ACEstat: A DIY Guide to Unlocking the Potential of Integrated Circuit Potentiostats for Open-Source Electrochemical Analysis.

Miniaturization of analytical instrumentation is paramount to enabling convenient in-field sensing. The recent thrust in potentiostat miniaturization for electrochemical sensing and general use has led to the development of commercial application specific integrated circuits (ASICs) that pack all the power of a benchtop instrument into one 5 mm × 5 mm chip. While the capabilities of these integrated circuits far exceed those of open-source potentiostats in the literature, the activation barrier for their implementation requires extensive electrical and software engineering expertise to overcome. In order to more rapidly bring the utility of ASIC potentiostats to researchers, we present a low size, weight, power, and cost (Low SWaP-C) Army Corps of Engineers potentiostat (ACEstat) based on the widely available ADuCM355 offered by Analog Devices. This potentiostat is a streamlined and fully programmable device that leverages industry-leading integrated hardware to perform electrochemical measurements such as cyclic voltammetry, pulse voltammetry, and electrochemical impedance spectroscopy. The ACEstat enables control over a wide range of test parameters and displays results through an intuitive, open-source graphical user interface available on mobile devices and computers. In this report, we present an approachable, do-it-yourself guide to unlocking the capabilities of this integrated circuit potentiostat by outlining the fabrication and programming details necessary to facilitate electroanalysis. Furthermore, we demonstrate the practicality of this device by detecting 2,4,6-trinitrotoluene (TNT) in water at sub-mg/L detection limits, highlighting its potential for in-field use.

Selecting an Optimal Faraday Cage To Minimize Noise in Electrochemical Experiments.

The ubiquitous Faraday cage, an experimental component particularly essential for nanoelectrochemical measurements, is responsible for neutralizing noise introduced by electromagnetic interference (EMI). Faraday cage designs abound in the literature, often exhibiting varying thicknesses, mesh sizes, and base materials. The fact that the Faraday cage composition most often goes unreported underscores the fact that many electrochemical researchers assume a 100% EMI reduction for any given design. In this work, this assumption is challenged from a theoretical and empirical perspective by highlighting the physical principles producing the Faraday effect. A brief history of the Faraday cage and a simplified theoretical approach introduce fundamental considerations regarding optimal design properties. In practice, time-domain noise profiles and corresponding Fourier transform frequency domain information for custom-built Faraday cages reveal that maximally conductive cages provide more optimal EMI exclusion.

A Generalized Potentiostat Adaptor for Multiplexed Electroanalysis.

Electrochemical measurements over an array of electrodes may be accomplished with one of three potentiostat architectures: a single-channel device which averages the signal from a number of interconnected electrodes, a multichannel device with dedicated circuits for each electrode, or a single-channel device with a multiplexer interface to isolate the signal from specific electrodes. Of these three architectures, the use of a multiplexer interface is best suited to facilitate measurements over individual electrodes without the need for large numbers of dedicated potentiostat channels. We present a versatile strategy for the development of flexible printed circuit (FPC) electrode arrays with accompanying multiplexing hardware to interface with single-channel potentiostats. The FPC array was fabricated with 78 individually addressable 0.3 mm diameter gold working electrodes and characterized using optical and scanning electron microscopy, energy dispersive spectroscopy, profilometry, impedance spectroscopy, and cyclic voltammetry to investigate the morphology, elemental composition, height profile, impedance characteristics, and electrochemical response, respectively. Interfacing the FPC array via a simple connector with three 32-channel ADG731 multiplexers permitted electrochemical measurements using single-channel commercial potentiostats. Voltammetric experiments were conducted to demonstrate the reliability, stability, and reproducibility of the FPC array and interfacing hardware. The combination of these devices represents an accessible hardware platform with robust, functionalizable electrodes, a simple connection interface with commercial potentiostats, and a low cost through the use of off-the-shelf components. Our reported strategy holds great promise to facilitate multiplexed electroanalysis in next-generation sensors to increase statistical sample size and multianalyte detection capabilities.

In Situ Preconcentration and Quantification of Cu2+ via Chelating Polymer-Wrapped Multiwalled Carbon Nanotubes.

