Asymmetric and Anharmonic Electrode Kinetics: Evaluation of a Model for Electron Transfer with Concerted Rupture of Weak, Inner Shell Interactions

A surface-integrated form of the widely used (anharmonic) Lennard-Jones 12–6 interaction potential, the Lennard-Jones 9–3 potential, is used to develop a quadratic activation/driving force relationship that gives rise to asymmetric Tafel plots for electron transfer occurring with simultaneous interaction rupture. The Tafel plots are shown to exhibit linearity over a wide potential range, depending on the ratio of the Gibbs interaction well to the solvent reorganisation free energy. The fit of the model to experimental data for a ferrocene-based self-assembled monolayer (SAM) bathed by aqueous perchloric acid suggests ion pairing between ferricenium and perchlorate ions. This crude and primitive model readily enables experimentalists to obtain a parametric understanding of the physicochemical dynamics underpinning interaction rupture in concert with electron transfer, which may empower routes to improve the efficiency of a plethora of topical electrochemical technologies

A mechanistic study of the EC′ mechanism – the split wave in cyclic voltammetry and square wave voltammetry

In this paper, a detailed investigation of electrochemical reactions coupled with homogenous chemical steps using cyclic voltammetry (CV) and square wave voltammetry (SWV) was carried out to study the electrocatalytic (EC’) mechanism. In CV, parameters including scan rate, electrode material and redox reactant were investigated while in SWV, parameters including substrate concentrations and frequencies were altered to demonstrate EC’ mechanism. Mechanistic studies focused on the EC’ mechanism using L-cysteine with ferrocenecarboxylic acid and 1,1 ′-ferrocenedicarboxylic acid respectively. Voltammetric responses were recorded and under conditions of high chemical rate constant and low substrate concentration, a split wave was observed in both CV and SWV studies

Evolution of the Reverse Shock Emission from SNR 1987A

We present new (2004 July) G750L and G140L Space Telescope Imaging Spectrograph (STIS) data of the H-alpha and Ly-alpha emission from supernova remnant (SNR) 1987A. With the aid of earlier data, from Oct 1997 to Oct 2002, we track the local evolution of Ly-alpha emission and both the local and global evolution of H-alpha emission. In addition to emission which we can clearly attribute to the surface of the reverse shock, we also measure comparable emission, in both H-alpha and Ly-alpha, which appears to emerge from supernova debris interior to the surface. New observations taken through slits positioned slightly eastward and westward of a central slit show a departure from cylindrical symmetry in the H-alpha surface emission. Using a combination of old and new observations, we construct a light curve of the total H-alpha flux, F, from the reverse shock, which has increased by a factor ~ 4 over about 8 years. However, due to large systematic uncertainties, we are unable to discern between the two limiting behaviours of the flux - F ~ t (self-similar expansion) and F ~ t^5 (halting of the reverse shock). Such a determination is relevant to the question of whether the reverse shock emission will vanish in less than about 7 years (Smith et al. 2005). Future deep, low- or moderate-resolution spectra are essential for accomplishing this task.Comment: 28 pages, 12 figures. Accepted by Ap

Radiation modeling in the Earth and Mars atmospheres using LRO/CRaTER with the EMMREM Module

Abstract We expand upon the efforts of Joyce et al. (2013), who computed the modulation potential at the Moon using measurements from the Cosmic Ray Telescope for the Effects of Radiation (CRaTER) instrument on the Lunar Reconnaissance Orbiter (LRO) spacecraft along with data products from the Earth-Moon-Mars Radiation Environment Module (EMMREM). Using the computed modulation potential, we calculate galactic cosmic ray (GCR) dose and dose equivalent rates in the Earth and Mars atmospheres for various altitudes over the course of the LRO mission. While we cannot validate these predictions by directly comparable measurement, we find that our results conform to expectations and are in good agreement with the nearest available measurements and therefore may be used as reasonable estimates for use in efforts in risk assessment in the planning of future space missions as well as in the study of GCRs. PREDICCS (Predictions of radiation from REleASE, EMMREM, and Data Incorporating the CRaTER, COSTEP, and other solar energetic particles measurements) is an online system designed to provide the scientific community with a comprehensive resource on the radiation environments of the inner heliosphere. The data products shown here will be incorporated into PREDICCS in order to further this effort and daily updates will be made available on the PREDICCS website (http://prediccs.sr.unh.edu). Key Points We model GCR dose and dose equivalent rates in Earth and Mars atmospheres Dose rates are in reasonable agreement with nearby measurements Data products will soon be made available on PREDICCS website

