(Keynote) Bioelectrocatalytic Systems Based on Microcapsules, Glyconanoparticles and Microcavities

For four decades, the functionalization of electrodes by biomaterials based on electrogenerated polymers, carbon nanotubes and / or nano-objects, was widely used in the field of analytical chemistry and energy conversion. Recently, we redesigned enzymatic bioelectrodes in order to produce original objects. An innovative concept of reagentless biosensors based on enzymatic reduction of oxygen was developed by trapping and releasing the substrate of the enzyme (catechol) from the structure of the biosensor. A polyurethane support modified by two perforated microcapsules filled with catechol was easily transformed into a bioelectrode by the successive deposition of multiwalled carbon nanotubes and a mixture of laponite clay and tyrosinase enzyme [1]. On the other hand, the development of glyconanoparticles resulting from the self-assembly of block copolymers composed of polystyrene and cyclodextrin as an inclusion site will be reported. These glyconanoparticles, which are stable in suspension in aqueous media, have an outer layer composed of cyclodextrin [2]. The latter allows a post-functionalization of the nanoparticle by hydrophobic molecules through host-guest interactions. It appears that it is possible to modulate the site density of βCD at the surface of the shell of the hybrid glyconanoparticles while maintaining its inclusion properties. Moreover, the anchoring of glyconanoparticles to the surface of electrodes has been carried out by host-guest interactions with electrogenerated polymers. The efficient immobilization of the nanoparticles allows the anchoring of multilayers of biotinylated glucose oxidase. Finally, a new generation of bioelectrodes for oxygen reduction and electrical energy production will be described. This approach is based on the design of flat electrodes made of permeable and conductive materials defining a very thin microcavity with a large surface area containing, in a microvolume, enzymes in powder form. The concept has been demonstrated with bilirubin oxidase (BOD) for the electroenzymatic reduction of oxygen in water. Besides the influence of the amount of enzyme trapped in the microcavity on the performance of the bioelectrode, the functionalization of the electrodes by adsorption of redox mediators or compounds allowing an orientation of the BOD favorable to electron transfer was also explored. After 5 months of storage in an aqueous buffer, the bioelectrode exhibits 20% of its initial electro-enzymatic activity. Y. Nedellec, C. Gondran, K. Gorgy, S. MC Murtry, O. El Mazria, P. Agostini, S. Cosnier. Biosens. Bioelectron., 180, 113137-113141(2021). M. Carrière, P. H. M. Buzzetti, K. Gorgy, M. Mumtaz, C. Travelet, R. Borsali, S. Cosnier. Nanomaterials 11 (2021) 1162. doi.org/10.3390/nano11051162.