Temporal phenomena in inductively coupled chlorine and argon-chlorine discharges

Reproducible modulations in low-pressure, inductively coupled discharges operating in chlorine and argon-chlorine mixtures have been observed and studied. Changes in the light output, floating potential, negative ion fraction, and charged particle densities were observed. Here we report two types of unstable operational modes in an inductively coupled discharge. On the one hand, when the discharge was matched, to minimize reflected power, instabilities were observed in argon-chlorine plasmas over limited operating conditions of input power and gas pressure. The instability window decreased with increasing chlorine content and was observed for chlorine concentrations between 30% and 60% only. However, when operating at pressures below 5 mTorr and the discharge circuit detuned to increase the reflected power, modulations were observed in a pure chlorine discharge. These modulations varied in nature from a series of sharp bursts to a very periodic behavior and can be controlled, by variation of the matching conditions, to produce an apparent pulsed plasma environment. (C) 2005 American Institute of Physics.

High harmonic generation in the relativistic limit

The generation of extremely bright coherent X-ray pulses in the femtosecond and attosecond regime is currently one of the most exciting frontiers of physics - allowing, for the first time, measurements with unprecedented temporal resolution(1-6). Harmonics from laser - solid target interactions have been identified as a means of achieving fields as high as the Schwinger limit(2,7) (E = 1.3 x 10(16) V m(-1)) and as a highly promising route to high-efficiency attosecond (10(-18) s) pulses(8) owing to their intrinsically phase-locked nature. The key steps to attain these goals are achieving high conversion efficiencies and a slow decay of harmonic efficiency to high orders by driving harmonic production to the relativistic limit(1). Here we present the first experimental demonstration of high harmonic generation in the relativistic limit, obtained on the Vulcan Petawatt laser(9). High conversion efficiencies (eta> 10(-6) per harmonic) and bright emission (> 10(22) photons s(-1) mm(-2) mrad(-2) (0.1% bandwidth)) are observed at wavelengths <4 nm ( the 'water-window' region of particular interest for bio-microscopy).

Broken symmetry and pseudogaps in ropes of carbon nanotubes

We investigate the influence of tube-tube interactions in ropes of (10,10) carbon nanotubes, and find that these effects induce a pseudogap in the density of state (DOS) of the rope of width 0.1 eV at the Fermi level. In an isolated (n,n) carbon nanotube there are two bands that cross in a linear fashion at the Fermi level, making the nanotube metallic with a DOS that is constant in a 1.5 eV wide window around the Fermi energy. The presence of the neighbouring tubes causes these two bands to repel, opening up a band gap that can be as large as 0.3 eV. The small dispersion in the plane perpendicular to the rope smears out this gap for a rope with a large cross-sectional area, and we see a pseudogap at the Fermi energy in the DOS where the DOS falls to one third of its value for the isolated tube. This phenomenon should affect many properties of the behavior of ropes of (n,n) nanotubes, which should display a more semimetallic character than expected in transport and doping experiments, with the existence of both hole and electron carriers leading to qualitatively different thermopower and Hall-effect behaviors from those expected for a normal metal. Band repulsion like this can be expected to occur for any tube perturbed by a sufficiently strong interaction, for example, from contact with a surface or with other tubes.

Time dependence of rotational state populations of excited hydrogen molecules in an RF excited plasma reactor

We report on time-dependent population distributions of excited rotational states of hydrogen in a capacitively coupled RF discharge. The common model to obtain the gas temperature from the rotational distribution is not applicable at all times during the discharge cycle due to the time dependence of the EEDF. The apparent temperature within a cycle assumes values between 350 K and 450 K for the discharge parameters of this experiment. We discuss the optimum time window within the discharge cycle that yields the best approximation to the actual temperature. Erroneous results can be obtained, in principle, with time-integrated measurements; we find, however, that in the present case the systematic error amounts to only approximately 20 K. This is due to the fact that the dominant contribution to the average intensity arises during that time window for which the assumptions underlying the analysis are best fulfilled. A similar analysis can be performed for N+2 rotational bands with a small amount of nitrogen added to the discharge gas. These populations do not exhibit the time variations found in the case of H2.

