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Biomedical subjects

P N Bartlett

Publications and source records attributed to P N Bartlett.

16 recordsLinked to original sources

Easily coupled whispering gallery plasmons in dielectric nanospheres embedded in gold films.

A new self-aligned robust method for coupling to whispering gallery modes (WGMs) of submicron microspheres utilizes their periodic arrangement without relying on nanopositioned external coupling devices. The microspheres are embedded in a nanostructured gold surface supporting delocalized plasmonic crystal modes that mediate the coupling, and can be tuned by the geometry. Detailed measurements of the angle- and orientation-dependent reflectivity reveal localized plasmonic WGMs whose energies scale with sphere diameter and agree closely with Mie calculations. Coupling between these plasmonic WGMs leads to mode splitting and the formation of plasmonic minibands of a controllable bandwidth.

Journal Article↗

Plasmonic band gaps and trapped plasmons on nanostructured metal surfaces.

Nanostructured metal surfaces comprised of periodically arranged spherical voids are grown by electrochemical deposition through a self-assembled template. Detailed measurements of the angle- and orientation-dependent reflectivity reveal the spectral dispersion, from which we identify the presence of both delocalized Bragg and localized Mie plasmons. These couple strongly producing bonding and antibonding mixed plasmons with anomalous dispersion properties. Appropriate plasmon engineering of the void morphology selects the plasmon spatial and spectral positions, allowing these plasmonic crystal films to be optimized for a wide range of sensing applications.

Journal Article↗

Tunable resonant optical microcavities by self-assembled templating.

Micrometer-scale optical cavities are produced by a combination of template sphere self-assembly and electrochemical growth. Transmission measurements of the tunable microcavities show sharp resonant modes with Q factors of >300 and 25-fold local enhancement of light intensity. The presence of transverse optical modes confirms the lateral confinement of photons. Calculations show that submicrometer mode volumes are feasible. The small mode volumes of these microcavities promise to lead to a wide range of applications. in microlasers, atom optics, quantum information, biophotonics, and single-molecule detection.

Journal Article↗

The demonstration of an enhanced microelectrochemical transistor for measurements in neutral solution at low analyte concentration.

We report a new, sensitive detection method for the measurement of analytes based on the combination of conducting polymer technology and redox enzyme electrochemistry. This method provides a simple measurement method potentially enabling point of care testing on disposable electrodes in under 60 s. The measurement does not require a reference or counter electrode and the analytical signal is recorded by an ammeter measuring milliampere currents through a polymer transistor. Even at very low analyte concentration, the signal is not subject to significant noise.

Aminophenols↗

The measurement of alkaline phosphatase at nanomolar concentration within 70 s using a disposable microelectrochemical transistor.

We report a new approach to the measurement of alkaline phosphatase concentration based on the use of a disposable poly(aniline) microelectrochemical transistor. The measurement is carried out in a two cell configuration in which the poly(aniline) microelectrochemical transistor operates in acid solution and is connected to the alkaline buffer solution containing the analyte by a salt bridge. Disposable microelectrochemical transistors were reproducibly fabricated by electrochemical deposition of poly(aniline) onto photolithographically fabricated gold microband arrays. Using these devices alkaline phosphatase was detected by employing p-aminophenyl phosphate as the substrate for the enzyme and using glucose and glucose oxidase to recycle the p-aminophenol generated upon enzyme catalysed hydrolysis of the phosphate. Recycling the p-aminophenol with glucose and glucose oxidase amplified the detection of alkaline phosphatase approximately tenfold. Using this approach we obtain linear calibration curves for alkaline phosphatase up to 5 nM within 70 s on single use devices.

Alkaline Phosphatase↗

Optical properties of nanostructured metal films.

Nanostructured metal films of platinum, gold and silver up to 675 nm thick we prepared by electrochemical deposition through templates of 700 nm diameter polystyrene spheres assembled as hexagonal close packed monolayer on an evaporated gold surface followed by removal of the template by dissolution in tetrahydrofuran. The reflection spectra of the films at normal incidence were recorded as a function of film thickness and the spectra correlated with the local visual appearance of the film and the surface structure from SEM. For thin films, below one quarter sphere height, the spectra show a single reflectivity dip at a wavelength just below the sphere diameter consistent with surface-plasmon grating-like behaviour. For the thicker films several reflectivity dips are observed which move towards longer wavelength with increasing film thickness. This behaviour is shown to be consistent with a model in which light reflected from the top of the structure interferes with light reflected from within the spherical segment cavities in the film.

