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Conditions under which the bipolar reference electrode (BPRE) acts as a true reference electrode or an unusually stable quasi-reference electrode (BPQRE) are elucidated. This novel reference electrode overcomes many drawbacks of fritted electrodes.

The collision of two or more water microdroplets adsorbed on an electrified surface has been tracked by ECL imaging, uncovering the dynamic complexity of the resulting water microdroplet.

Chemical reactivity in droplets is often assumed to mimic reactivity in bulk, continuous water. Here, we study the catalytic oxidation of cysteine by electrogenerated hexacyanoferrate(III) in microliter droplets. These droplets are adsorbed onto glassy carbon macroelectrodes and placed into an immiscible 1,2-dichloroethane phase. We combined cyclic voltammetry, optical microscopy, and finite element simulations to quantify the apparent bimolecular rate constant, k(c,app), in microdroplets and bulk water. Statistical analyses reveal that the apparent bimolecular rate constant (k(c,app)) values formicrodroplets are larger than those in the continuous phase. Reactant adsorption to the droplet boundary has previously been implicated as the cause of such rate accelerations. Finite element modeling of this system suggests that molecular adsorption to the liquid|liquid interface cannot alone account for our observations, implicating kinetics of the bimolecular reaction either at the boundary or throughout the microliter volume. Our results indicate that cysteine oxidation by electrogenerated hexacyanoferrate(III) can be accelerated within a microenvironment, which may have profound implications on understanding biological processes within a cell.

Cocaine is one of the most commonly trafficked and abused drugs in the United States, and deployable field tests are important for rapid identification in nonlaboratory settings. At present, colorimetric tests exist for in-field determination, but these fundamentally suffer from interferent effects. Cocaine is an organic salt that is readily water soluble as a cation and almost insoluble in the deprotonated neutral form. Here, we take advantage of the electrochemical window of water to increase the pH at the electrode surface by driving water reduction, effectively electroprecipitating the cocaine base. The precipitate on the electrode surface is then electrochemically oxidized by a voltammetric sweep through sufficiently positive potentials. We demonstrate excellent selectivity to cocaine compared to common adulterants, such as procaine, lidocaine, benzocaine, caffeine, and levamisole. Finally, we detect cocaine on a carbon fiber microelectrode, demonstrating miniaturizability and allowing access to low-resistance media (e.g., tap water).

Chemistry in confined volumes, such as aqueous droplets, is different from bulk, continuous water. However, few techniques are available to probe interfacial reactivity in complex, multiphase environments. Here, we demonstrate preferential electroreduction at the oil|water|conductor (three-phase) interface. Electrodeposition of cobalt and nickel results in ring-like structures that can be characterized with tens of nanometer precision in scanning electron microscopy and energy dispersive x-ray spectroscopy. To demonstrate the generalizability of these observations, we demonstrate that electroreduction of resazurin to fluorescent resorufin occurs preferentially at the three-phase boundary and does not strongly depend on droplet geometry. We suggest that our observations can be explained by adsorption to the liquid|liquid interface and the interfacial electric field. These results, grounded in three-phase boundary reactivity, are highly important across all fields of chemistry and biology because they highlight how the interface can change chemistry in unexpected ways.

We present a facile method to detect methamphetamine in aerosols by trapping aerosols in a soap bubble wall for electroanalysis. A microwire was placed through a soap bubble wall as a sensing electrode along with a 1 mm diameter platinum wire as the counter/reference electrode. The resulting electrochemical cell and electrode geometry are unique and allow for reproducible electrochemistry between bubble walls. We first provide a thorough investigation of the cell and electrode geometry and an electrochemical characterization of ferrocene methanol in a soap bubble wall composed of 0.1 M KCl and 0.1% Triton X-100 (v/v). To visualize the boundary where the bubble wets the microwire (the effective electrode area) with tens of nanometer resolution, we electrodeposited platinum on carbon microwire. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the bubble contact (i.e., cylindrical electrode height) is 157 ± 30 μm. Correlated digital microscopy suggests that the wetting reaches

