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Biomedical subjects

R G Compton

Publications and source records attributed to R G Compton.

13 recordsLinked to original sources

Laminated microelectrodes: a simple approach to the construction of inexpensive microelectrodes with a variety of geometries.

Designs for reusable microelectrodes, which are easy to assemble and so do not require special technical skills or services for their construction, are presented. Three types of microelectrodes are fabricated by lamination of metal foil, wire, and wire grids, producing microband, microdisk, and a linear array of microdisk geometries. The electrodes themselves do not need to be polished prior to their use but are observed to be slightly recessed from the surrounding insulating surface. Good agreement is observed between experimental steady-state voltammetric results in nonaqueous solutions and the relevant analytical theory for the voltammetric current.

Journal Article↗

Bioanalytical utility of sonovoltammetry.

Dopamine dissolved within egg homogenate was used as a model system to study the effects of electrode contamination and its subsequent reactivation through ultrasonically mediated in situ cleaning effects. The merits in conducting electroanalytical investigations under the influence of the ultrasonic field were also appraised. Maintaining the ultrasound field during oxidative measurements was found to yield hydrodynamic profiles that were linear over the concentration range 2-20 microM dopamine. The resulting sonolinear sweep voltammograms were compared with conventional rotating disk measurements, with the former found to provide significantly increased limiting currents that were attenuable through the manipulation of the field intensity. The problem of retaining selectivity in the presence of high concentrations of ascorbate was also assessed with the addition of cupric ion prior to commencing the measurements found to efficiently negate an otherwise substantive interference.

Dopamine↗

Electroanalytical exploitation of quinone-thiol interactions: application to the selective determination of cysteine.

Square wave voltammetry was applied to the detection of cysteine through the use of an indirect assay that exploits the reaction of the thiol with a quinone indicator. Voltammetric discrimination between unreacted quinone and the corresponding quinone-cysteine adduct is possible with clear resolution of the latter peak providing a linear response from 5 to 47 microM. The selectivity of the approach was assessed with no interference from cystine, lysine, paracetamol or 4-aminophenol. The response recorded in the presence of a massive excess of ascorbic acid was also investigated and the integrity of the approach confirmed. The effects of other sulfhydryl thiols, homocysteine and glutathione, were also assessed and found to present no appreciable change in the voltammetric profile. The practical utility of the approach was investigated through examining the response to cysteine in urine.

Benzoquinones↗

Voltammetric investigation of hair dye constituents: application to the quantification of p-phenylenediamine.

The application of electrochemical techniques to the determination of common hair dye constituents was investigated. Cyclic voltammetry was used to probe the electrode response to p-phenylenediamine (PPD), 4-chlororesorcinol and m-aminophenol with square wave voltammetry used to effect quantitative measurements. The nature of the electrode response was characterised and issues of surface fouling resulting from the deposition of electrogenerated reaction products were addressed. A procedure designed to allow the facile determination of PPD in hair care products is presented.

Carbon↗

The electroanalytical detection and determination of copper in heavily passivating media: ultrasonically enhanced solvent extraction by N-benzoyl-N-phenyl-hydroxylamine in ethyl acetate coupled with electrochemical detection by sono-square wave stripping voltammetry analysis.

N-benzoyl-N-phenyl-hydroxylamine dissolved in ethyl acetate was employed as a ligand for the solvent extraction of copper. Ultrasonic emulsification was shown to be effective both in the extraction of copper from an aqueous phase into ethyl acetate and its recovery or "back extraction" into a fresh clean aqueous solution. Experimental determination of thermodynamic parameters governing the extraction process via UV/visible spectroscopy is reported. This permitted theoretical predictions for the amount of copper transferred into the final aqueous solution to be fitted to experimental data. Quantitative analysis of copper removed via double sono-extraction from an aqueous medium hostile to voltammetric analysis proceeded via sono-square wave anodic stripping voltammetry analysis (sono-SWASV). This resulted in very high sensitivity in the relatively clean medium. The technique was then applied to the analysis of copper in the soft drink 'Ribena Light'. In the absence of sample preparation by solvent extraction sono-SWASV yields a measurable peak current for copper. However it is irreproducible and erratic due to passivating effects, possibly attributed to the sugars, natural flavourings and colourings present. Following sono-solvent extraction, the overall copper concentration could be obtained with a detection limit of 2 microg L(-1). Biphasic sono-extraction synergistically coupled with the recognized technique sono-SWASV presents an attractive technique for copper analysis in electrode passivating media. The technique necessarily removes contaminants present in the test solution since these will prefer to remain in the initial aqueous phase, or will transfer to the organic phase but are unlikely to be doubly transferred into the 'clean' final aqueous phase.

