Thermoplastic Electrode Arrays in Electrochemical Paper-Based Analytical Devices.

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.

Personal Exposure to PM2.5 Black Carbon and Aerosol Oxidative Potential using an Automated Microenvironmental Aerosol Sampler (AMAS).

Traditional methods for measuring personal exposure to fine particulate matter (PM2.5) are cumbersome and lack spatiotemporal resolution; methods that are time-resolved are limited to a single species/component of PM. To address these limitations, we developed an automated microenvironmental aerosol sampler (AMAS), capable of resolving personal exposure by microenvironment. The AMAS is a wearable device that uses a GPS sensor algorithm in conjunction with a custom valve manifold to sample PM2.5 onto distinct filter channels to evaluate home, school, and other (e.g., outdoors, in transit, etc.) exposures. Pilot testing was conducted in Fresno, CA where 25 high-school participants ( n = 37 sampling events) wore an AMAS for 48-h periods in November 2016. Data from 20 (54%) of the 48-h samples collected by participants were deemed valid and the filters were analyzed for PM2.5 black carbon (BC) using light transmissometry and aerosol oxidative potential (OP) using the dithiothreitol (DTT) assay. The amount of inhaled PM2.5 was calculated for each microenvironment to evaluate the health risks associated with exposure. On average, the estimated amount of inhaled PM2.5 BC (µg day-1) and OP [(µM min-1) day-1] was greatest at home, owing to the proportion of time spent within that microenvironment. Validation of the AMAS demonstrated good relative precision (8.7% among collocated instruments) and a mean absolute error of 22% for BC and 33% for OP when compared to a traditional personal sampling instrument. This work demonstrates the feasibility of new technology designed to quantify personal exposure to PM2.5 species within distinct microenvironments.

Patternable Solvent-Processed Thermoplastic Graphite Electrodes.

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-1). The thermoplastic binder enables the electrodes to be hot embossed, molded, templated, and/or cut with a CO2 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.

Purple Bacteria and 3D Redox Hydrogels for Bioinspired Photo-bioelectrocatalysis.

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.

Enhanced electrochemical oxidation of ethanol using a hybrid catalyst cascade architecture containing pyrene-TEMPO, oxalate decarboxylase and carboxylated multi-walled carbon nanotube.

The work presented herein demonstrates a hybrid bi-catalytic architecture for the complete electrochemical oxidation of ethanol. The new catalytic system contains pyrene-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) immobilized on the surface of carboxylated multi-walled carbon nanotubes (MWCNT-COOH), and oxalate decarboxylase enzyme (OxDc) immobilized onto a carbon cloth electrode. Electrolysis revealed a stable amperometric curve and an excellent current density value over a duration of 10 h. In addition, the hybrid system immobilized on the carbon electrode exhibits outstanding stability after electrolysis. Nuclear magnetic resonance (NMR) and gas chromatography (GC) demonstrate that the hybrid electrode system is able to oxidize ethanol to CO2 after 10 h of electrolysis. Overall, this study illustrates the enhancement of an enzymatic biofuel cell through the hybrid multi-catalytic systems, which exhibit high oxidation rates for all substrates involved in complete ethanol oxidation, enabling the collection of up to 12 electrons per molecule of ethanol.

Emerging investigator series: oxidative potential of diesel exhaust particles: role of fuel, engine load, and emissions control.

Exposure to diesel exhaust particles (DEP) has been linked to adverse human health outcomes. DEPs are reactive and can directly or indirectly lead to oxidative stress, which promotes inflammation in the body. The oxidative potential (OP) of DEPs is not well understood, particularly for combustion with alternative fuels, under different engine loads, and in combination with modern emissions control devices. In this study, we measured the OP of DEPs using a dithiothreitol assay (OP-DTT) from a modern-day non-road diesel engine for two different fuels (conventional diesel and soy-based biodiesel), two different engine loads (idle and 50% load), and with and without an emissions control system. The OP-DTT of DEPs was sensitive to the fuel used and the presence of an emissions control system but not to the engine load. On average, the use of biodiesel resulted in factor of ∼6 reduction in OP-DTT normalized to the DEP mass and a factor of ∼12 reduction in OP-DTT normalized to the fuel consumed. The use of the emissions control, on average, resulted in a factor of ∼6 reduction in OP-DTT normalized to the DEP mass and a three order of magnitude decrease in OP-DTT normalized to the fuel consumed. When studied in conjunction with the DEP composition, the OP-DTT seemed to correlate most strongly with elemental carbon (EC), followed by semi-volatile organic vapors. Assays performed on DEPs where EC was deliberately filtered out suggested that the species responsible for the OP-DTT might be correlated with EC but would need to be water soluble (e.g., quinones). The semi-volatile organic vapors accounted for more than a quarter of the OP-DTT of DEPs collected on the quartz filters. Finally, sensitivity studies performed with a different filter membrane (i.e., Teflon®) and solvent (i.e., dichloromethane) tended to increase the OP-DTT value. OP-DTT is emerging as an important metric for studying the adverse effects of DEPs and PM2.5 on human health; results of this work help define the sources and components of diesel PM2.5 that contribute to OP-DTT.

Polycaprolactone-enabled sealing and carbon composite electrode integration into electrochemical microfluidics.

Combining electrochemistry with microfluidics is attractive for a wide array of applications including multiplexing, automation, and high-throughput screening. Electrochemical instrumentation also has the advantage of being low-cost and can enable high analyte sensitivity. For many electrochemical microfluidic applications, carbon electrodes are more desirable than noble metals because they are resistant to fouling, have high activity, and large electrochemical solvent windows. At present, fabrication of electrochemical microfluidic devices bearing integrated carbon electrodes remains a challenge. Here, a new system for integrating polycaprolactone (PCL) and carbon composite electrodes into microfluidics is presented. The PCL : carbon composites have excellent electrochemical activity towards a wide range of analytes as well as high electrical conductivity (∼1000 S m-1). The new system utilizes a laser cutter for fast, simple fabrication of microfluidics using PCL as a bonding layer. As a proof-of-concept application, oil-in-water and water-in-oil droplets are electrochemically analysed. Small-scale electrochemical organic synthesis for TEMPO mediated alcohol oxidation is also demonstrated.

A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms.

Monitoring reactive intermediates can provide vital information in the study of synthetic reaction mechanisms, enabling the design of new catalysts and methods. Many synthetic transformations are centred on the alteration of oxidation states, but these redox processes frequently pass through intermediates with short life-times, making their study challenging. A variety of electroanalytical tools can be utilised to investigate these redox-active intermediates: from voltammetry to in situ spectroelectrochemistry and scanning electrochemical microscopy. This perspective provides an overview of these tools, with examples of both electrochemically-initiated processes and monitoring redox-active intermediates formed chemically in solution. The article is designed to introduce synthetic organic and organometallic chemists to electroanalytical techniques and their use in probing key mechanistic questions.

Scalable and safe synthetic organic electroreduction inspired by Li-ion battery chemistry.

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.