The rapid rise of technology in the modern world has led to an increased demand for energy. Consequently, it is essential to increase the efficiency of current energy-producing systems due to the poor activity of their catalysts. Nanoparticles play a significant role in energy storage and conversion; however, electrodeposition of nanoparticles is difficult to achieve due to surface heterogeneities, nanoparticle diffusion layer overlap, and the inability to electrodeposit multi-metallic nanoparticles with stoichiometric control. These problems can be solved through nanodroplet-mediated electrodeposition, a technique where water nanodroplets are filled with metal salt precursors that form stable nanoparticles when they collide with a negatively-biased electrode. Further, this method has demonstrated control over nanoparticle size and morphology, displaying a wide variety of applications for the generation of materials with excellent catalytic properties. Historically, the cost of nanodroplet-mediated electrodeposition experimentation is prohibitive because practitioners use 0.1 M to 0.5 M tetrabutylammonium perchlorate (TBAP) dissolved in the oil phase (∼10 mL). Such high concentrations of electrolytes have been used to lower ohmic drop and provide ions to maintain charge balance during electrodeposition. Here, we show that supporting electrolyte is not necessary for the oil phase. In fact, one can use a suitable salt (such as lithium perchlorate) in the aqueous phase to achieve nanoparticle electrodeposition. This simple change, grounded in an understanding of ion transfer, drives down the cost per experiment by nearly three orders of magnitude, representing a necessary step forward in enabling practical nanoparticle electrodeposition from water nanodroplets. This approach is a promising procedure for future cost-effective energy conversion systems relying on electrocatalytic nanoparticles.

Precise determination of boundaries in co-culture systems is difficult to achieve with scanning electrochemical microscopy alone. Thus, biological scanning electrochemical microscope platforms generally consist of a scanning electrochemical microscope positioner mounted on the stage of an inverted microscope for correlated electrochemical and optical imaging. Use of a fluorescence microscope allows for site-specific fluorescence labeling to obtain more clearly resolved spatial and electrochemical data. Here, we construct a unique hyperspectral assisted-biological scanning electrochemical microscope platform to widen the scope of biological imaging. Specifically, we incorporate a variable fluorescence bandpass source into a biological scanning electrochemical microscope platform for simultaneous optical, spectral, and electrochemical imaging. Not only does this platform serve as a cost-effective alternative to white light laser imaging, but additionally it provides multi-functional analysis of biological samples. Here, we demonstrate the efficacy of our platform to discern the electrochemical contribution of site-specific cells by optically and spectroscopically resolving boundaries as well as cell types within a complex biological system.

Perfluorooctane sulfonate (PFOS) is one of the most lethal per- and poly-fluoroalkyl substances (PFAS). Generally, exposure effects are studied through case-controlled studies, cohort studies, or cell assays. Unfortunately, most studies involving two-dimensional cell cultures require cell lysis or fixation. For

Over the past decade, many groups have shown that chemistry changes drastically in confined volumes compared to large volumes. As a robust analytical chemistry tool, electrochemistry has augmented to the...

While there are numerous publications on laser-assisted fabrication and characterization of Pt nanoelectrodes, the exact replication of those procedures is not as straightforward as following a single recipe across laboratories....

Nanodroplet-mediated electrodeposition is a reliable method for electrodepositing nanoparticles by confining a small amount of metal-salt precursor in water nanodroplets (radius ∼400 nm) suspended in an oil continuous phase. This technique provides a great advantage in terms of nanoparticle size, morphology, and porosity. For an electrochemical reaction to proceed in the aqueous nanodroplet, the electroneutrality condition must be maintained. Classically, [NB

Over 200 years ago, Alessandro Volta published his observations of a steady voltage when a piece of electrolyte-soaked cardboard was sandwiched between two dissimilar metals. This observation initiated a century of argument as to the origin of voltaic electricity (contact vs chemical) and catalyzed practical advances, such as the first demonstration of water electrolysis by William Nicholson and Anthony Carlisle within a few months of Volta’s announcement. A deep dive into the literature demonstrates that practitioners at the time were disadvantaged in their quest for a detailed understanding of the pile. For instance, the idea of salt dissociation into charged ions and the discovery of the electron did not come to light until nearly an entire century after the pile made its first debut. A thorough survey of the literature also indicates that original piles, which were composed of silver or copper as the cathode and zinc as the anode, operated by the dissolution of zinc at the anode and the reduction of some species at the cathode. A cathodic reaction commonly implicated is the hydrogen evolution reaction (HER). Here, we demonstrate that the oxygen reduction reaction (ORR) contributes to the cathodic half-reaction from pH 0 to 14, suggesting that the true mechanism of the voltaic pile depends on the mixed potential set by the HER/ORR and zinc oxidation. While the main point of this article is to implicate dissolved oxygen, we end the article with suggestions for experimental modifications to promote hands-on learning.