Journal Article↗

Sonoelectroanalysis--an overview.

The coupling of power-ultrasound with well established but under-exploited electrochemical stripping voltammetry has led to the emergence of a powerful new analytical technique--sonoelectroanalysis. Where classical electroanalytical techniques were plagued with electrode-fouling and/or sensitivity limitations, the introduction of ultrasound into the system has given great increases in analytical efficiency and substrate applicability, predominantly through enhanced mass transport and electrode surface activation. This revitalised analytical technology has been applied to a range of modern analytical problems, allowing sensitive determination of a wide number of analytes from a variety of otherwise hostile matrices, including copper in beer and blood, lead in wine, petrol and river bed sediment, vanadium in aqueous media, nitrite in egg and manganese in instant tea granules. This paper gives an overview of these recent advances.

Alcoholic Beverages↗

Sonoelectroanalytical detection of lead at a bare copper electrode.

The sonochemically facilitated, mercury free detection of Pb2+ at a copper electrode has been investigated as a means of simplifying the quantification of this important analyte and to minimise the interference of copper ion. The procedure relies upon maximising the formation of Pb-Cu intermetallic compounds leading to the emergence of a single, easily quantifiable stripping signal. Linear responses to Pb2+ were obtained with a sensitivity comparable to that obtained at a bare glassy carbon electrode. Interference from Cu2+, Zn2+ and Cd2+ was assessed on the copper electrode with no appreciable change in the Pb2+ voltammetric profile observed. In contrast, bare glassy carbon showed a significant change in Pb2+ voltammetric profile as Cu2+ was added, due to the formation of intermetallic species.

Calibration↗

Ultrasonically enhanced leaching: removal and destruction of cyanide and other ions from used carbon cathodes.

The used carbon cathodes ('Spent Pot Lining', SPL) from aluminium smelting are typically contaminated with F-, CN- and Na+ which must be removed before disposal to produce material which satisfies environmental guidelines in respect of maximum rates of ion release. Leaching of powdered and crushed carbon samples in aqueous solution were studied in the presence and absence of ultrasound. First, it was demonstrated that the total leaching of F-, CN- and Na+ from the carbon powder could be accomplished after approximately 20 min of sonication using ultrasound. Second, carbon particles (< 5 mm) showed leaching characteristics under ultrasound which were in good quantitative agreement with the National River Authority (NRA) test under silent conditions; the former being a much more rapid (approximately 1 h compared to 24 h for the NRA test) but equivalent method to the latter standard test. Third, the removed CN- ions were found to be destroyed in the presence of ultrasound, possibly via the oxidative action of hydrogen peroxide generated by the sonication of water.

Journal Article↗

Sonoelectrochemical and sonochemical effects of cavitation: correlation with interfacial cavitation induced by 20 kHz ultrasound.