Comparison between fluid simulations and experiments in inductively coupled argon/chlorine plasmas

Comparisons of 2D fluid simulations with experimental measurements of Ar/Cl-2 plasmas in a low-pressure inductively coupled reactor are reported. Simulations show that the wall recombination coefficient of Cl atom (gamma) is a crucial parameter of the model and that neutral densities are very sensitive to its variations. The best agreement between model and experiment is obtained for gamma = 0.02, which is much lower than the value predicted for stainless steel walls (gamma = 0.6). This is consistent with reactor wall contaminations classically observed in such discharges. The electron density, negative ion fraction and Cl atom density have been investigated under various conditions of chlorine and argon concentrations, gas pressure and applied rf input power. The plasma electronegativity decreases with rf power and increases with chlorine concentration. At high pressure, the power absorption and distribution of charged particles become more localized below the quartz window. Although the experimental trends are well reproduced by the simulations, the calculated charged particle densities are systematically overestimated by a factor of 3-5. The reasons for this discrepancy are discussed in the paper.

Extended electrochemical windows made accessible by room temperature ionic liquid/organic solvent electrolyte systems

The electrochemical windows of acetonitrile solutions doped with 0.1 m concentrations of several ionic liquids were examined by cyclic voltammetry at gold and platinum microelectrodes. These results were compared with those observed in the commonly used 0.1 m tetrabutylammonium perchlorate/acetonitrile system as well as with neat ionic liquids. The use of a trifluorotris(pentofluoroethyl)phosphate-based ionic liquid, specifically, as supporting electrolyte in acetonitrile solutions affords a wider anodic window, which is attributed to the high stability of the anionic component of these intrinsically conductive and thermally robust compounds.

Oxidation of N,N,N ',N '-tetraalkyl-para-phenylenediamines in a series of room temperature ionic liquids incorporating the bis(trifluoromethylsulfonyl)imide anion

The five room temperature ionic liquids: 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([CnMIM][N(Tf)(2)], n = 2, 4, 8, 10) and n-hexyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N-6222][N(Tf)(2)]) were investigated as solvents in which to study the electrochemical oxidation of N,N,N',N'-tetramethyl-para-phenylenediamine (TMPD) and N,N,N',N'-tetrabutyl-paraphenylenediamine (TBPD), using 20 mul micro-samples under vacuum conditions. The effect of dissolved atmospheric gases on the accessible electrochemical window was probed and determined to be less significant than seen previously for ionic liquids containing alternative anions. Chronoamperometric transients recorded at a microdisk electrode were analysed via a process of non-linear curve fitting to yield values for the diffusion coefficients of the electroactive species without requiring a knowledge of their initial concentration. Comparison of experimental and simulated cyclic voltammetry was then employed to corroborate these results and allow diffusion coefficients for the electrogenerated species to be estimated. The diffusion coefficients obtained for the neutral compounds in the five ionic liquids via this analysis were, in units of 10(-11) m(2) s(-1), 2.62, 1.87, 1.12, 1.13 and 0.70 for TMPD. and 1.23, 0.80, 0.40, 0.52 and 0.24 for TBPD (listed using the same order for the ionic liquids as stated above). The most significant consequence of changing the cationic component of the ionic liquid was found to be its effect on the solvent viscosity; the diffusion coefficient of each species was found to be approximately inversely proportional to viscosity across the series of ionic liquids, in accordance with Walden's rule. (C) 2003 Elsevier B.V. All rights reserved.

Chitosan nanoparticle as protein delivery carrier - Systematic examination of fabrication conditions for efficient loading and release

Chitosan nanoparticles fabricated via different preparation protocols have been in recent years widely studied as carriers for therapeutic proteins and genes with varying degree of effectiveness and drawbacks. This work seeks to further explore the polyionic coacervation fabrication process, and associated processing conditions under which protein encapsulation and subsequent release can be systematically and predictably manipulated so as to obtain desired effectiveness. BSA was used as a model protein which was encapsulated by either incorporation or incubation method, using the polyanion tripolyphosphate (TPP) as the coacervation crosslink agent to form chitosan-BSA-TPP nanoparticles. The BSA-loaded chitosan-TPP nanoparticles were characterized for particle size, morphology, zeta potential, BSA encapsulation efficiency, and subsequent release kinetics, which were found predominantly dependent on the factors of chitosan molecular weight, chitosan concentration, BSA loading concentration, and chitosan/TPP mass ratio. The BSA loaded nanoparticles prepared under varying conditions were in the size range of 200-580 nm, and exhibit a high positive zeta potential. Detailed sequential time frame TEM imaging of morphological change of the BSA loaded particles showed a swelling and particle degradation process. Initial burst released due to surface protein desorption and diffusion from sublayers did not relate directly to change of particle size and shape, which was eminently apparent only after 6 h. It is also notable that later stage particle degradation and disintegration did not yield a substantial follow-on release, as the remaining protein molecules, with adaptable 3-D conformation, could be tightly bound and entangled with the cationic chitosan chains. In general, this study demonstrated that the polyionic coacervation process for fabricating protein loaded chitosan nanoparticles offers simple preparation conditions and a clear processing window for manipulation of physiochemical properties of the nanoparticles (e.g., size and surface charge), which can be conditioned to exert control over protein encapsulation efficiency and subsequent release profile. The weakness of the chitosan nanoparticle system lies typically with difficulties in controlling initial burst effect in releasing large quantities of protein molecules. (C) 2007 Elsevier B.V. All rights reserved.

