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Bioelectrocatalysis is a green, sustainable, efficient method to produce value-added chemicals, clean biofuels and degradable materials. As an alternative approach to modern biomanufacturing technology, bioelectrocatalysis fully combines the merits of both biocatalysis and electrocatalysis to realize the green, efficient production of target products from electricity. Here, we review the development status of bioelectrocatalysis, discussing the current challenges and looking toward future development directions. First, we detail the structure, function and modification methods of bioelectrocatalysis. Next, we describe the mechanism of electron transfer, including mediated electron transfer and directed electron transfer. Third, we discuss the impact of the electrode on bioelectrocatalysis. Then we analyse and summarize the application of bioelectrocatalysis methods in the production of chemicals, biofuels and materials. Finally, we detail future developments and perspectives on bioelectrocatalysis for electrosynthesis. Electrochemical reactions can provide necessary redox equivalents for biocatalysis. In this Review, Minteer and co-workers summarize the current status and challenges of enzymatic and microbial bioelectrocatalysis for the green and efficient production of target products using electricity.

Energy storage is an integral part of modern society. A contemporary example is the lithium (Li)-ion battery, which enabled the launch of the personal electronics revolution in 1991 and the first commercial electric vehicles in 2010. Most recently, Li-ion batteries have expanded into the electricity grid to firm variable renewable generation, increasing the efficiency and effectiveness of transmission and distribution. Important applications continue to emerge including decarbonization of heavy-duty vehicles, rail, maritime shipping, and aviation and the growth of renewable electricity and storage on the grid. This perspective compares energy storage needs and priorities in 2010 with those now and those emerging over the next few decades. The diversity of demands for energy storage requires a diversity of purpose-built batteries designed to meet disparate applications. Advances in the frontier of battery research to achieve transformative performance spanning energy and power density, capacity, charge/discharge times, cost, lifetime, and safety are highlighted, along with strategic research refinements made by the Joint Center for Energy Storage Research (JCESR) and the broader community to accommodate the changing storage needs and priorities. Innovative experimental tools with higher spatial and temporal resolution, in situ and operando characterization, first-principles simulation, high throughput computation, machine learning, and artificial intelligence work collectively to reveal the origins of the electrochemical phenomena that enable new means of energy storage. This knowledge allows a constructionist approach to materials, chemistries, and architectures, where each atom or molecule plays a prescribed role in realizing batteries with unique performance profiles suitable for emergent demands.

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.

The study and application of transition metal hydrides (TMHs) has been an active area of chemical research since the early 1960s 1 , for energy storage, through the reduction of protons to generate hydrogen 2 , 3 , and for organic synthesis, for the functionalization of unsaturated C–C, C–O and C–N bonds 4 , 5 . In the former instance, electrochemical means for driving such reactivity has been common place since the 1950s 6 but the use of stoichiometric exogenous organic- and metal-based reductants to harness the power of TMHs in synthetic chemistry remains the norm. In particular, cobalt-based TMHs have found widespread use for the derivatization of olefins and alkynes in complex molecule construction, often by a net hydrogen atom transfer (HAT) 7 . Here we show how an electrocatalytic approach inspired by decades of energy storage research can be made use of in the context of modern organic synthesis. This strategy not only offers benefits in terms of sustainability and efficiency but also enables enhanced chemoselectivity and distinct, tunable reactivity. Ten different reaction manifolds across dozens of substrates are exemplified, along with detailed mechanistic insights into this scalable electrochemical entry into Co–H generation that takes place through a low-valent intermediate. A perspective is given on how an electrocatalytic approach, inspired by decades of energy storage studies, can be used in the context of efficient cobalt-hydride generation with a variety of applications in modern organic synthesis.

The production of synthetic ammonia remains dependent on the energy- and capital-intensive Haber–Bosch process. Extensive research in molecular catalysis has demonstrated ammonia production from dinitrogen, albeit at low production rates. Mechanistic understanding of dinitrogen reduction to ammonia continues to be delineated through study of molecular catalyst structure, as well as through understanding the naturally occurring nitrogenase enzyme. The transition to Haber–Bosch alternatives through robust, heterogeneous catalyst surfaces remains an unsolved research challenge. Catalysts for electrochemical reduction of dinitrogen to ammonia are a specific focus of research, due to the potential to compete with the Haber–Bosch process and reduce associated carbon dioxide emissions. However, limited progress has been made to date, as most electrocatalyst surfaces lack specificity towards nitrogen fixation. In this Review, we discuss the progress of the field in developing a mechanistic understanding of nitrogenase-promoted and molecular catalyst-promoted ammonia synthesis and provide a review of the state of the art and scientific needs for heterogeneous electrocatalysts. The artificial synthesis of ammonia remains one of the most important catalytic processes worldwide, over 100 years after its development. In this Review, recent developments in enzymatic, homogeneous and heterogeneous catalysis towards the conversion of nitrogen to ammonia are discussed, with a particular focus on how mechanistic understanding informs catalyst design.

