after irradiation, the time-courses being fitted by a pseudo-first-order kinetic expression with k1 = k2[RSH]. Values of k2 (M-1 S-1) were: 2.1 x 10(5) (GSH, Z = -1), 1.4 x 10(6) (2-mercaptoethanol, Z = 0), 1.2 x 10(7) (cysteamine, Z = +1), 6.6 x 10(7) (WR-1065 or N-(2-mercaptoethyl)-1,3-diamino?? propane, Z = +2). The approximately 6-fold increase in rate with each unit increase in Z is attributed to concentration of cationic thiols near DNA as a consequence of counter-ion condensation and reduced levels of anionic thiols near DNA owing to co-ion depletion. The results are quantitatively consistent with chemical repair as a significant mechanism for radioprotection of cells by neutral and cationic thiols under aerobic conditions, but indicate that repair by GSH will compete effectively with oxygen only at low oxygen tension.

Measurements of negative ion densities by absorption spectroscopy

A novel diagnostic technique for the measurement of negative ions is presented. The absorption of a cw-laser beam with a wavelength close to the maximum of the photodetachment cross section is measured. The laser beam undergoes multiple reflections through the discharge volume using a multipass cell there a Herriott arrangement). Proof-of-principle measurements of negative hydrogen ions in a hybrid volume source are presented. The measured H- density is in agreement with results of conventional, Langmuir probe-based photodetachment measurements. (C) 1998 American Institute of Physics. [S0003-6951(98)02119-6].

A COMPARISON OF EXPERIMENTAL AND THEORETICAL ELECTRON-ENERGY DISTRIBUTION-FUNCTIONS IN A MULTICUSP ION-SOURCE

Experimental and theoretical electron energy distribution functions (EEDFS) measured in and calculated for the driver of a multicusp ion source operating in hydrogen are compared. The results show that atomic physics based theoretical models can accurately predict the EEDF in such discharges if some appropriate experimentally determined quantities are used as input parameters. The magnitude and shape of the EEDF is found to be particularly sensitive to the effective surface area to volume ratio for electrons.

ENHANCED VOLUME PRODUCTION OF NEGATIVE-IONS IN THE POST DISCHARGE OF A MULTICUSP HYDROGEN DISCHARGE

In this paper we demonstrate a new concept in the production of negative hydrogen ions in a low-pressure multicusp discharge. The discharge voltage is modulated to produce a non-Maxwellian, hot-electron plasma during the current pulse, followed by a cool Maxwellian electron plasma in the post discharge. This procedure, of separating in time the required hot and cold electron plasmas required for volume H- production, is called a temporal filter. The time evolution of the electron energy distribution function is measured using the time-resolved second derivative of a Langmuir probe characteristic. Time-resolved measurements of the negative ion density are made using laser photodetachment. The measurements show that the negative ion density in the center of the source, at a gas pressure of 0.07 Pa, increases by a factor of 2 when the discharge is switched off. At this low pressure the average H- beam current extracted from the source, when operated with a discharge current of 1 A in the pulse modulated mode exceeds the H- beam current from a 5 A continuously operated source. The increase in efficiency of the pulsed source is explained in terms of a two-step H- production mechanism.

Fully kinetic simulation of ion acoustic and dust-ion acoustic waves

A series of numerical simulations is presented, based on a recurrence-free Vlasov kinetic model using kinetic phase point trajectories. All plasma components are modeled kinetically via a Vlasov evolution equation, then coupled through Poisson’s equation. The dynamics of ion acoustic waves in an electron-ion and in a dusty (electron-ion-dust) plasma configuration are investigated, focusing on wave decay due to Landau damping and, in particular, on the parametric dependence of the damping rate on the dust concentration and on the electron-to-ion temperature ratio. In the absence of dust, the occurrence of damping was observed, as expected, and its dependence to the relative magnitude of the electron vs ion temperature(s) was investigated. When present, the dust component influences the charge balance, enabling dust-ion acoustic waves to survive Landau damping even in the extreme regime where Te???Ti. The Landau damping rate is shown to be minimized for a strong dust concentration or/and for a high value of the electron-to-ion temperature ratio. Our results confirm earlier theoretical considerations and contribute to the interpretation of experimental observations of dust-ion acoustic wave characteristics.

