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Effect of Gold Nanoparticles on the Structure and Electron‐Transfer Characteristics of Glucose Oxidase Redox Polyelectrolyte‐Surfactant Complexes
Authors:Dr M Lorena Cortez  Dr Waldemar Marmisollé  Dr Diego Pallarola  Dr Lía I Pietrasanta  Dr Daniel H Murgida  Dr Marcelo Ceolín  Dr Omar Azzaroni  Dr Fernando Battaglini
Affiliation:1. INQUIMAE ‐ Departamento de Química Inorgánica Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, CONICET, Ciudad Universitaria, Pabellón 2, C1428EHA Buenos Aires (Argentina);2. Instituto de Investigaciones Fisicoquímicas Tas y Aplicadas (INIFTA), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CONICET, CC 16 Suc. 4 (1900) La Plata (Argentina);3. Centro de Microscopías Avanzadas and Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 1, C1428EHA Buenos Aires (Argentina)
Abstract:Efficient electrical communication between redox proteins and electrodes is a critical issue in the operation and development of amperometric biosensors. The present study explores the advantages of a nanostructured redox‐active polyelectrolyte–surfactant complex containing Os(bpy)2Clpy]2+ (bpy=2,2′‐bipyridine, py= pyridine) as the redox centers and gold nanoparticles (AuNPs) as nanodomains for boosting the electron‐transfer propagation throughout the assembled film in the presence of glucose oxidase (GOx). Film structure was characterized by grazing‐incidence small‐angle X‐ray scattering (GISAXS) and atomic force microscopy (AFM), GOx incorporation was followed by surface plasmon resonance (SPR) and quartz‐crystal microbalance with dissipation (QCM‐D), whereas Raman spectroelectrochemistry and electrochemical studies confirmed the ability of the entrapped gold nanoparticles to enhance the electron‐transfer processes between the enzyme and the electrode surface. Our results show that nanocomposite films exhibit five‐fold increase in current response to glucose compared with analogous supramolecular AuNP‐free films. The introduction of colloidal gold promotes drastic mesostructural changes in the film, which in turn leads to a rigid, amorphous interfacial architecture where nanoparticles, redox centers, and GOx remain in close proximity, thus improving the electron‐transfer process.
Keywords:electron transfer  glucose catalysis  glucose oxidase  gold nanoparticles  mesostructure  redox polyelectrolyte
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