Kinetic analysis of the reaction between electrogenerated superoxide and carbon dioxide in the room temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and hexyltriethylammonium bis(trifluoromethylsulfonyl)imide

The reduction of oxygen in the presence of carbon dioxide has been investigated by cyclic voltammetry at a gold microdisk electrode in the two room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N-6222] [N(Tf)(2)]). With increasing levels of CO2, cyclic voltammetry shows an increase in the reductive wave and diminishing of the oxidative wave, indicating that the generated superoxide readily reacts with carbon dioxide. The kinetics of this reaction are investigated in both ionic liquids. The reaction was found to proceed via a DISP1 type mechanism in [EMIM][N(Tf)(2)] with an overall second-order rate constant of 1.4 +/- 0.4 x 10(3) M-1 s(-1). An ECE or DISP1 mechanism was determined to be the most likely pathway for the reaction in [N-6222][N(Tf)(2)], with an overall second-order rate constant of 1.72 +/- 0.45 x 10(3) m(-1) s(-1).

Gamma ray-induced bystander effect in tumour glioblastoma cells: a specific study on cell survival, cytokine release and cytokine receptors.

Recent experimental evidence has challenged the paradigm according to which radiation traversal through the nucleus of a cell is a prerequisite for producing genetic changes or biological responses. Thus, unexposed cells in the vicinity of directly irradiated cells or recipient cells of medium from irradiated cultures can also be affected. The aim of the present study was to evaluate, by means of the medium transfer technique, whether interleukin-8 and its receptor (CXCR1) may play a role in the bystander effect after gamma irradiation of T98G cells in vitro. In fact the cell specificity in inducing the bystander effect and in receiving the secreted signals that has been described suggests that not only the ability to release the cytokines but also the receptor profiles are likely to modulate the cell responses and the final outcome. The dose and time dependence of the cytokine release into the medium, quantified using an enzyme linked immunosorbent assay, showed that radiation causes alteration in the release of interleukin-8 from exposed cells in a dose-independent but time-dependent manner. The relative receptor expression was also affected in exposed and bystander cells.

Deuterium in the Galactic Centre as a result of recent infall of low-metallicity gas

The Galactic Centre is the most active and heavily processed region of the Milky Way, so it can be used as a stringent test for the abundance of deuterium (a sensitive indicator of conditions in the first 1,000 seconds in the life of the Universe). As deuterium is destroyed in stellar interiors, chemical evolution models 1 predict that its Galactic Centre abundance relative to hydrogen is D/H = 5 x 10(-12), unless there is a continuous source of deuterium from relatively primordial (low-metallicity) gas. Here we report the detection of deuterium (in the molecule DCN) in a molecular cloud only 10 parsecs from the Galactic Centre. Our data, when combined with a model of molecular abundances, indicate that D/H = (1.7 +/- 0.3) x 10(-6), five orders of magnitude larger than the predictions of evolutionary models with no continuous source of deuterium. The most probable explanation is recent infall of relatively unprocessed metal-poor gas into the Galactic Centre (at the rate inferred by Wakker(2)). Our measured D/H is nine times less than the local interstellar value, and the lowest D/H observed in the Galaxy. We conclude that the observed Galactic Centre deuterium is cosmological, with an abundance reduced by stellar processing and mixing, and that there is no significant Galactic source of deuterium.

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.

Highly resolved absolute cross-sections for dissociative electron attachment to SF5CF3

Using two complementary experimental methods, we have measured partial (mass-resolved) cross-sections for dissociative electron attachment to the molecule trifluoromethyl sulfurpentafluoride (SF5CF3) at the gas temperature T-G = 300 K over a broad range of electron energies (E = 0.001-12 eV). The absolute scale for these cross-sections was obtained with reference to the thermal (T = 300 K) rate coefficient for anion formation (8.0(3) x 10(-8) cm(3) s(-1)). Below 1 eV, SF5- is the dominant product anion and formed through the lowest anion state which cuts the neutral SF5CF3 potential close to the S-C equilibrium distance. The highly resolved laser photoelectron attachment data exhibit a downward Wigner cusp at 86meV, indicating that the nu(4)(alpha(1)) vibrational mode is important for the primary attachment dynamics. Both SF5- and F- anions are formed with similar yields through the first excited resonance located near 3.6eV. Towards higher energies, the anions CF3-, SF4-, and SF3- are also produced. Summation of the partial cross-sections yields a total absolute cross-section for anion formation over the energy range 0.001-12 eV. This is used to calculate the dependence of the rate coefficient for dissociative electron attachment over a broad range of electron temperatures for the fixed gas temperature T-G = 300 K; good agreement is found between the calculated values and those obtained in a drift tube experiment. In addition to the experimental work, semiempirical R-matrix calculations have been Carried out for the energy dependence of the cross-section for SF5- formation. The experimental findings are semi-quantitatively recovered. (C) 2008 Elsevier B.V. All rights reserved.

