(Invited) Electroactive Redox Polymers, Redox Glyconanoparticles and Supramolecular Assemblies Based on Nanotubes for Bioelectrochemical Applications

Abstract

For four decades, the development of biointerfaces has been the subject of increasing research efforts in the field of analytical chemistry and energy conversion. In particular, the functionalization of electrodes by biomaterials based on electrogenerated polymers and / or carbon nanotubes, is widely used for the design of biosensors and biofuel cells. Nanotube deposits were successfully functionalized by electropolymerization or π−π stacking interactions with pyrene derivatives exhibiting both affinity or covalent binding interactions towards redox molecules or proteins. Some new approaches for developing nanostructured biomaterials based on functionalized tungsten disulfide nanotubes and self-supporting film of carbon nanotubes (buckypapers) will be illustrated with enzymes as biosensing element [1]. In particular, WS2 nanotubes functionalized with carboxylic acid functions were used for the tyrosinase immobilization in order to form an amperometric biosensor towards catechol and dopamine. Moreover, heteropolyoxometalates (C4H10N)6[P2Mo18O62] and (C6H8NO)4[H2P2W18O62] were immobilized within carbon nanotube matrix and used as mediators for the electron transfer with FAD dependent glucose dehydrogenase [2]. The glucose detection was performed with a sensitivity of 198 mAmolL-1cm-2, and a good reproducibility. A new generation of flexible buckypaper electrodes was produced by using linear polynorbornene polymers containing multiple pyrene groups as crosslinker [3]. In addition, the use of bifunctionalized polymers (pyrene and NHS groups) leads to robust buckypapers with the covalent binding of redox groups or enzymes [4].We have been also interested in the development and characterization of glyconanoparticles (vesicles, micelle aggregates) obtained from the self-assembly of block copolymers composed of polystyrene as a hydrophobic tail and cyclodextrin as a hydrophilic part. These glyconanoparticles, which are stable in suspension in aqueous media, have an outer layer composed of cyclodextrin which allows a post-functionalization of the nanoparticle by hydrophobic molecules through host-guest interactions. These nanoparticles are thus a versatile platform for fixing a wide range of redox mediators. Two types of redox nanoparticles in solution for the electrical connection of enzymes have been developed: nanoparticle modified by 9,10-phenanthrenequinone and nanoparticle modified by ABTS modified by two pyrene groups. This innovative approach will be applied to the electrical wiring of enzymes in solution for the elaboration of solubilized enzymatic fuel cell [5,6]. Acknowledgements The author wishes to acknowledge the support from the Sino-French international research network GDRI 0876 “New nanostructured materials and biomaterials for renewable electrical energy sources” for providing facilities. This work is partly supported by the French National Research Agency (ANR-18-CE09-0022-01).[1]