Reductive electrosynthesis has faced long-standing challenges in applications to complex organic substrates at scale. Here, we show how decades of research in lithium-ion battery materials, electrolytes, and additives can serve as an inspiration for achieving practically scalable reductive electrosynthetic conditions for the Birch reduction. Specifically, we demonstrate that using a sacrificial anode material (magnesium or aluminum), combined with a cheap, nontoxic, and water-soluble proton source (dimethylurea), and an overcharge protectant inspired by battery technology [tris(pyrrolidino)phosphoramide] can allow for multigram-scale synthesis of pharmaceutically relevant building blocks. We show how these conditions have a very high level of functional-group tolerance relative to classical electrochemical and chemical dissolving-metal reductions. Finally, we demonstrate that the same electrochemical conditions can be applied to other dissolving metal–type reductive transformations, including McMurry couplings, reductive ketone deoxygenations, and epoxide openings.

A range of electroanalytical tools can be applied to studying redox reactions, probing key mechanistic questions in synthetic chemistry.

Since their invention in the 1950s, composite carbon electrodes have been employed in a wide variety of applications, ranging from batteries and fuel cells to chemical sensors, because they are easy to make and pattern at millimeter scales. Despite their widespread use, traditional carbon composite electrodes have substandard electrochemistry relative to metallic and glassy carbon electrodes. As a result, there is a critical need for new composite carbon electrodes that are highly electrochemically active, have universal and easy fabrication into complex geometries, are highly conductive, and are low cost. Herein, a new solvent-based method is presented for making low-cost composite graphite electrodes containing a thermoplastic binder. The electrodes, which are termed thermoplastic electrodes (TPEs), are easy to fabricate and pattern, give excellent electrochemical performance, and have high conductivity (700 S m). The thermoplastic binder enables the electrodes to be hot embossed, molded, templated, and/or cut with a CO laser into a variety of intricate patterns. Crucially, these electrodes show a marked improvement in peak current, peak separation, and resistance to charge transfer over traditional carbon electrodes. The impact of electrode composition, surface treatment (sanding, polishing, plasma treatment), and graphite source were found to significantly impact fabrication, patterning, conductivity, and electrochemical performance. Under optimized conditions, electrodes generated responses similar to more expensive and difficult to fabricate graphene and highly oriented pyrolytic graphite electrodes. The TPE electrode system reported here provides a new approach for fabricating high performance carbon electrodes with utility in applications ranging from sensing to batteries.

Electrochemical paper-based analytical devices (ePADs) have garnered significant interest as an alternative to traditional benchtop methods due to their low cost and simple fabrication. Historically, ePADs have relied almost exclusively on single electrode detection, limiting potential gains in sensitivity and selectivity achievable with multiple electrodes. Herein we describe incorporation of thermoplastic electrode (TPE) arrays into flow ePADs. Quasi-steady flow was solely generated by capillary action through a fan-shaped paper device. The electrode arrays were fabricated using a simple solvent-assisted method with inexpensive materials (i.e., graphite and thermoplastic binder). These electrodes can be employed as an array of individually addressable detectors or connected as an interdigitated electrode array. The TPEs were characterized through SEM, optical profilometry and cyclic voltammetry. Chronoamperometry was used to characterize the flow-based TPE-ePADs. Trace detection of a ferrocene complex (FcTMA + ) was demonstrated through generation-collection experiments, achieving a limit of detection of 0.32 pmol. These TPE arrays containing ePADs show great promise as a rapid, sensitive, and low-cost sensor for point-of-need (PON) applications.

Demonstration of a simple melt based process to overcome the issue of poorly integrated, low activity and complicated methods of carbon electrode integration into microfluidics.

A major challenge for the implementation of intact bacterial cells in photo‐bioelectrochemical systems remains the hindered extracellular electron transfer. This study focuses on purple bacteria, photosynthetic microorganisms particularly interesting for the development of bioelectrochemical systems because of their versatile metabolisms. Although soluble monomeric redox mediators have been proven as effective systems for electron transfer mediation, their application in the field is not preferable owing to their toxicity and unwanted release into the environment. An abiotic/biotic photoanode is reported in which a bioinspired redox mediating system is implemented in a 3D geometry allowing to “electrically wire” intact bacterial cells. The 3D photoanode decreased the overpotential required for harvesting photoexcited electrons, operating at +0.073 V versus the saturated calomel electrode (SCE). Accordingly, the overpotential was significantly reduced compared with a pioneering Os‐redox polymer reported in literature, which required operation at +0.303 V versus SCE. These results provide the basis for further development of bio‐photoanodes for light‐powered biosensing and power generation.

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