Phenol degradation by powdered metal ion modified titanium dioxide photocatalysts

Conventional water purification and disinfection generally involve potentially hazardous substances, some of which known to be carcinogenic in nature. Titanium dioxide photocatalytic processes provide an effective route to destroy hazardous organic contaminants. This present work explores the possibility of the removal of organic pollutants (phenol) by the application of TiO2 based photocatalysts. The production of series of metal ions doped or undoped TiO2 were carried out via a sol–gel method and a wet impregnation method. Undoped TiO2 and Cu doped TiO2 showed considerable phenol degradation. The efficiency of photocatalytic reaction largely depends on the photocatalysts and the methods of preparation the photocatalysts. The doping of Fe, Mn, and humic acid at 1.0 M% via sol–gel methods were detrimental for phenol degradation. The inhibitory effect of initial phenol concentration on initial phenol degradation rate reveals that photocatalytic decomposition of phenol follows pseudo zero order reaction kinetics. A concentration of > 1 g/L TiO2 and Cu doped TiO2 is required for the effective degradation of 50 mg/L of phenol at neutral pH. The rise in OH- at a higher pH values provides more hydroxyl radicals which are beneficial of phenol degradation. However, the competition among phenoxide ion, Cl- and OH- for the limited number of reactive sites on TiO2 will be a negative influence in the generation of hydroxyl radical. The dependence of phenol degradation rate on the light intensity was observed, which also implies that direct sunlight can be a substitute for the UV lamps and that photocatalytic treatment of organic pollutants using this technique shows some promise.

Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction

We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)-trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry’s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol · dm-3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry’s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonates-based Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure.

The adsorption, storage and release of nitric oxide using ion exchanged zeolites

Zeolites exchanged with transition metal cations Co2+, Mn2+, Zn2+ and Cu2+ are capable of storing and delivering a large quantity of nitric oxide in a range of 1.2-2.7 mmolg(-1). The metal ion exchange impacts the pore volumes of zeolite FAU more significantly than LTA. The storage of NO mainly involves coordination of NO to metal cation sites. By exposing zeolites to a moisture atmosphere, the stored nitric oxide can be released. The NO release takes more than 2 hours for the NO concentration decreasing below similar to 5ppb in outlet gas. Its release rate can be controlled by tailoring zeolite frameworks and optimising release conditions.

High sensitivity (1 ppm) hydrogen detection using an unconventional Pd/n-InP Schottky device

Hydrogen is detected using a Pd/n-InP Schottky diode in which the elongated, very thin Pd electrode is of greater resistance than the underlying semiconductor substrate. Four-probe measurements of the device resistance, as a function of hydrogen concentration, are made by contacting only the Pd electrode, with a sensitivity of 1 ppm being achieved. On hydrogen exposure the device resistance drops from an initial high value, characteristic of the Pd electrode alone, to a lower value due to a hydrogen-induced lowering of the Schottky barrier that opens up the InP substrate as a parallel current carrying channel.

The complex effects of the slow-releasing hydrogen sulfide donor GYY4137 in a model of acute joint inflammation and in human cartilage cells