Dust and the type II-Plateau supernova 2004dj

We present mid-infrared (MIR) spectroscopy of a Type II-plateau supernova, SN 2004dj, obtained with the Spitzer Space Telescope, spanning 106--1393d after explosion. MIR photometry plus optical/near-IR observations are also reported. An early-time MIR excess is attributed to emission from non-silicate dust formed within a cool dense shell (CDS). Most of the CDS dust condensed between 50d and 165d, reaching a mass of $0.3x^(-5)Msun. Throughout the observations much of the longer wavelength (>10microns) part of the continuum is explained as an IR echo from interstellar dust. The MIR excess strengthened at later times. We show that this was due to thermal emission from warm, non-silicate dust formed in the ejecta. Using optical/near-IR line-profiles and the MIR continua, we show that the dust was distributed as a disk whose radius appeared to be slowly shrinking. The disk radius may correspond to a grain destruction zone caused by a reverse shock which also heated the dust. The dust-disk lay nearly face-on, had high opacities in the optical/near-IR regions, but remained optically thin in the MIR over much of the period studied. Assuming a uniform dust density, the ejecta dust mass by 996d was 0.5+/-0.1 x 10^(-4)Msun, and exceeded 10^(-4)Msun by 1393d. For a dust density rising toward the center the limit is higher. Nevertheless, this study suggests that the amount of freshly-synthesized dust in the SN 2004dj ejecta is consistent with that found from previous studies, and adds further weight to the claim that such events could not have been major contributors to the cosmic dust budget.

Characterisation of the photocatalyst Pilkington Activ (TM): a reference film photocatalyst?

Pilkington Glass Activ(TM) represents a possible suitable successor to P25 TiO2, especially as a benchmark photocatalyst film for comparing other photocatalyst or PSH self-cleaning films. Activ(TM) is a glass product with a clear, colourless, effectively invisible, photocatalytic coating of titania that also exhibits PSH. Although not as active as a film of P25 TiO2, Activ(TM) vastly superior mechanical stability, very reproducible activity and widespread commercial availability makes it highly attractive as a reference photocatalytic film. The photocatalytic and photo-induced superhydrophilitic (PSH) properties of Activ(TM) are studied in some detail and the results reported. Thus, the kinetics of stearic acid destruction (a 104 electron process) are zero order over the stearic acid range 4-129 monolayers and exhibit formal quantum efficiencies (FQE) of 0.7 X 10(-5) and 10.2 x 10(-5) molecules per photon when irradiated with light of 365 +/- 20 and 254 nm, respectively; the latter appears also to be the quantum yield for Activ(TM) at 254 nm. The kinetics of stearic acid destruction exhibit Langmuir-Hinshelwood-like saturation type kinetics as a function of oxygen partial pressure, with no destruction occurring in the absence of oxygen and the rate of destruction appearing the same in air and oxygen atmospheres. Further kinetic work revealed a Langmuir adsorption type constant for oxygen of 0.45 +/- 0.16 kPa(-1) and an activation energy of 19 +/- 1 Kj mol(-1). A study of the PSH properties of Activ(TM) reveals a high water contact angle (67) before ultra-bandgap irradiation reduced to 0degrees after prolonged irradiation. The kinetics of PSH are similar to those reported by others for sol-gel films using a low level of UV light. The kinetics of contact angle recovery in the dark appear monophasic and different to the biphasic kinetics reported recently by others for sol-gel films [J. Phys. Chem. B 107 (2003) 1028]. Overall, Activ(TM) appears a very suitable reference material for semiconductor film photocatalysis. (C) 2003 Elsevier Science B.V All rights reserved.

