TY - JOUR A1 - Sivanesan, Arumugam A1 - Ly, Khoa H. A1 - Adamkiewicz, Witold A1 - Stiba, Konstanze A1 - Leimkühler, Silke A1 - Weidinger, Inez M. T1 - Tunable electric field enhancement and redox chemistry on TiO2 Island films via covalent attachment to Ag or Au nanostructures JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Ag-TiO2 and Au-TiO2 hybrid electrodes were designed by covalent attachment of TiO2 nanoparticles to Ag or Au electrodes via an organic linker. The optical and electronic properties of these systems were investigated using the cytochrome b(5) (Cyt b(5)) domain of sulfite oxidase, exclusively attached to the TiO2 surface, as a Raman marker and model redox enzyme. Very strong SERR signals of Cyt b(5) were obtained for Ag-supported systems due to plasmonic field enhancement of Ag. Time-resolved surface-enhanced resonance Raman spectroscopic measurements yielded a remarkably fast electron transfer kinetic (k = 60 s(-1)) of Cyt b(5) to Ag. A much lower Raman intensity was observed for Au-supported systems with undefined and slow redox behavior. We explain this phenomenon on the basis of the different potential of zero charge of the two metals that largely influence the electronic properties of the TiO2 island film. Y1 - 2013 U6 - https://doi.org/10.1021/jp4032578 SN - 1932-7447 VL - 117 IS - 22 SP - 11866 EP - 11872 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Frasca, Stefano A1 - Milan, Anabel Molero A1 - Guiet, Amandine A1 - Goebel, Caren A1 - Perez-Caballero, Fernando A1 - Stiba, Konstanze A1 - Leimkühler, Silke A1 - Fischer, Anna A1 - Wollenberger, Ursula T1 - Bioelectrocatalysis at mesoporous antimony doped tin oxide electrodes-Electrochemical characterization and direct enzyme communication JF - ELECTROCHIMICA ACTA N2 - In this paper we report immobilization and bioelectrocatalysis of human sulfite oxidase (hSO) on nanostructured antimony doped tin oxide (ATO) thin film electrodes. Two types of ATO thin film electrodes were prepared via evaporation induced self-assembly of ATO nanoparticle sols. The use of a porogen results in different porosity and film thickness. Nevertheless both electrode types reveal similar quasi reversible electrochemical behavior for positive and negatively charged small mediators. Facile and durable immobilization of catalytically active enzyme in a direct electron transfer configuration was achieved without further chemical modification of the ATO surfaces. Interestingly, the binding of hSO onto the ATO surface seems to be not only of electrostatic nature, but also originates from a strong interaction between the histidine-tag of the enzyme and the supporting material. This is suggested from stable sulfite dependent bioelectrocatalytic signals at high ionic strength and imidazole desorption experiments. As such, ATO appears as a promising conductive platform for the immobilization of complex enzymes and their application in bioelectrocatalysis. (C) 2013 Elsevier Ltd. All rights reserved. KW - Antimony doped tin dioxide KW - Sulfite oxidase KW - Direct electrochemistry KW - Biosensor KW - Bioelectrocatalysis Y1 - 2013 U6 - https://doi.org/10.1016/j.electacta.2013.03.144 SN - 0013-4686 SN - 1873-3859 VL - 110 IS - 2 SP - 172 EP - 180 PB - PERGAMON-ELSEVIER SCIENCE LTD CY - OXFORD ER -