Long-Range Interfacial Electrochemical Electron Transfer of Pseudomonas aeruginosa Azurin−Gold Nanoparticle Hybrid Systems

Abstract

We have prepared a “hybrid” of the blue copper protein azurin (Pseudomonas aeruginosa) and a 3 nm gold nanoparticle (AuNP). The AuNP/azurin hybrid was assembled on a Au(111)-electrode surface in a two-step process. The AuNP was first attached to the Au(111) electrode via Au−S chemisorption of a 4,4′-biphenyldithiol (4,4′-BPDT) monolayer. This was followed by 1-decanethiol modification of the bound AuNP and hydrophobic binding of azurin to the AuNP. The Au(111)/AuNP/azurin system was characterized by atomic force microscopy (AFM), cyclic voltammetry (CV), and in situ electrochemical scanning tunneling microscopy (in situ STM). AFM and STM point to the feasibility of preparing both dense and sparsely populated AuNP monolayers. CV shows two pairs of voltammetric peaks at high scan rates, both around the azurin equilibrium potential. One pair of redox peaks follows closely that of azurin hydrophobically immobilized directly on a Au(111)/1-tetradecanethiol reference surface. The other pair, tentatively assigned to the AuNP/azurin hybrid, shows a 20-fold electron transfer rate enhancement over the reference system. This dual pattern is supported by in situ STM which shows two distinct contrasts. A strong contrast most likely arises either from azurin-free AuNPs or from AuNP-free azurin displaced onto the Au(111)/4,4′-BPDT surface. The other contrast, assigned to the AuNP/azurin hybrid, is weaker and fluctuates in time. Mechanisms of electronic conductivity of the AuNP/azurin system are discussed.