Mutagenicity and DNA damage studies of N-acyloxy-N-alkoxyamides--the role of electrophilic nitrogen

N-Acyloxy-N-alkoxyamides are anomeric amides that are direct-acting mutagens. They have been shown to damage DNA in the major and the minor grooves in a pH and sequence-selective manner. In acidic media, they damage adenines at N3 in the minor groove but above neutral pH, only guanine is damaged at N7 in the major groove. Both the acyloxy leaving group and the alkoxy group at the amide nitrogen are responsible for their electrophilicity and Salmonella mutagenicities in TA 100 and DNA damage data confirm that the mutagens react with DNA in an intact form, rather than by solvolysis to electrophilic nitrenium ions in the cytosol, or in vitro, prior to reacting with DNA. Hydrophobicity plays a role in both mutagenicity and DNA damage.     

Detection of specific antibodies using immunosubtraction and capillary electrophoresis instrumentation

Solution-phase immunoassays based on capillary electrophoresis (CE) separations have been shown to be rapid and simple to perform. The potential for sample matrix interference and incompatibility with multiplexing conditions for antibody detection when dealing with real samples, however, has prompted the development of an assay that utilizes an immunosubtraction methodology. A model assay for the detection of specific antibodies that relies on solid-phase extraction, CE and laser-induced fluorescence (LIF) detection is described. The method, called immunocapture-immunosubtraction (ICIS), incorporates an antibody capture/purification protocol using magnetic particles. The detection of specific antibodies is achieved by CE-LIF analysis of a probe solution following incubation with the captured antibodies. As an example of the ICIS assay's capabilities, the relative quantification of anti-fluorescein in serum is presented.     

Disposable highly ordered pyrolytic graphite-like electrodes: Tailoring the electrochemical reactivity of screen printed electrodes

We demonstrate that the electron transfer properties of disposable screen printed electrodes can be readily tailored via the introduction of a polymeric formulation into the ink used to fabricate these electrochemical platforms. This approach allows the role of the binder on the underpinning electrochemical properties to be explored and allows the electrochemical reactivity of the screen printed electrodes to be tailored from that of edge plane to basal plane of highly ordered pyrolytic graphite.     

Thermal explosion for a slab with spatially varying surface temperature

Summary The thermal stability of reacting slabs whose surface temperature is a function of position is investigated. It is assumed that the variation is not large so that a perturbation approach may be adopted. Conditions for criticality are sought both for periodic distributions and others. A related problem where the boundary is perturbed but maintained at constant temperature is also considered.

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Zusammenfassung Die thermische Stabilität von chemisch reagierenden Platten mit örtlich variierender Oberflächentemperatur wird untersucht. Es wird angenommen, daß die Temperaturunterschiede gering sind. Dann kann eine Perturbationsmethode angewendet werden. Die kritischen Bedingungen für periodische und aperiodische Verteilungen werden angegeben. Ebenso wird ein verwandtes Problem behandelt, bei dem der Verlauf des Plattenrandes leicht gestört, aber auf einer konstanten Temperatur gehalten wird.

     

Criticality and transition in the initiation of thermal explosion by light

Summary The work of Lin, Richardson & Eyring and Boddington, Feng & Gray on the theory of the initiation of thermal explosion by steady intense light is developed further. In the large activation energy limit analytic solution is possible and conditions for criticality are deduced for large and small values of light-intensity parameter. The disappearance of criticality is examined numerically for the full range of light-intensity parameter. Results are compared with those obtained by using a simple constant reaction-rate assumption.     

Gold Nanoparticle Modified Screen Printed Electrodes for the Trace Sensing of Arsenic(III) in the Presence of Copper(II)

Gold ensembles for the trace level sensing of arsenic(III) in the presence of copper(II) are reported. The gold ensembles are fabricated using citrate capped gold nanoparticles which are chemically synthesised in an aqueous solution with an aliquot of this simply cast onto an economical and disposable screen printed electrode. After drying at room temperature, the gold ensembles are ready for use. The gold ensembles are explored towards the sensing of arsenic(III) in the presence of copper(II) using anodic stripping voltammetry where the corresponding stripping peaks are well resolved and using this protocol it is possible to readily detect 3 µg L^?1 (3 ppb) with a detection limit of 0.4 µg L^?1 (0.4 ppb). Proof‐of‐concept is also shown for the sensing of arsenic(III) in a canal water sample. Given the low cost of the sensor and ease of fabrication, the gold ensembles hold promise for the sensing of arsenic(III) in water samples where copper(II) may be present.     