Laser-Driven Ultrafast Field Propagation on Solid Surfaces

The interaction of a 3x10(19) W/cm(2) laser pulse with a metallic wire has been investigated using proton radiography. The pulse is observed to drive the propagation of a highly transient field along the wire at the speed of light. Within a temporal window of 20 ps, the current driven by this field rises to its peak magnitude similar to 10(4) A before decaying to below measurable levels. Supported by particle-in-cell simulation results and simple theoretical reasoning, the transient field measured is interpreted as a charge-neutralizing disturbance propagated away from the interaction region as a result of the permanent loss of a small fraction of the laser-accelerated hot electron population to vacuum.

Vasoactivity of AG014699, a clinically active small molecule inhibitor of poly(ADP-ribose) polymerase: a contributory factor to chemopotentiation in vivo?

Purpose: Poly(ADP-ribose) polymerase (PARP) plays an important role in DNA repair, and PARP inhibitors can enhance the activity of DNA-damaging agents in vitro and in vivo. AG014699 is a potent PARP inhibitor in phase II clinical development. However, the range of therapeutics with which AG014699 could interact via a DNA-repair based mechanism is limited. We aimed to investigate a novel, vascular-based activity of AG014699, underlying in vivo chemosensitization, which could widen its clinical application.

Experimental Design: Temozolomide response was analyzed in vitro and in vivo. Vessel dynamics were monitored using “mismatch” following the administration of perfusion markers and real-time analysis of fluorescently labeled albumin uptake in to tumors established in dorsal window chambers. Further mechanistic investigations used ex vivo assays of vascular smooth muscle relaxation, gut motility, and myosin light chain kinase (MLCK) inhibition.

Results: AG014699 failed to sensitize SW620 cells to temozolomide in vitro but induced pronounced enhancement in vivo. AG014699 (1 mg/kg) improved tumor perfusion comparably with the control agents nicotinamide (1 g/kg) and AG14361 (forerunner to AG014699; 10 mg/kg). AG014699 and AG14361 relaxed preconstricted vascular smooth muscle more potently than the standard agent, hydralazine, with no impact on gut motility. AG014699 inhibited MLCK at concentrations that relaxed isolated arteries, whereas AG14361 had no effect.

Conclusion: Increased vessel perfusion elicited by AG014699 could increase tumor drug accumulation and therapeutic response. Vasoactive concentrations of AG014699 do not cause detrimental side effects to gut motility and may increase the range of therapeutics with which AG014699 could be combined with for clinical benefit.

Variation of strand break yield for plasmid DNA irradiated with high-Z metal nanoparticles.

PURPOSE: Poly(ADP-ribose) polymerase (PARP) plays an important role in DNA repair, and PARP inhibitors can enhance the activity of DNA-damaging agents in vitro and in vivo. AG014699 is a potent PARP inhibitor in phase II clinical development. However, the range of therapeutics with which AG014699 could interact via a DNA-repair based mechanism is limited. We aimed to investigate a novel, vascular-based activity of AG014699, underlying in vivo chemosensitization, which could widen its clinical application. EXPERIMENTAL DESIGN: Temozolomide response was analyzed in vitro and in vivo. Vessel dynamics were monitored using "mismatch" following the administration of perfusion markers and real-time analysis of fluorescently labeled albumin uptake in to tumors established in dorsal window chambers. Further mechanistic investigations used ex vivo assays of vascular smooth muscle relaxation, gut motility, and myosin light chain kinase (MLCK) inhibition. RESULTS: AG014699 failed to sensitize SW620 cells to temozolomide in vitro but induced pronounced enhancement in vivo. AG014699 (1 mg/kg) improved tumor perfusion comparably with the control agents nicotinamide (1 g/kg) and AG14361 (forerunner to AG014699; 10 mg/kg). AG014699 and AG14361 relaxed preconstricted vascular smooth muscle more potently than the standard agent, hydralazine, with no impact on gut motility. AG014699 inhibited MLCK at concentrations that relaxed isolated arteries, whereas AG14361 had no effect. CONCLUSION: Increased vessel perfusion elicited by AG014699 could increase tumor drug accumulation and therapeutic response. Vasoactive concentrations of AG014699 do not cause detrimental side effects to gut motility and may increase the range of therapeutics with which AG014699 could be combined with for clinical benefi

