The engineering of renewable and sustainable protein-based light-to-energy converting systems is an emerging field of research. Here, we report on the development of supramolecular light-harvesting electrodes, consisting of the redox protein cytochrome c working as a molecular scaffold as well as a conductive wiring network and photosystem I as a photo-functional matrix element. Both proteins form complexes in solution, which in turn can be adsorbed on thiol-modified gold electrodes through a self-assembly mechanism. To overcome the limited stability of self-grown assemblies, DNA, a natural polyelectrolyte, is used as a further building block for the construction of a photo-active 3D architecture. DNA acts as a structural matrix element holding larger protein amounts and thus remarkably improving the maximum photocurrent and electrode stability. On investigating the photophysical properties, this system demonstrates that effective electron pathways have been created.

Artificial light-driven signal chains are particularly important for the development of systems converting light into a current, into chemicals or for light-induced sensing. Here, we report on the construction of an all-protein, light-triggered, catalytic circuit based on photosystem I, cytochrome c (cyt c) and human sulfite oxidase (hSOX). The defined assembly of all components using a modular design results in an artificial biohybrid electrode architecture, combining the photophysical features of PSI with the biocatalytic properties of hSOX for advanced light-controlled bioelectronics. The working principle is based on a competitive switch between electron supply from the electrode or by enzymatic substrate conversion.

A precursor-based approach has been employed for the construction of scalable, transparent 3D photobioelectrodes based on PSI and cyt c. An improved transparancy and high photocurrents can be achieved as compared to nanoparticle-based preparation methods.

In this work, we report on the successful assembly of cyanobacterial photosystem I (PSI) on carbon nanotubes for light-to-current conversion applications. For this purpose, glassy carbon electrodes (GCE) have been modified with multi-walled carbon nanotubes (MWCNTs). The surface of the MWCNTs has been adjusted in a non-invasive way by the use of a carboxylated pyrene derivative to achieve a covalent fixation of PSI. Our results show a cathodic photocurrent response and functionality of the biohybrid electrode upon illumination. The experiments verify that the photocurrent generation can clearly be attributed to a functional PSI on the electrode interface. An additional implementation of cytochrome c (cyt c) into this electrode architecture results in a 25fold enhancement of cathodic photocurrent response (0.8 to 18 mA cm À2 at À100 mV and 100 mW cm À2 ), which can be attributed to an improved connection of PSI with the underlying electrode.

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