Metallic impurity free carbon nanotube paste electrodes

Electrodes modified with carbon nanomaterials find wide ranging applications in electrochemistry such as in energy generation and storage through to applications in electroanalysis. A substantial limitation is the presence of metallic impurities which vary between batches and can produce erroneous results. Consequently we have explored the electrochemical properties of metallic impurity free carbon nanotube paste electrodes using potassium ferrocyanide and hydrogen peroxide as model compounds. In terms of the latter utilising cyclic voltammetry, a linear range from 0.75 to 3 mM with a limit of detection of 0.19 mM is possible using the electrochemical oxidation of hydrogen peroxide while using the electrochemical reduction of the target analyte, a linear range from 0.5 to 249 mM is possible with a detection limit of 0.43 mM.The ultra-small size of the carbon nanotubes and fabrication methodology result in a tightly bound carbon nanotube electrode surface which does not exhibit thin-layer behaviour resulting in highly reproducible electrodes with the %RSD found to be 5.5%. These analytical ranges, detection limits and reproducibility are technologically useful.The carbon nanotubes utilised are completely free from metallic impurities and do not require lengthy processing to remove impurities and consequently have no variation in the purity of the nanomaterial between batches as is commonly the case for other available carbon nanotube material. The impurity free nature of this nanomaterial allows for highly reproducible and intelligent sensors based on carbon nanotubes to be understood and realised for the first time.     

Cosmetic Electrochemistry II: Rapid and Facile Production of Metallic Electrocatalytic Ensembles

We demonstrate a facile methodology for the production of metallic electrocatalytic microdomain ensembles for a range of analytical sensing challenges. A commercially available off‐the‐shelf cosmetic product can change the voltammetric characteristics of a metallic macro‐electrode created electrolytically into that of a random ensemble of metallic microelectrode domains. Proof‐of‐concept is shown for three examples: a palladium ensemble for hydrazine sensing, a gold ensemble for arsenic(III) detection via anodic stripping voltammetry and platinum ensembles for the direct oxidation of arsenic(III). Last we demonstrate that the fabrication of metallic microdomains can be simplified by sputter coating screen printed electrochemical sensing platforms which are beneficially constructed using this cosmetic methodology. Given the facile fabrication and low cost of the underlying electrode substrate and the cosmetic modifier, the widespread implementation of this novel fabrication methodology is expected.     

An Euler system source term that develops prototype Z‐pinch implosions intended for the evaluation of shock‐hydro methods

In this paper, a phenomenological model for a magnetic drive source term for the momentum and total energy equations of the Euler system is described. This body force term is designed to produce a Z‐pinch like implosion that can be used in the development and evaluation of shock‐hydrodynamics algorithms that are intended to be used in Z‐pinch simulations. The model uses a J × B Lorentz force, motivated by a 0‐D analysis of a thin shell (or liner implosion), as a source term in the equations and allows for arbitrary current drives to be simulated. An extension that would include the multi‐physics aspects of a proposed combined radiation hydrodynamics (rad‐hydro) capability is also discussed. The specific class of prototype problems that are developed is intended to illustrate aspects of liner implosions into a near vacuum and with idealized pre‐fill plasma effects. In this work, a high‐resolution flux‐corrected‐transport method implemented on structured overlapping meshes is used to demonstrate the application of such a model to these idealized shock‐hydrodynamic studies. The presented results include an asymptotic solution based on a limiting‐case thin‐shell analytical approximation in both (x, y) and (r, z). Additionally, a set of more realistic implosion problems that include density profiles approximating plasma pre‐fill and a set of perturbed liner geometries that excite a hydro‐magnetic like Rayleigh–Taylor instability in the implosion dynamics are demonstrated. Finally, as a demonstration of including and evaluating multiphysics effects in the Euler system, a simple radiation model is included and self‐convergence results for two types of (r, z) implosions are presented. Copyright © 2008 John Wiley & Sons, Ltd.