Sonoelectrochemical measurements at macro-electrodes under extreme conditions with a very short distance between ultrasonic horn tip and electrode and different ultrasound intensity levels are shown to result in violent cavitation detected in form of current peaks superimposed on the average limiting current. Analysis of the current data obtained for the oxidation of ferrocene in dimethylformamide (0.1 M NBu4PF6) at a 4 mm diameter Pt disc electrode and for the reduction of Ru(NH3)6(3+) in aqueous 0.1 M KCl at a 6 mm diameter Pt disc electrode consistently indicate a change of the physicochemical nature of sonoelectrochemical processes under extreme conditions. The sonoelectrochemical measurement of the rate constant for the carbon bromide bond cleavage of a 3-bromobenzophenone radical anion electrogenerated at a glassy carbon electrode in dimethylformamide solution in the presence of power ultrasound is shown to yield evidence for a breakdown of the conventional mass transport model of a planar diffusion layer under extreme conditions. The change can be correlated to the number of current data points deviating more than 10% from the mean of the current due to violent cavitation processes superimposed onto the average limiting current. Further, a study of the sonochemical destruction of aqueous dilute cyanide solution (in 0.1 M NaOH) demonstrates a correlation between the electrochemically detected cavitation violence and the sonochemical activity. Factors that govern the violence of interfacial cavitation appear to be directly proportional to the factors that make cavitation in the bulk solution chemically efficient.

Journal Article↗

Sono-cathodic stripping voltammetry of manganese at a polished boron-doped diamond electrode: application to the determination of manganese in instant tea.

Ultrasonically assisted cathodic stripping voltammetry at a boron-doped diamond electrode was developed for the detection of manganese. Differential-pulse voltammetry was used to give the analytical signal from a cathodic strip of electrodeposited MnO2; linearity was observed from 10(-11) M to at least 3 x 10(-7) M, with 10(-11) M being the detection limit for a 2 min deposition. The procedure involves both ultrasonic-anodic deposition of MnO2 and ultrasonic-cathodic stripping. This novel analytical tool is robust, reproducible, mercury free, oxygen insensitive and highly specific towards manganese. The differential-pulse sono-cathodic stripping voltammetric technique was used to determine successfully the manganese content of two instant tea samples, giving excellent agreement with independent AAS analyses.

Boron↗

A novel approach for the quantitative kinetic study of reactions at solid/liquid interfaces in the presence of power ultrasound.

A novel cell and procedure is described which permits the quantitative mechanistic study of ultrasonically enhanced reactions which occur at solid/liquid interfaces. A model of a controlled and calculable time-average rate of mass transport to and from the interface is used in order to compare experimental results with theoretical predictions based on mechanistic reaction schemes. In this way concentrations of mechanistically significant species near the interface can be related to those in bulk solution and hence the sonochemical effects of ultrasound dissected from those arising purely from mass transport. The effect of ultrasound is demonstrated for the reaction dissolution of p-chloranil in the presence of aqueous base and for the reaction of the same substrate with the aromatic amine, N,N-dimethyl-phenylenediamine, both systems which have been studied previously in the absence of ultrasound. Complementary atomic force microscopy images are also reported.

Journal Article↗

Ultrasound in photoelectrochemistry: a new approach to the enhancement of the efficiency of semiconductor electrode processes.

A novel photoelectrochemical experiment which simultaneously allows the illumination of a TiO2 semiconductor electrode surface and the application of power ultrasound emission is described. The horn probe of an immersion horn transducer is modified by an oxide coated titanium tip and placed in a conventional three electrode electrochemical cell which allows light from a monochromated source to be focussed onto the electrode surface. Well-defined photocurrents are observed in aqueous media and for the photoinduced oxidation of water in acetonitrile and of 2.4-dichlorophenol in acetonitrile. The effect of ultrasound is to shift the observed photocurrent responses to more negative potentials and therefore to enhance the observed processes. Several possible interpretations associated with the complex effects induced by ultrasound are considered and a model based mainly on the extreme change of mass transport at the semiconductor/solution interface is suggested. Considerably enhanced performance for non-Nernstian processes, such as those observed in photoelectrochemical reactions at semiconductor electrodes, can be achieved in the presence of ultrasound.

Journal Article↗

A modified electrode for the electrochemical reduction of isoflurane.

The popular anaesthetic gas isoflurane is found to be electrochemically inert on a wide range of conventional electrode materials in both aqueous and non-aqueous solvents. However the chemically modified electrode produced by depositing the novel electroactive polymer, poly(vinylfluoranthene), onto a platinum electrode is shown to mediate electron transfer to the anaesthetic thus bringing about its electro-reduction and so offers the promise of amperometric electrochemical sensors based on this electrode.

Electrochemistry↗