Biomedical subjects

P R Unwin

Publications and source records attributed to P R Unwin.

8 recordsLinked to original sources

PubMed2001

High resolution imaging of the distribution and permeability of methyl viologen dication in bovine articular cartilage using scanning electrochemical microscopy.

Scanning electrochemical microscopy (SECM) has been used in the induced transfer (SECMIT) mode to image the permeability of a probe cation, methyl viologen (MV(2+)), in samples of articular cartilage. An ultramicroelectrode (UME), scanned just above the surface of a sample, is used to amperometrically detect the probe solute. The resulting depletion of MV(2+) in solution induces the transfer of this cation from the sample into the solution for detection at the UME. The current provides quantitative information on local permeability, provided that the sample-UME distance is known. It is shown that the necessary topographical information can be obtained using the amperometric response for the oxidation of Ru(CN)(4-)(6), which does not permeate into the cartilage matrix. This procedure was validated by marking samples in situ, after electrochemical imaging, with subsequent examination by ex situ interferometry and optical microscopy. Wide variations in the permeability of MV(2+) have been detected by SECMIT. These observations represent the first demonstration of the inhomogeneous permeability of a cation in cartilage on a micrometre scale. The permeability maps show similar features to the proteoglycan distribution, identified by toluidine blue staining, and it is likely that proteoglycans are the main determinant of MV(2+) permeability in articular cartilage.

Animals↗

PubMed2001

Electron transfer reactions at gold nanoparticles.

It is demonstrated that scanning electrochemical microscopy can be used to investigate the kinetics of electron transfer reactions catalysed by metal nanoparticles supported on an insulating substrate.

Journal Article↗

PubMed2001

Noncontact electrochemical imaging with combined scanning electrochemical atomic force microscopy.

Combined scanning electrochemical atomic force microscopy (SECM-AFM) is a recently introduced scanned probe microscopy technique where the probe, which consists of a tip electrode and integrated cantilever, is capable of functioning as both a force sensor, for topographical imaging, and an ultramicroelectrode for electrochemical imaging. To extend the capabilities of the technique, two strategies for noncontact amperometric imaging-in conjunction with contact mode topographical imaging-have been developed for the investigation of solid-liquid interfaces. First, SECM-AFM can be used to image an area of the surface of interest, in contact mode, to deduce the topography. The feedback loop of the AFM is then disengaged and the stepper motor employed to retract the tip a specified distance from the sample, to record a current image over the same area, but with the tip held in a fixed x-y plane above the surface. Second, Lift Mode can be employed, where a line scan of topographical AFM data is first acquired in contact mode, and the line is then rescanned to record SECM current data, with the tip maintained at a constant distance from the target interface, effectively following the contours of the surface. Both approaches are exemplified with SECM feedback and substrate generation-tip collection measurements, with a 10-microm-diameter Pt disk UME serving as a model substrate. The approaches described allow electrochemical images, acquired with the tip above the surface, to be closely correlated with the underlying topography, recorded with the tip in intimate contact with the surface.

Journal Article↗

PubMed2000

Combined scanning electrochemical-atomic force microscopy.

A combined scanning electrochemical microscope (SECM)-atomic force microscope (AFM) is described. The instrument permits the first simultaneous topographical and electrochemical measurements at surfaces, under fluid, with high spatial resolution. Simple probe tips suitable for SECM-AFM, have been fabricated by coating flattened and etched Pt microwires with insulating, electrophoretically deposited paint. The flattened portion of the probe provides a flexible cantilever (force sensor), while the coating insulates the probe such that only the tip end (electrode) is exposed to the solution. The SECM-AFM technique is illustrated with simultaneous electrochemical-probe deflection approach curves, simultaneous topographical and electrochemical imaging studies of track-etched polycarbonate ultrafiltration membranes, and etching studies of crystal surfaces.

Electrochemistry↗

PubMed2000

Scanning electrochemical microscopy as a local probe of oxygen permeability in cartilage.

