Surface Plasmon Resonance Enhanced Real-Time Photoelectrochemical Protein Sensing by Gold Nanoparticle-Decorated TiO2 Nanowires

Recently developed photoelectrochemical (PEC) sensing systems represent a unique potential detection method for real-time analysis of chemical/biological molecules, while the low absorption of TiO2 nanomaterials in the visible wavelength region and the slow surface charge transfer efficiency limit the ultimate sensitivity. Here we develop a gold nanoparticle-decorated TiO2 nanowire sensor for PEC detection of protein binding. The direct attachment of Au nanoparticles to TiO2 nanowires offers strong surface plasmon resonance for electrochemical field effect amplification, yielding a ∼100% increase of photocurrent density. In addition, the surface functionalization of gold nanoparticles allows for direct capturing of target proteins near the Au/TiO2 interface and thus substantially enhances the capability of attenuation of energy coupling between Au and TiO2, leading to much-improved sensor performance. As a proof of concept, cholera toxin subunit B has been robustly detected by the TiO2–Au nanowire sensor functionalized with ganglioside GM1, with a high sensitivity of 0.167 nM and excellent selectivity. Furthermore, the real-time feature of photoelectrochemical sensing enables direct measurement of binding kinetics between cholera toxin subunit B and GM1, yielding association and disassociation rate constants and an equilibrium constant Kd of 4.17 nM. This surface plasmon resonance-enhanced real-time, photoelectrochemical sensing design may lead to exciting biodetection capabilities with high sensitivity and real-time kinetic studies.