High-efficiency charge transfer on SERS-active semiconducting K2Ti6O13 nanowires enables direct transition of photoinduced electrons to protein redox centers

Abstract

Photoinduced charge transfer (PICT) plays a crucial role in the chemical mechanism of surface-enhanced Raman scattering (SERS), in which small organic molecules are generally used as probes. Herein, semiconducting K2Ti6O13 nanowires (NWs) are synthesized and are found to exhibit high SERS activity probed by 4-mercaptobenzoic acid (4-MBA). Density functional theory (DFT) calculations reveal high-efficiency CT on the K2Ti6O13 nanowires. Furthermore, PICT on the K2Ti6O13 NWs is for the first time evidenced by a redox protein, cytochrome c (Cyt c). Under optimized experimental conditions, the transformation of oxidized Cyt c to its reduced state clearly verifies the electron transfer (ET) from the K2Ti6O13 nanowire to the protein. The ET mechanism is explored based on energy levels of semiconductors and molecular dynamics simulations, thus revealing the importance of energy level matching and electron tunneling from the semiconductor surface to the redox center. This study indicates a great potential of multiple-layered K2Ti6O13 NWs in the application of SERS on semiconducting materials and more importantly, it provides a new route for the rational design of protein-semiconductor interfaces for investigating electron transfer processes of redox proteins and biocatalytic reactions.