The role of hydrogen sulfide (H2 S) in inflammation remains unclear with both pro- and anti-inflammatory actions of this gas described. We have now assessed the effect of GYY4137 (a slow-releasing H2 S donor) on lipopolysaccharide (LPS)-evoked release of inflammatory mediators from human synoviocytes (HFLS) and articular chondrocytes (HAC) in vitro. We have also examined the effect of GYY4137 in a complete Freund's adjuvant (CFA) model of acute joint inflammation in the mouse. GYY4137 (0.1-0.5 mM) decreased LPS-induced production of nitrite (NO2 (-) ), PGE2 , TNF-a and IL-6 from HFLS and HAC, reduced the levels and catalytic activity of inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) and reduced LPS-induced NF-?B activation in vitro. Using recombinant human enzymes, GYY4137 inhibited the activity of COX-2, iNOS and TNF-a converting enzyme (TACE). In the CFA-treated mouse, GYY4137 (50 mg/kg, i.p.) injected 1 hr prior to CFA increased knee joint swelling while an anti-inflammatory effect, as demonstrated by reduced synovial fluid myeloperoxidase (MPO) and N-acetyl-ß-D-glucosaminidase (NAG) activity and decreased TNF-a, IL-1ß, IL-6 and IL-8 concentration, was apparent when GYY4137 was injected 6 hrs after CFA. GYY4137 was also anti-inflammatory when given 18 hrs after CFA. Thus, although GYY4137 consistently reduced the generation of pro-inflammatory mediators from human joint cells in vitro, its effect on acute joint inflammation in vivo depended on the timing of administration.

Energetic beams of negative and neutral hydrogen from intense laser plasma interaction

We present observations of intense beams of energetic negative hydrogen ions and fast neutral hydrogen atoms in intense (5 × 10 W/cm) laser plasma interaction experiments, which were quantified in numerical calculations. Generation of negative ions and neutral atoms is ascribed to the processes of electron capture and loss by a laser accelerated positive ion in the collisions with a cloud of droplets. A comparison with a numerical model of charge exchange processes provides information on the cross section of the electron capture in the high energy domain.

On the existence and stability of electrostatic structures in non-Maxwellian electron-positron-ion plasmas

Electrostatic solitary waves in plasmas are the focus of many current studies of localized electrostatic disturbances in both laboratory and astrophysical plasmas. Here, an investigation of the nonlinear dynamics of plasma evolving in two dimensions, in the presence of excess superthermal background electrons and positrons, is undertaken. We investigate the effect of a magnetic field on weakly nonlinear ion acoustic waves. Deviation from the Maxwellian distribution is effectively modelled by the kappa model. A linear dispersion relation is derived, and a decrease in frequency and phase speed in both parallel and perpendicular modes can be seen, when the proportion of positrons to electrons increases. We show that ion acoustic solitary waves can be generated during the nonlinear evolution of a plasma fluid, and their nonlinear propagation is governed by a Zakharov-Kuznetsov (ZK) type equation. A multiple scales perturbation technique is used to derive the ZK equation. The solitary wave structures are dependent on the relation between the system parameters, specifically the superthermality of the system, the proportion of positron content, magnetic field strength, and the difference between electron and positron temperature. The parametric effect of these on electrostatic shock structures is investigated. In particular, we find that stronger superthermality leads to narrower excitations with smaller potential amplitudes. Increased positron concentration also suppresses both the amplitude and the width of solitary wave structures. However, the structures are only weakly affected by temperature differentials between electrons and positrons in our model. © 2013 AIP Publishing LLC.

Freak waves and electrostatic wavepacket modulation in a quantum electron-positron-ion plasma

The occurrence of rogue waves (freak waves) associated with electrostatic wavepacket propagation in a quantum electron-positron-ion plasma is investigated from first principles. Electrons and positrons follow a Fermi-Dirac distribution, while the ions are subject to a quantum (Fermi) pressure. A fluid model is proposed and analyzed via a multiscale technique. The evolution of the wave envelope is shown to be described by a nonlinear Schrödinger equation (NLSE). Criteria for modulational instability are obtained in terms of the intrinsic plasma parameters. Analytical solutions of the NLSE in the form of envelope solitons (of the bright or dark type) and localized breathers are reviewed. The characteristics of exact solutions in the form of the Peregrine soliton, the Akhmediev breather and the Kuznetsov-Ma breather are proposed as candidate functions for rogue waves (freak waves) within the model. The characteristics of the latter and their dependence on relevant parameters (positron concentration and temperature) are investigated. © 2014 IOP Publishing Ltd.