Organic β‐cyclodextrin Nanoparticle: An Efficient Building Block Between Functionalized Poly(pyrrole) Electrodes and Enzymes

Abstract

Thanks to an increased surface area, nanomaterials such as carbon nanotubes, graphene, [5][6][7][8][9][10][11][12][13] semi-conductor quantum dots, [14,15] have significantly increased the power density of biofuel cells and capacitors as well as the analytical performance of biosensors in terms of sensitivity and detection limit. In addition, metallic nanoparticles [16][17][18] have aroused great interest in the elaboration of electrode materials due to their physical and chemical properties such as high surface/volume ratio and relatively high electrical conductivity. Their main drawback lies in the post-chemical treatment of their surface to obtain reactive groups such as carboxyl, thiol, or amino groups, for example, for anchoring biomolecules. These steps are often complex and time consuming. [19] Recently, an attractive alternative to these metallic nanoparticles has been reported and consists of organic nanoparticles generated by selfassembly of amphiphilic glycopolymers in water. In particular, glyconanoparticles (GNPs) composed of polystyrene-block-βcyclodextrin (PS-b-βCD) constitute in aqueous medium, stable and polyvalent nanospheres easily functionalizable by inclusion of hydrophobic compounds in the cavities of the β-cyclodextrin shell. These host-guest interactions of the nanoparticle shell have been used successfully to immobilize redox hydrophobic compounds such tetrazine-naphthalimide, [20] bispyrene-(2,2′azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), [21] phenanthrene-quinone, [22] anthraquinone-sulfonate. [23] Some of these resulting redox nanoparticles were applied in suspension successfully for efficient electrical connection of enzymes and the development of a solubilized enzymatic fuel cells. [22] However, these GNPs have only been used in aqueous suspension and have never been tested as a building block for the design of nanostructured (bio)materials of electrode for biosensing application or energy conversion. In this context, we report here the possibility to attach these nanoparticles on an electrode surface by specific host-guest interactions and compared this approach to a simple adsorption. Owing to the high affinity of adamantane to form inclusion complexes with Glyconanoparticles (GNPs) made by self-assembly of carbohydrate-based polystyrene-block-β-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(pyrroleadamantane), and copolymer, poly(pyrrole-adamantane)/poly(pyrrole-lactobionamide) via host-guest interactions between adamantane and β-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 g...

Cyclodextrin Host–Guest Recognition in Glucose-Monitoring Sensors

“…In response to the increasing demand for GM systems, Buzzetti et al developed glyconanoparticles (GNPs) using a carbohydrate-based polystyrene-block-β-CD copolymer as a building block. 123 The GNPs were firmly immobilized on electrochemically generated polymers, including poly(pyrroleadamantane) and copolymer poly(pyrrole-adamantane)/poly-(pyrrole-lactobionamide), through host−guest interactions between adamantane and β-CD. To evaluate the potential of GNPs for targeted anchoring of biological macromolecules, a glucose oxidase enzyme modified with adamantane groups (GOx-Ad) was used.…”

PEGylated Network Nanostructured by Gold Nanoparticles for Electrochemical Sensing of Aromatic Redox and Nonredox Analytes

“…11−13 Polymeric films doped with CD molecules or dendrimers were also reported. 14,15 Highly selective and sensitive chemical and biochemical sensors based on nanomaterials modified with βCDs, including gold nanoparticles (AuNPs) modified with βCDs or glycol nanoparticles, were described by Lenik et al 16,17 and Cosnier and co-workers, 18,19 respectively. The aim of the present work was to combine the above approaches using nanoparticles modified with CDs and polymers as one integrated material for the preparation of sensing films on electrodes.…”

“…Due to the multifunctional properties of CDs, they have often been used as active components in electrochemical sensors . Several materials have been employed for the construction of CD-modified electrodes, including carbon paste, carbon nanotubes, glassy carbon (GC), or graphene electrodes. − Gold electrodes were modified with thiolated derivatives of CDs. − Polymeric films doped with CD molecules or dendrimers were also reported. , Highly selective and sensitive chemical and biochemical sensors based on nanomaterials modified with βCDs, including gold nanoparticles (AuNPs) modified with βCDs or glycol nanoparticles, were described by Lenik et al , and Cosnier and co-workers, , respectively.…”