As an essential component of amino acids and nucleic acids, nitrogen (N) is a key element of life. For atmospheric (dinitrogen, N2) and environmental (nitrate and nitrite, NO3− and NO2−) sources of N to be utilized in amino acid synthesis in various forms of life, it must first be reduced to ammonia (NH3). The Haber–Bosch process, in which N2 is reduced to NH3 at elevated temperature and pressure, represents a major NH3 production process that has had a great impact on the agricultural crop industry. This Minireview discusses the recent electrochemistry of three key enzymes of the global biogeochemical N cycle (nitrogenase, nitrate reductase, and nitrite reductase), in view of moving toward the creation of alternative NH3 production biotechnologies. Bioelectrosynthesis: The global biogeochemical N cycle is comprised of seven key steps. This Minireview evaluates recent electrochemical studies of three key enzymes of the nitrogen cycle: nitrogenase, nitrate reductase, and nitrite reductase (see figure).

There have been significant advancements in the electrosynthesis of fuels and organic molecules, making it an increasingly sustainable and cost‐effective alternative to traditional chemical redox reagents. Early versions of these systems faced challenges in chemoselectivity due to high applied overpotentials, which have been mitigated with the introduction of molecular electrocatalysts, like metal salens (MSalens). These MSalens reduce the required overpotentials, increase turnover numbers (TON), and have simple modularity within their ligand structure allowing for tunable selectivity. While these MSalen electrocatalysts are typically used homogeneously for engineering simplicity, downstream separations are often costly and time‐consuming. Immobilization of MSalens addresses these issues by enabling synthesis at lower potentials, achieving high selectivity, and facilitating straightforward separations. This review explores the application of MSalens in electrosynthesis and immobilized molecular electrocatalysts in organic electrosynthesis. This article discusses the use of CoSalen as an immobilized electrocatalyst in electrosynthesis. It explores various applications of these catalysts and presents immobilization strategies for different molecular catalysts. The article also examines the use of other immobilized electrocatalysts in synthetic organic electrochemistry, aiming to shed light on their possible applications in organic electrosynthetic processes.

The use of enzyme-based biosensors for the detection and quantification of analytes of interest such as contaminants of emerging concern, including over-the-counter medication, provides an attractive alternative compared to more established techniques. However, their direct application to real environmental matrices is still under investigation due to the various drawbacks in their implementation. Here, we report the development of bioelectrodes using laccase enzymes immobilized onto carbon paper electrodes modified with nanostructured molybdenum disulfide (MoS2). The laccase enzymes were two isoforms (LacI and LacII) produced and purified from the fungus Pycnoporus sanguineus CS43 that is native to Mexico. A commercial purified enzyme from the fungus Trametes versicolor (TvL) was also evaluated to compare their performance. The developed bioelectrodes were used in the biosensing of acetaminophen, a drug widely used to relieve fever and pain, and of which there is recent concern about its effect on the environment after its final disposal. The use of MoS2 as a transducer modifier was evaluated, and it was found that the best detection was achieved using a concentration of 1 mg/mL. Moreover, it was found that the laccase with the best biosensing efficiency was LacII, which achieved an LOD of 0.2 µM and a sensitivity of 0.108 µA/µM cm2 in the buffer matrix. Moreover, the performance of the bioelectrodes in a composite groundwater sample from Northeast Mexico was analyzed, achieving an LOD of 0.5 µM and a sensitivity of 0.015 µA/µM cm2. The LOD values found are among the lowest reported for biosensors based on the use of oxidoreductase enzymes, while the sensitivity is the highest currently reported.

In enzyme-catalysed metabolic pathways, substrate channelling often directs the movement of intermediates from one active site to the next. Intramolecular tunnels, electrostatic interactions and chemical swing arms pass intermediates from one enzyme to the next, enhancing pathway catalysis. Introducing mechanisms of bounded diffusion in chemical cascades can increase selectivity, transient rates and overall yield. Millions of years of evolution have produced biological systems capable of efficient one-pot multi-step catalysis. The underlying mechanisms that facilitate these reaction processes are increasingly providing inspiration in synthetic chemistry. Substrate channelling, where intermediates between enzymatic steps are not in equilibrium with the bulk solution, enables increased efficiencies and yields in reaction and diffusion processes. Here, we review different mechanisms of substrate channelling found in nature and provide an overview of the analytical methods used to quantify these effects. The incorporation of substrate channelling into synthetic cascades is a rapidly developing concept, and recent examples of the fabrication of cascades with controlled diffusion and flux of intermediates are presented.

The development of robust bioanalytical devices and biosensors for infectious pathogens is progressing well with the advent of new materials, concepts, and technology. The progress is also stepping towards developing high throughput screening technologies that can quickly identify, differentiate, and determine the concentration of harmful pathogens, facilitating the decision-making process for their elimination and therapeutic interventions in large-scale operations. Recently, much effort has been focused on upgrading these analytical devices to an intelligent technological platform by integrating them with modern communication systems, such as the internet of things (IoT) and machine learning (ML), to expand their application horizon. This review outlines the recent development and applications of bioanalytical devices and biosensors to detect pathogenic microbes in environmental samples. First, the nature of the recent outbreaks of pathogenic microbes such as foodborne, waterborne, and airborne pathogens and microbial toxins are discussed to understand the severity of the problems. Next, the discussion focuses on the detection systems chronologically, starting with the conventional methods, advanced techniques, and emerging technologies, such as biosensors and other portable devices and detection platforms for pathogens. Finally, the progress on multiplex assays, wearable devices, and integration of smartphone technologies to facilitate pathogen detection systems for wider applications are highlighted.