The use of scanning electrochemical microscopy, a high-resolution chemical imaging technique, to probe the distribution and mobility of solutes in articular cartilage is described. In this application, a mobile ultramicroelectrode is positioned close ( approximately 1 microm) to the cartilage sample surface, which has been equilibrated in a bathing solution containing the solute of interest. The solute is electrolyzed at a diffusion-limited rate, and the current response measured as the ultramicroelectrode is scanned across the sample surface. The topography of the samples was determined using Ru(CN)(6)(4-), a solute to which the cartilage matrix was impermeable. This revealed a number of pit-like depressions corresponding to the distribution of chondrocytes, which were also observed by atomic force and light microscopy. Subsequent imaging of the same area of the cartilage sample for the diffusion-limited reduction of oxygen indicated enhanced, but heterogeneous, permeability of oxygen across the cartilage surface. In particular, areas of high permeability were observed in the cellular and pericellular regions. This is the first time that inhomogeneities in the permeability of cartilage toward simple solutes, such as oxygen, have been observed on a micrometer scale.

Animals↗

PubMed1997

Quantitative spatially resolved measurements of mass transfer through laryngeal cartilage.

The scanning electrochemical microscope (SECM) is a scanned probe microscope that uses the response of a mobile ultramicroelectrode (UME) tip to determine the reactivity, topography, and mass transport characteristics of interfaces with high spatial resolution. SECM strategies for measuring the rates of solute diffusion and convection through samples of cartilage, using amperometric UMEs, are outlined. The methods are used to determine the diffusion coefficients of oxygen and ruthenium(III) hexamine [Ru(NH3)6(3+)] in laryngeal cartilage. The diffusion coefficient of oxygen in cartilage is found to be approximately 50% of that in aqueous electrolyte solution, assuming a partition coefficient of unity for oxygen between cartilage and aqueous solution. In contrast, diffusion of Ru(NH3)6(3+) within the cartilage sample cannot be detected on the SECM timescale, suggesting a diffusion coefficient at least two orders of magnitude lower than that in solution, given a measured partition coefficient for Ru(NH3)6(3+) between cartilage and aqueous solution, Kp = [Ru(NH3)6(3+)]cartilage/[RU(NH3)6(3+)]solution = 3.4 +/- 0.1. Rates of Ru(NH3)6(3+) osmotically driven convective transport across cartilage samples are imaged at high spatial resolution by monitoring the current response of a scanning UME, with an osmotic pressure of approximately 0.75 atm across the slice. A model is outlined that enables the current response to be related to the local flux. By determining the topography of the sample from the current response with no applied osmotic pressure, local transport rates can be correlated with topographical features of the sample surface, at much higher spatial resolution than has previously been achieved.

Animals↗

PubMed1997

New electrochemical techniques for probing phase transfer dynamics at dental interfaces in vitro.

Phase transfer reactions such as dissolution, precipitation, sorption, and desorption are important in a wide range of processes on dental hard tissue surfaces. An overview is provided of several new complementary electrochemical techniques which are capable of probing the dynamics of such processes at solid/liquid interfaces from millimeter- to nanometer-length scales, with a variable time resolution down to the sub-millisecond level. Techniques considered include channel flow methods with electrochemical detection, which allow reactions at solid/liquid interfaces to be studied under well-defined and calculable mass transport regimes. Scanning electrochemical microscopy allows the chemical activity of interfaces to be mapped at higher spatial and temporal resolutions. This technique, which utilizes a scanning ultramicroelectrode, has been used extensively for the study of dissolution processes of ionic crystals, as well as in imaging the action of fluid-flow-blocking agents on dentin surfaces, which act via precipitation. So that interfaces at the nanometer level can be probed, an integrated electrochemical-atomic force microscope has been developed which enables the local solution conditions to be controlled electrochemically while topographical changes are mapped simultaneously.

Adsorption↗

PubMed1988

Sedation for endoscopy: midazolam or diazepam and pethidine?

One hundred patients received either diazepam given with pethidine, antagonized with naloxone, or midazolam alone in a double-blind randomized study of sedation for upper gastrointestinal endoscopy. Midazolam produced better amnesia for the procedure (P less than 0.0001) but diazepam and pethidine resulted in less retching during the procedure (P less than 0.01) and less sedation after the procedure, as judged by a simple performance test (P less than 0.02) and patient recall of results (P less than 0.02).

Adult↗