Microarrays of near-field optical probes with adjustable dimensions

We present the fabrication and the characterization of high-density microarrays comprising thousands of near-field optical probes. Two types of microarrays have been prepared by adapting the SNOM methodology: arrays of uncoated fiber nanotips (i.e. apertureless probes) and arrays of apertures with adjustable subwavelength dimensions. Such arrays were fabricated by retaining the coherent structure of monomode optical fiber bundles and therefore keeping their imaging properties. The size of the apertures in a microarray was tuned at the nanometer scale by modifying the fabrication parameters. Far-field characterization of these near-field probe arrays shows completely different behavior depending both on their architecture and on their characteristic size. The angular distribution of the far-field intensity transmitted through the aperture arrays is used to determine the optical size of such diffracting apertures. Aperture radii ranging from 95 to 250 nm were found in good agreement with SEM data. Furthermore, each nanoaperture of the array is optically independent in the far-field regime. Eventually, this study demonstrates potential applications of these imaging arrays as parallel near-field optical probes in both configurations (apertureless and with apertures).     

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.     

Fabrication of a Macroporous Microwell Array for Surface‐Enhanced Raman Scattering

Here, a colloidal templating procedure for generating high‐density arrays of gold macroporous microwells, which act as discrete sites for surface‐enhanced Raman scattering (SERS), is reported. Development of such a novel array with discrete macroporous sites requires multiple fabrication steps. First, selective wet‐chemical etching of the distal face of a coherent optical fiber bundle produces a microwell array. The microwells are then selectively filled with a macroporous structure by electroless template synthesis using self‐assembled nanospheres. The fabricated arrays are structured at both the micrometer and nanometer scale on etched imaging bundles. Confocal Raman microscopy is used to detect a benzenethiol monolayer adsorbed on the macroporous gold and to map the spatial distribution of the SERS signal. The Raman enhancement factor of the modified wells is investigated and an average enhancement factor of 4 × 10⁴ is measured. This demonstrates that such nanostructured wells can enhance the local electromagnetic field and lead to a platform of ordered SERS‐active micrometer‐sized spots defined by the initial shape of the etched optical fibers. Since the fabrication steps keep the initial architecture of the optical fiber bundle, such ordered SERS‐active platforms fabricated onto an imaging waveguide open new applications in remote SERS imaging, plasmonic devices, and integrated electro‐optical sensor arrays.     

Kinetic investigations of the electrochemical bromination of peracetylated d-glucal in organic solvents

Cyclic voltammetry and ultramicroelectrodes were used to investigate the kinetic aspects of the electrochemical bromination of 3,4,6-tri-O-acetyl-d-glucal (1) in acetonitrile (AN), dichloromethane (DCM), and dimethylsulfoxide (DMSO). Qualitative and quantitative results, determined notably from the kinetic parameter [glucal]/v representing the competition between glucal concentration and time, clearly showed that glucal bromination depended on the nature of both the solvent and the in situ electrogenerated reactive brominated species (Br₂ or Br₃⁻) obtained from the oxidation of a bromide salt. It was especially shown that Br₂ reacted more rapidly than Br₃⁻ towards (1). On the other hand, the reactivity of both brominated species appeared to follow the solvent polarity order since the highest reactivity was obtained in DMSO whereas the lowest one was found in DCM.     

Carbon nanotube fiber microelectrodes: design, characterization, and optimization

We report on the preparation and interesting electrochemical behavior of carbon nanotube fiber microelectrodes (CNTFM). By combining the advantages of carbon nanotubes (CNT) with those of fiber electrodes, this type of microelectrode differs from CNT modified or CNT containing composite electrodes, because it's made of only CNT without any other components like additives or binders. The active CNT surface is easily regenerated. The performance of CNTFMs has been characterized, among others, by surface modification with phosphomolybdic acid. It is shown that adsorption behavior of these catalyst molecules is highly improved with a controlled orientation of CNT. A better CNT alignment inside the fiber can be achieved by a hot stretching procedure.     

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.     

Phenylarsine oxide inhibits ex vivo HIV-1 expression

Phenylarsine oxide (PAO), which is described as an inhibitor of tyrosine phosphatase activity, inhibits H2O2 release from human peripheral blood mononuclear cells (PBMCs) as measured by electrochemistry. Since human immunodeficiency virus type 1 (HIV-1) replication is known to be favored under oxidative stress conditions, ex vivo experiments using uninfected PBMCs, primary monocytes or a latently infected promonocytic U1 cell line show that HIV-1 replication and reactivation, monitored by p24 antigen measurement, are inhibited by PAO in a time- and concentration-dependent manner. These observations can be linked with the inhibition of NF-kappa B activation when uninfected monocytes are induced by either tumor necrosis factor alpha (TNF-alpha) phorbol 12-myristate 13-acetate (PMA) or lipopolysaccharide (LPS).     

Fast and easy enzyme immobilization by photoinitiated polymerization for efficient bioelectrochemical devices

Immobilization and electrical wiring of enzymes is of particular importance for the elaboration of efficient biosensors and can be cumbersome. Here, we report a fast and easy protocol for enzyme immobilization, and as a proof of concept, we applied it to the immobilization of bilirubin oxidase, a labile enzyme. In the first step, bilirubin oxidase is mixed with a redox hydrogel "wiring" the enzyme reaction centers to electrodes. Then, this adduct is covered by an outer layer of PEGDA made by photoinitiated polymerization of poly(ethylene-glycol) diacrylate (PEGDA) and a photoclivable precursor, DAROCUR. This two-step protocol is 18 times faster than the current state-of-the-art protocol and leads to currents 25% higher. In addition, the outer layer of PEGDA acts as a protective layer increasing the lifetime of the electrode by 100% when operating continuously for 2000 s and by 60% when kept in dry state for 24 h. This new protocol is particularly appropriate for labile enzymes that quickly denaturate. In addition, by tuning the ratio PEGDA/DAROCUR, it is possible to make the enzyme electrodes even more active or more stable.     

Electrochemical Bromination of Peracetylated Glycals

Bromination of glycals with tribromides formed in situ from bromine and different bromide salts in dichloromethane (DCM) or acetonitrile (AN) was found to give predominantly the products of anti addition of bromine from the C‐6 side in high yields. The same selectivity, which was much higher compared to bromination with bromine alone, was achieved in bromination of these substrates by anodic generation of bromine from the same salts.     

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.