Unidirectional electron injection and accelerated proton transport in bacteriorhodopsin based Bio-p-n junctions

Hampered by the absence of evidence and theoretical model of biological semiconductors, the unidirectional electron transport via the p-n junction between functional proteins and abiotic materials remains a challenge for bioelectronics. Bacteriorhodopsin (bR), a representative transmembrane protein, has demonstrated exceptional optoelectronic effects in bR/semiconductor hybrid materials and offers a possible pathway for addressing this challenge. In the present work, for the first time, bR is proved to be an n-type semiconductor with an indirect electron transition. Through the photo-electrochemical method used for studying the p-n junction effect in the bR and p-type semiconductor combined electrodes, we reached several important conclusions: The self-corrosion of bR integrated Cu₂O electrodes is delayed for about 36 times; The photocurrent of bR integrated CuSCN electrodes is enhanced by about 400%, which is attributed to the directional migration of electrons via the p-n junction. Furthermore, the ultrafast kinetics we have explored, shows that the injection of electrons shortens the lifetime of the intermediate state O₆₄₀ from 37.3 μs to 20.1 μs, what means that the protons transport rate accompanying the bR photocycle process is accelerated. Therefore, we believe that the concept of the bio-p-n junction and the mechanism of electron coupled proton transport, which are discussed herein, will promote useful research on bioelectronic applications for bR and its homologs.