The interfacial properties of multiphase systems are often difficult to quantify. We describe the observation and quantification of immiscible solvent entrapment on a carbonaceous electrode surface using microscopy-coupled electrogenerated chemiluminescence (ECL). As aqueous microdroplets suspended in 1,2-dichloroethane collide with a glassy carbon electrode surface, small volumes of the solvent become entrapped between the electrode and aqueous phase, resulting in an overestimation of the true microdroplet/electrode contact area. To quantify the contribution of solvent entrapment decreasing the microdroplet contact area, we drive an ECL reaction within the microdroplet phase using tris(bipyridine)ruthenium(II) chloride ([Ru(bpy)3]Cl2) as the ECL luminophore and sodium oxalate (Na2C2O4) as the co-reactant. Importantly, the hydrophilicity of sodium oxalate ensures that the reaction proceeds in the aqueous phase, permitting a clear contrast between the aqueous and 1,2-dichloroethane present at the electrode interface. With the contrast provided by ECL imaging, we quantify the microdroplet radius, apparent microdroplet contact area (aqueous + entrapped 1,2-dichloroethane), entrapped solvent contact area, and the number of entrapped solvent pockets per droplet. These data permit the extraction of the true microdroplet/electrode contact area for a given droplet, as well as a statistical assessment regarding the probability of solvent entrapment based on microdroplet size.

Copper nanoparticles have emerged as promising electrocatalysts for energy storage and conversion. Generally, homogenous nanoparticle synthesis requires a stabilizing ligand, which may influence the electrocatalysis. Ligands can be avoided by direct nanoparticle electrodeposition. Here, we extend nanodroplet-mediated electrodeposition to the electrodeposition of copper nanoparticles from aqueous nanodroplets suspended in 0.1 M tetrabutylammonium hexafluorophosphate ([TBA][PF6]) and 1,2-dichloroethane. Stochastic electrochemistry on microelectrodes was used to elucidate nanoparticle growth kinetics for various solution conditions and substrate materials. A study on the effect of surfactants on nanoparticle morphology and growth kinetics demonstrated the surfactant's role as an avenue for morphological control. Nanoparticle morphology was studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). Energy-dispersive X-ray Spectroscopy (EDX) confirmed the presence of copper nanoparticles. TEM and Selected Area Electron Diffraction (SAED) confirmed nanoparticle size, morphology, and polycrystallinity. We demonstrate tunable nanoparticle size using cyclic voltammetry on single aqueous nanodroplets by altering the voltammetric sweeping potentials of copper electroreduction. Finite element simulations validate the voltammetric response and ability to control the nanoparticle size with nanometer resolution during a voltammetric sweep. These results inform the electrodeposition of copper nanoparticles from aqueous nanodroplets for important applications, such as the conversion of CO2 to hydrocarbon fuels.

Per- and polyfluoroalkyl substances (PFAS) are an emerging class of pervasive and harmful micropollutant. Next-generation sensors are necessary to detect PFAS at sub-nanomolar levels. Electrochemistry can measure analyte concentrations at sub-10 nM levels and offers a deployable platform; however, the lack of chemical reactivity of PFAS species requires electrode surface functionalization with a molecularly imprinted polymer (MIP). Previously, such sensors have required a well-characterized one-electron mediator (i.e., ferrocene carboxylic acid or ferrocene methanol) for detection. Natural waterways do not have an abundance of ferrocenyl compounds for quantification, implying that these mediators limit sensor practicality, deployability, and cost. Here, we take advantage of ambient oxygen present in river water to quantify one of the more harmful PFAS molecules, perfluorooctanesulfonate (PFOS), from 0 to 0.5 nM on a MIP-modified carbon substrate. Differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) generated calibration curves for PFOS in river water using oxygen as the mediator. Importantly, we show that electrochemical impedance spectroscopy is superior to voltammetric techniques: like ultramicroelectrodes, this technique can be used in low-conductivity matrices like river water with high reproducibility. Further, impedance provides a PFOS limit of detection of 3.4 pM. We also demonstrate that the common interferents humic acid and chloride do not affect the sensor signal. These results are a necessary step forward in developing deployable sensors that act as a first line of defense for detecting PFAS contamination at its earliest onset.

