Tuning Band Gap of Holoferritin by Metal Core Reconstitution with Cu, Co, and Mn

Abstract

Utility of ferritin in molecular electronics, especially in single molecule electronics based devices, has recently been proposed, since the iron core of holoferritin is semiconducting in nature. However, the practical aspects, e.g., how its electronic properties can be varied/tuned, need to be better addressed. In this direction, we have performed direct tunneling experiments using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) on several metal core reconstituted ferritins, where the reconstitution has been carried out using biocompatible metals like copper, cobalt, and manganese that are found naturally in the human body. We show, for the first time, that, by metal core reconstitution of the ferritin protein, the band gap of the protein can be tuned to different values (here, within the range 1.17-0.00 eV, considering iron-containing holoferritin and apoferritin as well). From the respective current-voltage curves and the well-defined band gaps, clear distinction can be made among the five different ferritins indicating that the metal core has direct contribution in the observed electrical conductivities of ferritins. It is further revealed that the electrical conductivities of the reconstituted ferritins are of the same order as that for the free metal conductivities, meaning that the relative changes in the free metal conductivities are reflected in the contributions of the metals in protein shell-confinement (i.e., the ∼8 nm core of ferritin). This finding could lead to a strategy for fine-tuning ferritin band gap by preselecting a metal on the basis of the free metal conductivity values.