Use of luminescent gold compounds in the design of thin-film oxygen sensors

The use of two gold compounds incorporated into thin plastic films as luminescence quenching oxygen sensors is described. The films are sensitive both to gaseous oxygen and to oxygen dissolved in nonaqueous media such as ethanol. The luminescence quenching of these sensors by oxygen obeys the Stern-Volmer equation and Stern-Volmer constants of 5.35 x 10(-3) and 0.9 x 10(-3) Torr(-1) are found, respectively, for the two dyes in a polystyrene polymer matrix. The sensitivity of the films is strongly influenced by the nature of the polymer matrix, and greatest sensitivity was found in systems based an the polymers polystyrene or cellulose acetate butyrate. Sensitivity was not found to be temperature dependent though raising the temperature hom 15 to 50 degrees C did result in a slight decrease in emission intensity and a hypsochromic shift in the emission wavelength. The rate of response and recovery of the sensors can be increased either by decreasing film thickness or by increasing the operating temperature. The operational and storage stability of these films is generally good though exposure to light should be avoided as one of the dyes tends to undergo photobleaching probably due to a photoinduced ligand substitution reaction.

Detection of streptomycin residues in whole milk using an optical immunobiosensor

The development of an assay for the detection of streptomycin residues in pasteurized whole milk using an optical biosensor (Biacore) is reported. Streptomycin-adipic hydrazide coupled to bovine thyroglobulin was used to produce a sheep polyclonal antibody. The antibody displayed excellent cross-reactivity with dihydrostreptomycin (106%). There was no significant cross-reaction with other aminoglycosides or common antibiotics. Streptomycin was also immobilized onto a CM5 sensor chip to provide a stable, reusable surface. The developed assay permitted the direct analysis of whole milk samples (similar to3.5% fat) without prior centrifugation and defatting. Results were available in 5 min. The limit of detection of the assay was determined as 4.1 ng/mL, well below the European maximum residue limit (MRL) of 200 ng/mL. Repeatability (or coefficient of variation) between runs was determined as 3.5% (100 ng/mL; 0.5 x MRL), 5.7% (200 ng/mL; MRL), and 7.6% (400 ng/mL; 2 x MRL).

The preparation, solubilisation and binding characteristics of a beta 2-adrenoceptor isolated from transfected Chinese hamster cells

beta2-Adrenoceptor agonists (beta -agonists) are well known for their growth promoting and repartitioning effects in many species. Although the use of these compounds to increase muscle mass in stockfarming is prohibited within the EU, under directive 96/22/EC, significant illegal use still occurs. With legal and illegal synthesis of new structurally related compounds, the detection of traditional beta -agonists and new derivatives becomes increasingly problematical. This method describes the isolation and solubilisation of a beta2-adrenoceptor from a transfected Chinese hamster ovary cell line, using the detergent digitonin. The solubilised receptor retained its activity and was isolated from the cell membrane at a concentration of 550 +/- 100 fmol mg(-1) of solubilised protein. Competition analysis using the tritiated antagonist dihydroalprenolol revealed receptor affinity for five structurally different beta -agonists, with IC50 values ranging from 2.1 +/- 0.76 X 10(-7) M for salmeterol to 1.1 +/- 0.62 x 10(-5) M for ractopamine. This study has demonstrated that transfected cell lines with a high expression of beta2-adrenoceptors are a convenient source of active receptor material. Solubilised beta (2)-adrenoceptors could form the basis of a multi-analyte screening assay for use in routine screening.

The preparation, solubilisation and binding characteristics of a beta 2-adrenoceptor isolated from transfected Chinese hamster cells

beta2-Adrenoceptor agonists (beta -agonists) are well known for their growth promoting and repartitioning effects in many species. Although the use of these compounds to increase muscle mass in stockfarming is prohibited within the EU, under directive 96/22/EC, significant illegal use still occurs. With legal and illegal synthesis of new structurally related compounds, the detection of traditional beta -agonists and new derivatives becomes increasingly problematical. This method describes the isolation and solubilisation of a beta2-adrenoceptor from a transfected Chinese hamster ovary cell line, using the detergent digitonin. The solubilised receptor retained its activity and was isolated from the cell membrane at a concentration of 550 +/- 100 fmol mg(-1) of solubilised protein. Competition analysis using the tritiated antagonist dihydroalprenolol revealed receptor affinity for five structurally different beta -agonists, with IC50 values ranging from 2.1 +/- 0.76 X 10(-7) M for salmeterol to 1.1 +/- 0.62 x 10(-5) M for ractopamine. This study has demonstrated that transfected cell lines with a high expression of beta2-adrenoceptors are a convenient source of active receptor material. Solubilised beta (2)-adrenoceptors could form the basis of a multi-analyte screening assay for use in routine screening.

