Low efficiency of charge extraction (and conversely charge injection) across biotic-abiotic interfaces constitutes an obstacle to the integration of biological and electronic systems in high-performance bioelectronic devices. Advances in the promotion of charge transport across these typically non-conductive interfaces will have far-reaching implications in important applications such as alternative energy generation, bioelectrosynthesis, diagnostics, and environmental monitoring. This review highlights the use of synthetic materials to improve electrical interfacing between biological systems and electrodes, focusing specifically on whole cell bioelectrochemical systems. By taking advantage of a rich variety of materials chemistry and synthetic methodologies, significant improvements to the facilitation of charge transport across abiotic-biotic interfaces have been realized. The modifications of the bioelectronic interfaces presented herein include the use of organic small molecules, semiconducting and redox active polymers, inorganic nanoparticles, carbon nanotubes, graphene, hybrid organic-inorganic systems, and micro-/nanoelectrodes. However, design rules to guide material selection and choices regarding device architecture remain ambiguous. Establishment of a clearer understanding of bioelectronic charge transfer phenomena, their constituent pathways, and means of stimulating or selecting for different pathways is still work in progress. As such, great opportunities exist for materials scientists to contribute to these topics through design and implementation.

It is important to tailor biotic-abiotic interfaces in order to maximize the utility of bioelectronic devices such as microbial fuel cells (MFCs), electrochemical sensors and bioelectrosynthetic systems. The efficiency of electron-equivalent extraction (or injection) across such biotic-abiotic interfaces is dependent on the choice of the microbe and the conductive electrode material. In this contribution, we show that spontaneous intercalation of a conjugated oligoelectrolyte, namely 4,4'-bis(4'-(N,N-bis(6''-(N,N,N-trimethylammonium)hexyl)amino)-styryl)stilbene tetraiodide (DSSN+), into the membranes of Escherichia coli leads to an increase in current generation in MFCs containing carbon-based electrodes. A combination of scanning electron microscopy (SEM) and confocal microscopy was employed to confirm the incorporation of DSSN+ into the cell membrane and biofilm formation atop carbon felt electrodes. Current collection was enhanced by more than 300% with addition of this conjugated oligoelectrolyte. The effect of DSSN+ concentration on electrical output was also investigated. Higher concentrations, up to 25 μM, lead to an overall increase in the number of charge equivalents transferred to the charge-collecting electrode, providing evidence in support of the central role of the synthetic system in improving device performance.

A near-IR-emitting conjugated oligoelectrolyte (COE), ZCOE, was synthesized, and its photophysical features were characterized. The biological affinity of ZCOE is compared to that of an established lipid-membrane-intercalating COE, DSSN+, which has blue-shifted optical properties making it compatible for tracking preferential sites of accumulation. ZCOE exhibits diffuse staining of E. coli cells, whereas it displays internal staining of select yeast cells which also show propidium iodide staining, indicating ZCOE is a “dead” stain for this organism. Staining of mammalian cells reveals complete internalization of ZCOE through endocytosis, as supported by colocalization with LysoTracker and late endosome markers. In all cases DSSN+ persists in the outer membranes, most likely due to its chemical structure more closely resembling a lipid bilayer.

Variation in conjugated oligoelectrolyte (COE) repeat units is shown to affect the rate of COE insertion into mammalian membrane patches and membrane patch stabilities. These findings suggest that it is possible to find COE structures that do not destroy membranes while at the same time allow for more facile transmembrane movement of ions/substrates.

Thick, tetrasulfide‐functionalized periodic mesoporous organosilica films are presented as chemically specific coatings on long‐period grating (LPG)‐inscribed fiber‐optic waveguides for the direct, parts per billion (ppb)‐level detection of Pb(II) species in solution.