Electrochemical measurement of antibody­‐antigen recognition biophysics: thermodynamics and kinetics of human chorionic gonadotropin (hCG) binding to redox-­tagged antibodies

The thermodynamics and kinetics of antigen binding under diffusive conditions to an electrode surface modified with ferrocene-tagged antibodies is studied within this work, and realised experimentally for the case of human chorionic gonadotropin (hGC) as the antigen with monoclonal anti-hCG antibodies immobilised on an electrode surface via a molecular wire platform. The formation of the antigen-antibody complex is monitored through the blocking of the ferrocene voltammetry, thereby enabling the fractional coverage of the electrode binding sites to be unravelled as a function of time. It is found that, at low antigen concentrations, a Frumkin adsorption isotherm fits the data, with repulsive interactions between bound antigens playing a significant rôle, with an affinity constant that is an order of magnitude larger than in the case of an untagged antibody, suggesting that the chemical hydrophobicity of the redox tag may encourage stronger binding. Comparison of the experimental temporal data with relevant diffusion-adsorption models under activation control allows for the extraction of the kinetic parameters; at zero coverage, the rate constants for adsorption and desorption are, respectively, larger and smaller than the untagged antibody. The kinetic study enables the confirmation that this type of platform may be utilised for rapid (15 min) and quantitative electroimmunoassay. This is validated through proof-of-concept analytical measurements, yielding a limit of detection around 25 mIU mL−1 (corresponding to 2.7 ng mL−1) – a value used clinically for urine hCG measurements corresponding to around four weeks of gestational age

Evaporative Mass Loss Measurement as a Quality Control Tool for Quality Assurance in the Manufacture of Inks Suitable for High Speed (≥60 m/min) Printing

In any manufacturing environment, it is always important to be able to embrace a culture of traceability of any non-conformed product. For the case of ink manufacture, operator confusion, leading to the mixing-up of solvents, or connecting the incorrect solvent drum to solvent lines, can lead to disastrous consequences that are not trivial for a quality control/quality assurance team to unravel. Accordingly, simple methods for assessing whether the correct solvents were added in the correct ratios to products empower this QA/QC requirement. In this paper, we examine the use of a trivial measurement of evaporative mass loss as a protocol for validating the conformance of manufactured ink to specification. Inspired by the transport-limit that occurs at ultramicroelectrodes in electrochemistry, we develop theory to analyse evaporation rate measurements, and illustrate how vaporisation at the liquid | gas interface is dominated by a diffusion anisotropy, owing to natural convection for organic solvents, manufactured resins and commercialised inks that have been used, inter alia, for the underground transport tickets in the cities of London and Paris. We further demonstrate that the use of incorrect solvents is readily seen through evaporation rate transients, thereby enabling this measurement for human factor mitigation during the ink manufacture process

Mapping High-velocity H-alpha and Lyman-alpha Emission from Supernova 1987A

We present new {\it Hubble Space Telescope} images of high-velocity H-$\alpha$ and Lyman-$\alpha$ emission in the outer debris of SN~1987A. The H-$\alpha$ images are dominated by emission from hydrogen atoms crossing the reverse shock. For the first time we observe emission from the reverse shock surface well above and below the equatorial ring, suggesting a bipolar or conical structure perpendicular to the ring plane. Using the H$\alpha$ imaging, we measure the mass flux of hydrogen atoms crossing the reverse shock front, in the velocity intervals ($-$7,500~$<$~$V_{obs}$~$<$~$-$2,800 km s$^{-1}$) and (1,000~$<$~$V_{obs}$~$<$~7,500 km s$^{-1}$), $\dot{M_{H}}$ = 1.2~$\times$~10$^{-3}$ M$_{\odot}$ yr$^{-1}$. We also present the first Lyman-$\alpha$ imaging of the whole remnant and new $Chandra$ X-ray observations. Comparing the spatial distribution of the Lyman-$\alpha$ and X-ray emission, we observe that the majority of the high-velocity Lyman-$\alpha$ emission originates interior to the equatorial ring. The observed Lyman-$\alpha$/H-$\alpha$ photon ratio, $\langle$$R(L\alpha / H\alpha)$$\rangle$ $\approx$~17, is significantly higher than the theoretically predicted ratio of $\approx$ 5 for neutral atoms crossing the reverse shock front. We attribute this excess to Lyman-$\alpha$ emission produced by X-ray heating of the outer debris. The spatial orientation of the Lyman-$\alpha$ and X-ray emission suggests that X-ray heating of the outer debris is the dominant Lyman-$\alpha$ production mechanism in SN 1987A at this phase in its evolution.Comment: 6 pages, 5 figures. ApJL - accepte