A case study with a novel geometry for pulsed laser deposition

Aluminium thin films were deposited by a laser ablation technique from solid cylindrical targets rotated on a lead screw. Both smooth-surfaced targets and targets with screw threads cut into the area to he irradiated were used. The targets were irradiated with a focused circular spot size of 2.5 mm in diameter, at a power density equal to 5.4 +/- 0.2 x 10(8) W cm(-2). The polar distribution of the ablated atomic material was found to vary as a function of the target screw thread pitch, with the exponent n, in the polar distribution f(theta) = cos(n) theta, varying from 13.5 +/- 1.3 for no pitch to a minimum of 5 +/- 0.7 for a screw thread pitch of 0.2 mm. The use of such novel target geometries forms a possible basis for increasing thickness uniformity during the pulsed laser deposition of thin films.

CHARACTERIZATION OF A LASER-PRODUCED PLASMA USING THE TECHNIQUE OF POINT-PROJECTION ABSORPTION-SPECTROSCOPY

The technique of point-projection spectroscopy has been shown to be applicable to the study of expanding aluminum plasmas generated by approximately 80 ps laser pulses incident on massive, aluminum stripe targets of approximately 125-mu-m width. Targets were irradiated at an intensity of 2.5 +/- 0.5 x 10(13) W/cm2 in a line focus geometry and under conditions similar to those of interest in x-ray laser schemes. Hydrogenic and heliumlike aluminum resonance lines were observed in absorption using a quasicontinuous uranium back-lighter plasma. Using a pentaerythrital Bragg crystal as the dispersive element, a resolving power of approximately 3500 was achieved with spatial resolution at the 5-mu-m level in frame times of the order of 100 ps. Reduction of the data for times up to 150 ps after the peak of the incident laser pulse produced estimates of the temperature and ion densities present, as a function of space and time. The one-dimensional Lagrangian hydrodynamic code MEDUSA coupled to the atomic physics non-local-thermodynamic-equilibrium ionized material package was used to simulate the experiment in planar geometry and has been shown to be consistent with the measurements.

Measurements of the hole boring velocity from Doppler shifted harmonic emission from solid targets

The fast ignitor scheme for inertial confinement fusion requires forward driving of the critical density surface by light pressure (hole boring) to allow energy deposition close to the dense fuel. The recession velocity of the critical density surface has been observed to be nu/c = 0.015 at an irradiance of 1.0 x 10(19) W cm(-2) at a wavelength of 1.05 micron, in quantitative agreement with modeling. (C) 1996 American Institute of Physics.

Chemical tuning of the interlayer magnetic coupling in TlCo2Se2-xSx

The system TlCo2Se2-xSx has been thoroughly investigated by neutron powder diffraction and SQUID magnetometry. TlCo2Se2-xSx is a layered tetragonal structure containing atomic cobalt layers separated by a distance of 6.4 angstrom in the sulphide and 6.8 angstrom in the selenide. The solid solubility of isovalent selenium and sulphur atoms in the structure makes it possible to continuously vary the interlayer distance and thereby tune the magnetic coupling between the Co-layers. At low temperatures, the Co-atoms are ferromagnetically ordered within the layers and magnetic moments lie in the ab-plane. However, these Co-moments form a helical magnetic structure that prevails for 0 <= x <= 1.5 with a gradual decrease of the angle between adjacent Co-layers from 122 degrees to 39 degrees. For x >= 1.75, a collinear ferromagnetic structure is stable. The relationship between the coupling angle and the Co-interlayer separation shows an almost linear behaviour. The helical phase contains no net spontaneous magnetic moment up to TlCo2SeS, where a small net magnetic moment appears that increases until the ferromagnetic structure is found for 1.75 <= x <= 2.0. (C) 2005 Elsevier B.V. All rights reserved.