At the most fundamental level, the behavior of tissue is governed by the activity of its single cells. A detailed examination of single-cell biology is necessary in order to gain a deeper understanding of disease progression. While single-cell genomics and transcriptomics are mature due to robust amplification strategies, the metabolome is difficult to quantify. Nanoelectrochemical techniques stand poised to quantify single-cell metabolism as a result of the fabrication of nanoelectrodes, which allow one to make intracellular electrochemical measurements. This article is concerned with intracellular nanoelectrochemistry, focusing on the sensitive and selective quantification of various metabolites within a single, living cell. We will review the strong literature behind this field, discuss the potential deleterious effects of passing charge inside cells, and provide future outlooks for this promising avenue of inquiry. We also present a mathematical relationship based on Faraday's Law and bulk electrolysis theory to examine the consumption of analyte within a cell due to passing charge at the nanotip.Graphical abstract.

Per- and polyfluoroalkyl substances (PFAS) are emerging as harmful environmental micropollutants. Generally, PFAS species are quantified by mass spectrometry, for which a collected sample is taken to a centralized facility. Robust techniques to quantify PFAS in the field are necessary to diagnose environmental contamination at the earliest onset of pollution. Here, we developed a molecularly imprinted polymer (MIP) electrode for the detection of perfluorooctanesulfonate (PFOS) and explored the MIP surface and the effects of interfering molecules. MIPs were formed by the anodic deposition of o-phenylenediamine (o-PD) in the presence of PFOS template molecules on a glassy carbon macroelectrode. The performance of the resulting MIP electrode was evaluated by the current obtained from the oxidation of ferrocene carboxylic acid as the electrochemical probe. The MIP electrode was able to detect PFOS with a detection limit of 0.05 nM, which is lower than the health advisory limit of 0.14 nM reported by the U.S. EPA. To better understand PFOS association into the MIP, a Langmuir binding model was developed based on the changes in electrochemical responses of the MIP. Fitting the model to the experimental data gave an association constant (KA) of 4.95 × 1012 over a PFOS concentration range of 0 to 0.05 nM. The binding isotherm of other commonly found substances in contaminated water sources such as chloride, humic acid, perfluorooctanoic acid (PFOA), and perfluorobutanesulfonate (PFBS) was also investigated. In the case of chloride and humic acid, the calculated KA values of 9.05 × 107 and 6.01 × 105, respectively, indicate relatively weak adsorption of these species on the MIP. However, PFOA, which is the carboxylate analog of PFOS, revealed a very close KA value (3.41 × 1012) to PFOS. A greater KA value (1.43 × 1013) was obtained for PFBS, which possesses the same functional group and a smaller molecular size compared to PFOS. The presented platform emphasizes the necessity to develop new strategies to make MIP sensors more specific if practical applications are to be pursued.

Per- and polyfluoroalkyl substances (PFAS) are emerging as a hazardous class of environmental micropollutant, and robust, sensitive, and inexpensive sensing modalities are needed to detect the earl...

Reactivity at phase boundaries is central to many areas of chemistry, from synthesis to heterogeneous catalysis. New tools are necessary to gain a more detailed understanding of processes occurring at these boundaries. We describe a series of experiments to visualize phase boundaries using electrogenerated chemiluminescence (ECL) on glassy carbon electrodes. By taking advantage of the solubilities of the ECL luminophore and the coreactant in different liquid phases, we demonstrate that the interface of various phases (i.e., the boundaries formed between a water microdroplet, 1,2-dichloroethane, and a glassy carbon electrode and the boundaries formed between an oxygen bubble, water, and a glassy carbon electrode) can be evaluated. We measured microdroplet contact radii, the three-phase boundary thickness, and growth dynamics of electrogenerated O2 bubbles. These experimental tools and the fundamental knowledge they yield will find applications in biology, nanoscience, synthesis, and energy storage and conversion, where understanding phase boundary chemistry is essential.

The progression of nanoscience necessitates quantitative tools to understand reactivity at the nanoscale. Here, we report a quantitative model that describes both the electrokinetic and diffusion-l...