Characterisation of fluidised bed granulation processes using in situ Raman spectroscopy

Previous work by the authors Walker et al. [2007b. Fluidised bed characterisation using Raman spectroscopy: applications to pharmaceutical processing. Chemical Engineering Science 62, 3832–3838] illustrated that Raman spectroscopy could be used to provide 3-D maps of the concentration and chemical structure of particles in motion in a fluidised bed, within a relatively short (120 s) time window. Moreover, we reported that the technique, as outlined, has the potential to give detailed in-situ information on how the structure and composition of granules/powders within the fluidised bed (dryer or granulator) vary with the position and evolve with time. In this study we extended the original work by shortening the time window of the Raman spectroscopic analysis to 10 s, which has allowed the in-situ real-time characterisation of a fluidised bed granulation process. Here we show an important new use of the technique which allows in-situ measurement of the composition of the material within the fluidised bed in three spatial dimensions and as a function of time. This is achieved by recording Raman spectra using a probe positioned within the fluidised bed on a long-travel x–y–z stage. In these experiments the absolute Raman intensity is used to provide a direct measure of the amount of any given material in the probed volume, i.e. a particle density. Particle density profiles have been calculated over the granulation time and show how the volume of the fluidised bed decreases with an increase mean granule size. The Raman spectroscopy analysis indicated that nucleation/coalescence in this co-melt fluidised hot melt granulation system occurred over a relatively short time frame (t<30 s). The Raman spectroscopic technique demonstrated accurate correlation with independent granulation experiments which provided particle size distribution analysis. The similarity of the data indicates that the Raman spectra accurately represent solids ratios within the bed, and thus the techniques quantitative capabilities for future use in the pharmaceutical industry.

Developments in X-ray laser pumping with travelling wave at Vulcan

Saturated output has been observed for both Ne and Ni-like X-ray lasers when Pumped in the transient mode. As these 'normal' transitions display very high gain, attempts have been made to observe a 2p --> 2s inner shell transition in Ne-like ions, which scale well towards the water window. Modelling of the pump conditions for Ge lasing at 6.2 run is presented. As the predicted gain is low the experiment was set up for 18 mm targets. Shots were taken on Ti, Fe, Ni and Ge. A similar to1.5 ps travelling wave pulse is applied at various times after the peak of a long, preforming Pulse. Various pump conditions were attempted but no inner shell X-ray laser was detected.

Electrochemistry in Room-Temperature Ionic Liquids: Potential Windows at Mercury Electrodes

The cathodic and anodic: potential limit of eleven different ionic liquids were determined at a mercury hemisphere electrode. Ionic liquids containing the phosphonium cation (tri(n-hexyl)tetradecylphosphonium, [P-14.6,P-6.6](+)) give the largest potential window, especially When Coupled to a trifluorotris(pentafluoroethyl)- [FAP](-). or bis(trifluoromethanesulfonyl)imide, [NTf2](-), anion.

Efficient, halide free synthesis of new, low cost ionic liquids: 1,3-dialkylimidazolium salts containing methyl- and ethyl-sulfate anions

New low-cost ionic liquids containing methyl- and ethyl-sulfate anions can be easily and efficiently prepared under ambient conditions by the reaction of 1-alkylimidazoles with dimethyl sulfate and diethyl sulfate. The preparation and characterization of a series of 1,3-dialkylimidazolium alkyl sulfate and 1,2,3-trialkylimidazolium alkyl sulfate salts are reported. 1,3-Dialkylimidazolium salts containing at least one non-methyl N-alkyl substituent are liquids at, or below room, temperature. Three salts were crystalline at room temperature, the single crystal X-ray structure of 1,3-dimethylimidazolium methyl sulfate was determined and shows the formation of discrete ribbons comprising of two anion-cation hydrogen-bonded chains linked via intra-chain hydrogen-bonding, but little, or no inter-ribbon hydrogen-bonding. The salts are stable, water soluble, inherently 'chloride-free', display an electrochemical window of greater than 4 V, and can be used as alternatives to the corresponding halide salts in metathesis reactions to prepare other ionic liquids including 1-butyl-3-methylimidazolium hexafluorophosphate.