Probing the nature of charge transfer at nano-bio interfaces: Peptides on metal oxide nanoparticles

Characterizing the nano-bio interface has been a long-standing endeavor in the quest for novel biosensors, biophotovoltaics, and biocompatible electronic devices. In this context, the present computational work on the interaction of two peptides, A6K (Ac-AAAAAAK-NH₂) and A7 (Ac-AAAAAAA-NH₂) with semiconducting TiO₂ nanoparticles is an effort to understand the peptide-metal oxide nanointerface. These investigations were spurred by recent experimental observations that nanostructured semiconducting metal oxides templated with A6K peptides not only stabilize large proteins like photosystem-I (PS-I) but also exhibit enhanced charge-transfer characteristics. Our results indicate that α-helical structures of A6K are not only energetically more stabilized on TiO₂ nanoparticles, but the resulting hybrids also exhibit enhanced electron transfer characteristics. This enhancement can be attributed to substantial changes in the electronic characteristics at the peptide-TiO₂ interface. Apart from understanding the mechanism of electron transfer (ET) in peptide-stabilized PS-I on metal oxide nanoparticles, the current work also has implications in the development of novel solar cells and photocatalysts.