Journal Article↗

Modified electrodes for NADH oxidation and dehydrogenase-based biosensors.

The direct electrochemical oxidation of beta-nicotinamide adenine dinucleotide (NADH) at clean electrodes proceeds through a radical cation intermediate at high overpotentials and is subject to rapid fouling. Consequently, there has been a considerable body of work over the last 20 years looking at ways in which to catalyse the reaction using a wide variety of different types of modified electrode. These studies have resulted in a good knowledge of the essential features required for efficient catalysis. In designing modified electrodes for NADH oxidation, it is not only important to identify suitable redox groups, which can catalyse NADH oxidation and can be attached to the electrode surface; it is also important to ensure facile charge transport between the immobilised redox sites in order to ensure that, in multilayer systems, the whole of the redox film contributes to the catalytic oxidation. One way to achieve this is by the use of electronically conducting polymers such as poly(aniline).

Biosensing Techniques↗

Waveguide surface plasmon resonance studies of surface reactions on gold electrodes.

We describe the fabrication and characterisation of gold-coated graded index channel waveguide sensors designed for simultaneous electrochemical and surface plasmon resonance studies. The active sensing electrode area is a thin gold film between 0.5 and 5 mm in length and 200 microm wide deposited on top of a 3 microm wide waveguide which forms one arm of a Y-junction while the other arm of the Y-junction serves as a reference. Using these devices we have measured simultaneously the changes in transmittance through the device whilst carrying out cyclic voltammetry in either sulfuric or perchloric acid solution or during the deposition of an UPD layer of copper at the gold surface. In all cases we obtain stable and reproducible results which demonstrate the very high sensitivity of the devices to sub-monolayer changes occurring at the gold electrode surface. The response of these integrated optoelectrochemical devices is discussed in terms of a numerical model for the propagation of light within the waveguide structure.

Journal Article↗

Confined plasmons in metallic nanocavities.

We investigate the properties of gold surfaces patterned using a nanoscale "lost wax" technique by electrochemical deposition through a self-assembled latex template. Near-spherical gold nanocavities within the resulting porous films support localized surface plasmons which couple strongly to incident light, appearing as sharp spectral features in reflectivity measurements. The energy of the resonances is easily tunable from ultraviolet to near infrared by controlling the diameter and height of the nanocavities. The energies of these features agree well with the Mie resonances of a perfect spherical void.

Journal Article↗

Electrochemical characterization of a templated insulating polymer-modified electrode.

The controllable permselective behavior oftemplated poly(1,2-diaminobenzene)-modified electrodes is illustrated. The electrochemical behavior of polymer films prepared from several media, conventional aqueous solution, liquid crystalline micellar solution, and liquid crystalline hexagonal phase solution, were compared using several cationic and anionic redox probes. Films deposited from the hexagonal liquid crystalline phase were shown to be ion selective, allowing positively charged ions through to react at the electrode surface while excluding negatively charged ions. This permselective behavior was unique to the hexagonally templated films and was not exhibited by films deposited from either the conventional aqueous or the micellar media (which were completely blocking to both types of ion). In addition, it was shown that by altering the ionic strength of the background electrolyte control over the charge selective behavior of the hexagonally templated films was possible.

Journal Article↗

Covalent attachment of osmium complexes to glucose oxidase and the application of the resulting modified enzyme in an enzyme switch responsive to glucose.

Pyridine-based osmium complexes bearing either a carboxylate or aldehyde group were covalently attached to glucose oxidase and were shown to work as mediators for the reoxidation of the enzyme. For the complex containing the carboxylate group, the binding was made through carbodiimide coupling to the amine residues in the protein. For the complex containing the aldehyde group, the reductive coupling was carried out by condensation with the amino groups on the protein in the presence of sodium cyanoborohydride. Electrochemical studies show evidence for both intramolecular and intermolecular redox mediation for the electrochemical reoxidation of the modified glucose oxidases in the presence of glucose. The modified enzymes adsorbed on glassy carbon and platinum show different electrochemical responses for the two electrode materials, suggesting that orientation of the adsorbed enzyme is induced due to the interaction of the osmium complex with the different surfaces. Construction of enzyme switches based on these modified enzymes was carried out, and their responses were compared with those obtained using native glucose oxidase and a soluble redox mediator.

