Biomedical subjects

Patrick Garrigue

Publications and source records attributed to Patrick Garrigue.

5 recordsLinked to original sources

PubMed2007

Macroporous ultramicroelectrodes for improved electroanalytical measurements.

Recent work on the preparation of highly organized macroporous electrodes and nanoporous ultramicroelectrodes has been combined and extended to elaborate macroporous ultramicroelectrodes (UMEs) by template synthesis using colloidal crystals and following two different and complementary methods. On the one hand, arched porous UMEs were prepared, and on the other hand, cylindrical porous UMEs were obtained by using cavity UMEs. These macroporous UMEs have an active surface area which is up to 2 orders of magnitude higher compared to that of a classical disk UME as characterized by cyclic voltammetry. To study their analytical performance, the macroporous UMEs have been modified with a redox-active thiol and also a model bioelectrocatalytical system containing a redox mediator, a cofactor, and glucose-dehydrogenase. In both cases the electrochemical signal is amplified by up to 2 orders of magnitude, which increases significantly the analytical performance of such electrodes and therefore opens up new applications for this kind of miniaturized electrochemical system.

Journal Article↗

PubMed2005

Remote NADH imaging through an ordered array of electrochemiluminescent nanoapertures.

In this report, we present an ordered array comprising thousands of nanoapertures for the electrochemiluminescent (ECL) detection of NADH. It was fabricated on the distal face of a coherent optical fiber bundle. Such a high-density array of nanoapertures combines optical, imaging and electrochemical properties. Indeed, each nanoaperture is surrounded by a gold nanoring, which acts as an electrode material. The behavior of the array was characterized by cyclic voltammetry and it shows excellent electrochemical performances. NADH is the analyte, which is measured in presence of Ru(bpy)3(2+). The ruthenium complex mediates the NADH oxidation and this coenzyme acts as a co-reactant in the ECL mechanism. ECL light is generated at the distal face of the array by each gold ring electrode. A fraction of this ECL light is collected by the corresponding nanoaperture, transmitted through the optical fiber bundle and finally imaged on the proximal face with a CCD camera. In this work, we show that NADH concentration is remotely detected by an oxidative-reductive ECL mechanism. We present also some preliminary results about the ECL process of NADH with Ru(bpy)3(2+). The ECL behavior of NADH on gold surface is reported. The influence of the applied potential on the collected light intensity was investigated. The variation of the ECL intensity measured through the nanoaperture array with NADH concentration is linear. Remote ECL detection of NADH is spatially resolved over a large area with a micrometer resolution through the array. Therefore, such array integrates several complementary functions: ECL light generation, collection, transmission and remote imaging in an array format.

Electrochemistry↗

PubMed2004

Remote fluorescence imaging of dynamic concentration profiles with micrometer resolution using a coherent optical fiber bundle.

Dynamic concentration profiles within the diffusion layer of an electrode were imaged in situ using fluorescence detection through a multichannel imaging fiber. In this work, a coherent optical fiber bundle is positioned orthogonal to the surface of an electrode and is used to report spatial and temporal micrometric changes in the fluorescence intensity of an initial fluorescent species. The fluorescence signal is directly related to the local concentration of a redox fluorescent reagent, which is electrochemically modulated by the electrode. Fluorescence images are collected through the optical fiber bundle during the oxidation of tris(2,2'-bipyridine)ruthenium(II) to ruthenium(III) at a diffusion-limited rate and allow the concentration profiles of Ru(II) reagent to be monitored in situ as a function of time. Tris(2,2'-bipyridine)ruthenium(II) is excited at 485 nm and emits fluorescence at 605 nm, whereas the Ru(III) oxidation state is not fluorescent. Our experiments emphasize the influence of two parameters on the micrometer spatial resolution: the numerical aperture of optical fibers within the bundle and the Ru(II) bulk concentration. The extent of the volume probed by each individual fiber of the bundle is discussed qualitatively in terms of a primary inner-filter effect and refractive index gradient. Experimentally measured fluorescence intensity profiles were found to be in very good agreement with concentration profiles predicted upon considering planar diffusion and thus validate the concept of this new application of imaging fibers. The originality of this remote approach is to provide a global view of the entire diffusion layer at a given time through one single image and to allow the time expansion of the diffusion layer to be followed quantitatively in real time.

Journal Article↗

PubMed2004

Electrochemical modulation of remote fluorescence imaging at an ordered opto-electrochemical nanoaperture array.

An array of nanometer-sized apertures capable of electrochemically modulating the fluorescence of a model analyte is presented. The device, which combines near-field optical methods and ultramicroelectrode properties in an array format, is based on an etched coherent optical fiber bundle. Indeed, the fabrication steps produced an ordered array where each optical nanoaperture is surrounded by a ring-shaped gold nanoelectrode. The chronoamperometric behavior of the array shows stable diffusion-limited quasi-steady-state response. The model analyte, tris(2,2'-bipyridine) ruthenium, emits fluorescence in the Ru(II) state, but not in the oxidized Ru(III) state. Fluorescence is excited by visible light exiting from each nanoaperture since light is confined to the tip apex by the gold coating. A fraction of the isotropically emitted luminescence is collected by the same nanoaperture, transmitted by the corresponding fiber core and eventually detected by a charge-coupled device (CCD) camera. The array format provides a fluorescence image resolved at the nanometric scale which covers a large micrometric area. Therefore the high-density array plays a bridging role between these two fundamental scales. We established that the opto-electrochemical nanoapertures are optically independent. Fluorescence of the sample collected by each nanoaperture is modulated by changing the potential of the nanoring electrodes. Reversible electrochemical switching of remote fluorescence imaging is performed through the opto-electrochemical nanoaperture array itself. Eventually this ordered structure of nanometer light sources which are electrochemically manipulated provides promising photonic or electro-optical devices for various future applications. For example, such an array has potential in the development of a combined SNOM-electrochemical nanoprobe array to image a real sample concomitantly at the nanometer and micrometer scale.

Journal Article↗

PubMed2004

Development of an ordered array of optoelectrochemical individually readable sensors with submicrometer dimensions: application to remote electrochemiluminescence imaging.

A novel array of optoelectrochemical submicrometer sensors for remote electrochemiluminescence (ECL) imaging is presented. This device was fabricated by chemical etching of a coherent optical fiber bundle to produce a nanotip array. The surface of the etched bundle was sputter-coated with a thin layer of indium tin oxide in order to create a transparent and electrically conductive surface that is insulated eventually by a new electrophoretic paint except for the apex of the tip. These fabrication steps produced an ordered array of optoelectrochemical sensors with submicrometer dimensions that retains the optical fiber bundle architecture. The electrochemical behavior of the sensor array was independently characterized by cyclic voltammetry and ECL experiments. The steady-state current indicates that the sensors are diffusively independent. This sensor array was further studied with a co-reactant ECL model system, such as Ru(bpy)(3)(2+)/TPrA. We clearly observed an ordered array of individual ECL micrometer spots, which corresponds to the sensor array structure. While the sensors of the array are not individually addressable electrochemically, we could establish that the sensors are optically independent and individually readable. Finally, we show that remote ECL imaging is performed quantitatively through the optoelectrochemical sensor array itself.

Algorithms↗