Performance of lyotropic liquid crystal-based photoelectrochemical capacitors for solar-to- electrical energy conversion

Regenerative photoelectrochemical capacitors, adapted from a experimental system previously reported (J. E. Halls, J. D. Wadhawan, Energy Environ. Sci., 2012, 5, 6541) and based on the doping of a lamellar lyotropic liquid crystal with visible light sensitizer tris(2,2'-bipyridyl)ruthenium(II), N-methylphenothiazine, zinc(II) ions and potassium chloride (as electrolyte) are examined in this work. The two dye species, by virtue of similarity in redox potentials and difference in size and lipophilicity, allow for electron transfer cascades to occur under illumination, which can be harnessed in a power-generating device through the use of a sacrificial counter electrode. In operation as a solar cell, a maximum light-to-electrical power conversion efficiency is reported as being ~5.0% under green light (530 nm centreband, 30 nm bandwidth, 2.2 mW cm-2 intensity), which extrapolates to the opportunistic value of 1% under one Sun conditions. The electrical characteristics of the devices under illumination afford specific capacitances of ca. 0.5-1.0 F g-1 and have fill factors ~20% which are close to the 25% expected for a perfect photogalvanic cell. The time constants of the reported devices (~1.5 s) are consistent with the notion of electroporation of the surfactant lamellae. The advantages of these mid-ranging photoelectrochemical capacitors are suggested as being their low cost and versatility afforded by their flexible liquid framework that appears to realign itself under conditions of open circuit

Electrochemical Quantification of D-Glucose during the Production of Bioethanol from Thermo-Mechanically Pre-treated Wheat Straw

Mechanical pre-treatment (disc refining) of wheat straw, at both atmospheric and elevated pressure, is shown to be an efficient process to access fermentable monosaccharides, with the potential to integrate within the infrastructure of existing first-generation bioethanol plants. The mild, enzymatic degradation of this sustainable lignocellulosic biomass affords ca. 0.10-0.13 g/g (dry weight) of D-glucose quantifiable voltammetrically in real time, over a two hundred-fold range in experimental laboratory scales (25 mL to 5.0 L), with pressure disc refining of the wheat straw enabling almost twice the amount of D-glucose to be generated during the hydrolysis stage than experiments using atmospheric refining (0.06 – 0.09 g/g dry weight). Fermentation of the resulting hydrolysate affords 0.08 – 0.10 g/g (dry weight) of ethanol over similar scales, with ethanol productivity at ca. 37 mg/(L h). These results demonstrate that minimal cellulose decomposition occurs during pressure refining of wheat straw, in contrast to hemicellulose, and suggest that the development of green, mechanochemical processes for the scalable and cost-effective manufacture of second-generation bioethanol requires improved cellulose decomposition

Phototriggered Secretion of Membrane Compartmentalized Bioactive Agents

A strategy for the light-activated release of bioactive compounds (BODIPY, colchicine, paclitaxel, and methotrexate) from membrane-enclosed depots is described. We have found that membrane-permeable bioagents can be rendered membrane impermeable by covalent attachment to cobalamin (Cbl) through a photocleavable linker. These Cbl-bioagent conjugates are imprisoned within lipid-enclosed compartments in the dark, as exemplified by their retention in the interior of erythrocytes. Subsequent illumination drives the secretion of the bioactive species from red blood cells. Photorelease is triggered by wavelengths in the red, far-red, and near-IR regions, which can be pre-assigned by affixing a fluorophore with the desired excitation wavelength to the Cbl-bioagent conjugate. Pre-assigned wavelengths allow different biologically active compounds to be specifically and unambiguously photoreleased from common carriers