Aspergillus niger↗

An instrument for simultaneous EQCM impedance and SECM measurements.

A novel combination of an electrochemical quartz crystal microbalance (EQCM) and a scanning electrochemical microscope (SECM) has been built. Unlike conventional EQCMs, the instrument described here allows rapid in situ measurement of the modulus of the quartz crystal's transfer function. Data analysis in the complex plane for the Butterworth-Van Dyke (BVD) equivalent circuit yields the real and the imaginary components R (damping resistance) and XL (reactive inductance) of the crystal's electroacoustic impedance around its resonant frequency of 10 MHz. The influence of different tip shapes of an approaching microelectrode on the electroacoustic impedance of the quartz crystal was studied and found to be minimal for certain geometries. The capability of the EQCM/SECM instrument was tested in cyclic voltammetric plating/stripping experiments using a copper(I) chloride solution of high concentration in 1 M HCl. Four parameters, XL, R, the substrate, and the tip current, can be recorded simultaneously. Depletion layer effects were observed and could be corrected for to yield accurate current efficiencies for potentiodynamic and potentiostatic copper plating. The amperometric response of the SECM tip positioned closely to the substrate reflects the concentration changes of electroactive ions in the diffusion layer of the substrate electrode.

Algorithms↗

Modified electrode surface in amperometric biosensors.

The electron transfer reactions of biological molecules are frequently very slow at ordinary electrodes. To overcome this problem, and thus to facilitate the direct coupling of biological redox reactions to electrodes for biosensor or bioelectronic applications, various types of modified electrode have been used. These include electrodes modified by the covalent attachment of species to the surface, by the reversible adsorption of promotors, or by the deposition of polymeric species, and the use of conducting polymers or conducting organic salts as electrode materials. Some of these different approaches are reviewed and their applications to biosensors and bioelectrochemistry are discussed.

Biosensing Techniques↗

Amperometric enzyme electrodes.

Three different types of amperometric enzyme electrode are described. The first type uses a conducting organic-salt electrode to oxidize NADH. Results for sensors for ethanol and for bile acids are presented. In the second type of sensor, flavoenzymes are directly oxidized on the surface of the conducting organic-salt electrode. Results for five different enzymes are described. The mechanism of the enzyme oxidation is discussed and the reaction is shown to take place by heterogeneous redox catalysis and not by homogeneous mediation. The enzymes are strongly adsorbed on the electrode; microelectrodes for in vivo studies can be constructed without a membrane. Results for in vivo studies of changing glucose levels in the brain of a freely moving rat are presented. The third type of sensor is designed to measure low levels of toxic gases such as H2S and HCN. This is done by monitoring the inhibition by the toxic gas of the activity of the respiratory enzyme cytochrome oxidase.

Animals↗

An amperometric enzyme electrode for monitoring brain glucose in the freely moving rat.

Brain glucose concentration was measured with an amperometric enzyme electrode using glucose oxidase (EC 1.1.3.4) irreversibly adsorbed onto an organic conducting salt. The responses of the electrode and its stability both in vitro and in vivo are described. Parellel changes in brain glucose and blood glucose (measured in samples from an implanted intra-atrial cannula) following injections of insulin are reported.

Animals↗

Strategies for the development of amperometric enzyme electrodes.

There are now a number of distinct strategies which can be employed to make amperometric enzyme electrodes. These include the use of homogeneous mediators, modified electrodes and organic conducting salts. In this paper we review these strategies and discuss their application to NAD(P)H dependent dehydrogenase and flavoprotein based biosensors. In addition we discuss recent work on the immobilisation of glucose oxidase in polypyrrole, poly-N-methylpyrrole, polyaniline and polyphenol films electrochemically grown at the electrode surface and on the covalent attachment of redox mediators to glucose oxidase in order to achieve direct electron transfer to the electrode.

Biosensing Techniques↗