Trace analysis of heavy metals in complex, environmentally relevant matrices remains a significant challenge for electrochemical sensors employing stripping voltammetry-based detection schemes. We present an alternative method capable of selectively preconcentrating Cu2+ ions at the electrode surface using chelating polymer-wrapped multiwalled carbon nanotubes (MWCNTs). An electrochemical sensor consisting of poly-4-vinyl pyridine (P4VP)-wrapped MWCNTs anchored to a poly(ethylene terephthalate) (PET)-modified gold electrode (r = 1.5 mm) was designed, produced, and evaluated. The P4VP is shown to form a strong association with Cu2+ ions, permitting preconcentration adjacent to the electrode surface for interrogation via cyclic voltammetry. The sensor exhibited a detection limit of 0.5 ppm with a linear range of 1.1-13.8 ppm (16.6-216 µM) and a relative standard deviation (RSD) of 4.9% at the Environmental Protection Agency (EPA) limit of 1.3 ppm. Evaluation in tap water, lake water, ocean water, and deionized water rendered similar results, highlighting the generalizability of the presented preconcentration strategy. The advantages of electrochemical analysis paired with polymeric chelation represent an effective platform for the design and deployment of heavy metal sensors for continuous monitoring of natural waters.

Instrumenting Polyodon spathula (Paddlefish) Rostra in Flowing Water with Strain Gages and Accelerometers.

The prominent rostrum of the North American Paddlefish, supported by a lattice-like endoskeleton, is highly durable, making it an important candidate for bio-inspiration studies. Energy dissipation and load-bearing capacity of the structure from extreme physical force has been demonstrated superior to that of man-made systems, but response to continuous hydraulic forces is unknown and requires special instrumentation for in vivo testing on a live fish. A single supply strain gage amplifier circuit has been combined with a digital three-axis accelerometer, implemented in a printed circuit board (PCB), and integrated with the commercial-off-the-shelf Adafruit Feather M0 datalogger with a microSD card. The device is battery powered and enclosed in silicon before attachment around the rostrum with a silicon strap "watch band." As proof-of-concept, we tested the instrumentation on an amputated Paddlefish rostrum in a water-filled swim tunnel and successfully obtained interpretable data. Results indicate that this design could work on live swimming fish in future in vivo experiments.

Preparation and Characterization of Polyhedral Oligomeric Silsesquioxane-Containing, Titania-Thiol-Ene Composite Photocatalytic Coatings, Emphasizing the Hydrophobic-Hydrophilic Transition.

Coatings prepared from titania-thiol-ene compositions were found to be both self-cleaning, as measured by changes in water contact angle, and photocatalytic toward the degradation of an organic dye. Stable titania-thiol-ene dispersions at approximately 2 wt % solids were prepared using a combination of high-shear mixing and sonication in acetone solvent from photocatalytic titania, trisilanol isobutyl polyhedral oligomeric silsesquioxane (POSS) dispersant, and select thiol-ene monomers, i.e., trimethylolpropane tris(3-mercaptopropionate) (TMPMP), pentaerythritol allyl ether (APE), and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT). The dispersed particle compositions were characterized by DLS and TEM. The synthetic methods employed yield a strongly bound particle/POSS complex, supported by IR, 29Si NMR, and TGA. The factors of spray techniques, carrier solvent volatility, and particle size and size distributions, in combination, likely all contribute to the highly textured but uniform surfaces observed via SEM and AFM. Polymer composites possessed thermal transitions (e.g., Tg) consistent with composition. In general, the presence of polymer matrix provided mechanical integrity, without significantly compromising or prohibiting other critical performance characteristics, such as film processing, photocatalytic degradation of adsorbed contaminants, and the hydrophobic-hydrophilic transition. In all cases, coatings containing photocatalytic titania were converted from superhydrophobic to superhydrophilic, as defined by changes in the water contact angle. The superhydrophilic state of samples was considered persistent, since long time durations in complete darkness were required to observe any significant hydrophobic return. In a preliminary demonstration, the photocatalytic activity of prepared coatings was confirmed through the degradation of crystal violet dye. This work demonstrates that a scalable process can be found to prepare titania-thiol-ene coatings having improved coating properties which also exhibit photocatalytic and self-cleaning attributes.