Hollow Bioelectrodes Based on Buckypaper Assembly. Application to the Electroenzymatic Reduction of O2.

A new concept of hollow electrode based on the assembly of two buckypapers creating a microcavity which contains a biocatalyst is described. To illustrate this innovative concept, hollow bioelectrodes containing 0.16-4 mg bilirubin oxidase in a microcavity were fabricated and applied to electroenzymatic reduction of O2 in aqueous solution. For hemin-modified buckypaper, the bioelectrode shows a direct electron transfer between multi-walled carbon nanotubes and bilirubin oxidase with an onset potential of 0.77 V vs. RHE. The hollow bioelectrodes showed good storage stability in solution with an electroenzymatic activity of 30 and 11% of its initial activity after 3 and 6 months, respectively. The co-entrapment of bilirubin oxidase and 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) in the microcavity leads to a bioelectrode exhibiting mediated electron transfer. After 23 h of intermittent operation, 5.66 × 10-4 mol of O2 were electroreduced (turnover number of 19,245), the loss of catalytic current being only 54% after 7 days.

Trialkoxyheptazine-Based Glyconanoparticles for Fluorescence in Aqueous Solutions and on Surfaces via Controlled Binding in Space.

The fluorescent organic 2,5,8-tris((adamantan-1-yl)-methoxy)-heptazine (HTZ-Ad) was solubilized in water by inclusion of adamantane groups into free ß-cyclodextrins or a cyclodextrin shell of glyconanoparticles. These glyconanoparticles with average diameters between 40 and 60 nm result from the self-assembly of polystyrene-block-ß-cyclodextrin copolymers. Under UV irradiation at 365 nm, the modified nanoparticles exhibit fluorescence emission in aqueous media as well as in their adsorbed state. This constitutes the first spectroscopic characterization of a trialkoxyheptazine in aqueous medium. The specific binding of the glyconanoparticles to a surface was achieved via host-guest interactions with an electrochemically generated poly(pyrrole-adamantane) film. An interdigitated microelectrode modified with poly(pyrrole-adamantane) film and glyconanoparticles was incubated in HTZ-Ad, resulting in a substrate with spatially controlled fluorescence. The same modified electrode was incubated with an aqueous suspension of glyconanoparticles previously functionalized by HTZ-Ad, resulting in a fluorescent 3D assembly.

Organic ß-cyclodextrin Nanoparticle: An Efficient Building Block Between Functionalized Poly(pyrrole) Electrodes and Enzymes.

Glyconanoparticles (GNPs) made by self-assembly of carbohydrate-based polystyrene-block-ß-cyclodextrin copolymer are used as a building block for the design of nanostructured biomaterials of electrode. The firm immobilization of GNPs is carried out on electrochemically generated polymer, poly(pyrrole-adamantane), and copolymer, poly(pyrrole-adamantane)/poly(pyrrole-lactobionamide) via host-guest interactions between adamantane and ß-cyclodextrin. The ability of GNPs for the specific anchoring of biological macromolecules is investigated using glucose oxidase enzyme modified by adamantane groups as a protein model (GOx-Ad). The immobilization of GOx-Ad is carried out by incubation of an aqueous enzyme solution on a coating of GNPs adsorbed on a platinum electrode. The presence of immobilized GOx-Ad is evaluated in aqueous glucose solution by potentiostating the underlying platinum electrode at 0.7 V/SCE for the electro-oxidation of H2 O2 generated by the enzyme. The analytical performance of the bioelectrodes for the detection of glucose is compared to control electrodes prepared without GNPs or without electropolymerized films. The better permeability of copolymer compared to polymer and the possibility to elaborate two alternating layers of GNPs and GOx-Ad are clearly observed. The best amperometric response is recorded with a multilayered bioelectrode displaying a wide linear range linear range of the calibration curve: 68 µmol L-1 to 0.1 mol L-1 .

Insights into carbon nanotube-assisted electro-oxidation of polycyclic aromatic hydrocarbons for mediated bioelectrocatalysis.

A series of polycyclic aromatics, naphthalene, phenanthrene, perylene, pyrene, 1-pyrenebutyric acid N-hydroxysuccinimide ester (pyrene NHS) and coronene, were immobilized via π stacking on carbon nanotube (CNT) electrodes and electro-oxidized in aqueous solutions. The obtained quinones were characterized and evaluated for the mediated electron transfer with FAD dependent glucose dehydrogenase during catalytic glucose oxidation.

Functionalizable Glyconanoparticles for a Versatile Redox Platform.

A series of new glyconanoparticles (GNPs) was obtained by self-assembly by direct nanoprecipitation of a mixture of two carbohydrate amphiphilic copolymers consisting of polystyrene-block-ß-cyclodextrin and polystyrene-block-maltoheptaose with different mass ratios, respectively 0-100, 10-90, 50-50 and 0-100%. Characterizations for all these GNPs were achieved using dynamic light scattering, scanning and transmission electron microscopy techniques, highlighting their spherical morphology and their nanometric size (diameter range 20-40 nm). In addition, by using the inclusion properties of cyclodextrin, these glyconanoparticles were successfully post-functionalized using a water-soluble redox compound, such as anthraquinone sulfonate (AQS) and characterized by cyclic voltammetry. The resulting glyconanoparticles exhibit the classical electroactivity of free AQS in solution. The amount of AQS immobilized by host-guest interactions is proportional to the percentage of polystyrene-block-ß-cyclodextrin entering into the composition of GNPs. The modulation of the surface density of the ß-cyclodextrin at the shell of the GNPs may constitute an attractive way for the elaboration of different electroactive GNPs and even GNPs modified by biotinylated proteins.