We demonstrate the application of open circuit potentiometry (OCP) to measure enzyme turnover kinetics, kturn. The electrode surface will become poised by the addition of a well-behaved redox pair, such as ferrocenemethanol/ferrocenium methanol (FcMeOH/FcMeOH+), which acts as the cosubstrate for the enzymatic process. A measurable change in potential results when an enzyme consumes the one-electron transfer mediator. Glucose oxidase was studied as a test-case, but the method is generalizable across oxidoreductase enzymes that rely on electron transfer mediators. In the presence of glucose and FcMeOH+, glucose oxidase delivers electrons to FcMeOH+, and the potential changes with respect to the Nernst equation. A theoretical model incorporating enzymatic rate expressions into the Nernst equation was derived to explain the observed potential transients, and experimental data fit theory well. A similar experiment was performed using amperometry on ultramicroelectrodes (UMEs). Here, the same enzymatic rate expression may be incorporated into the equation for steady-state flux to an UME to obtain kturn. While similar kinetic information was obtained from the potentiometric and amperometric responses, potentiometry is independent of electrode size and mass transfer effects. Finally, we show how kturn changes as a function of one-electron mediator. Our results may eventually find applications to biosensors, where electrode fouling plagues long-term sensor performance.

The field of electrochemical biosensors has been dominated by amperometric and voltammetric sensors; however, these are limited greatly in their signal dependence on electrode size. Open circuit potentiometric sensors are emerging as an alternative due to their signal insensitivity to electrode size. Here, we present a second-generation biosensor that uses a modified chitosan hydrogel to entrap a dehydrogenase or other oxidoreductase enzyme of interest. The chitosan is modified with a desired electron mediator such that in the presence of the analyte, the enzyme will oxidize or reduce the mediator, thus altering the measured interfacial potential. Using the above design, we demonstrate a swift screening method for appropriate enzyme-mediator pairs based on open circuit potentiometry, as well as the efficacy of the biosensor design using two dehydrogenase enzymes (FADGDH and ADH) and peroxidase. Using 1,2-naphthoquinone as the mediator for FADGDH, dynamic ranges from 0.1 to 50 mM glucose are achieved. We additionally demonstrate the ease of fabrication and modification, a lifetime of ≥28 days, insensitivity to interferents, miniaturization to the microscale, and sensor efficacy in the presence of the enzyme's natural cofactor. These results forge a foundation for the generalized use of potentiometric biosensors for a wide variety of analytes within biologically-relevant systems where oxygen can be an interferent.

d-Serine biosensing has been extensively reported based on enzyme sensors using flavin adenine dinucleotide (FAD) -dependent d-amino acid oxidase (DAAOx), based on the monitoring of hydrogen peroxide generated by the enzymatic reaction, which is affected by dissolved oxygen concentration in the measurement environment in in vivo use. Here we report a novel sensing principle for d-serine, transient potentiometry based d-serine sensor using engineered DAAOx showing quasi-direct electron transfer (DET) property. DAAOx Gly52Val mutant, revealed to possess dye-mediated dehydrogenase activity using artificial synthetic electron acceptors, while its oxidase activity was negligible. The enzyme was immobilized on electrode and was modified with amine-reactive phenazine ethosulfate, resulted an enzyme electrode showing quasi-DET type response. Although OCP based monitoring took more than several minutes to obtain steady state OCP value, the time dependent OCP change monitoring, transient potentiometry, provided rapid and sensitive sensor signals. While dOCP/dt based monitoring was suitable for sensing with longer than 5 s time resolution with d-serine concentration range between 0.5 mM and 5 mM, dOCP/d t based monitoring is suitable for d-serine monitoring with much shorter time resolution (less than 1 s) with high sensitivity with wider dynamic range (20 μM-30 mM). The maximum dOCP/d t was -39.2 ± 2.0 mV/s

Per- and polyfluoroalkyl substances (PFAS) are an emerging class of pervasive and harmful environmental micropollutant with negative health effects on humans. Therefore, there has been extensive research into the remediation (i.e., the detection, extraction, and destruction) of these chemicals. For efficient extraction and destruction, PFAS contamination must be detected at its onset; however, conventional PFAS detection methods rely on sample collection and transport to a centralized facility for testing, which is expensive and time-consuming. Electrochemistry offers a robust, inexpensive, and deployable sensing strategy that could detect pollution at its onset; however, the electrochemical inactivity of PFAS necessitates the use of a surface functionalization strategy. Molecularly imprinted polymers (MIPs), which are a popular surface functionalization strategy, have been around since the 1980s for specific electrochemical detection and have expanded electrochemical detection to analytes that are not electrochemically active. MIPs have been more recently demonstrated for the detection of a variety of PFAS species, but additional advances must be made for realization of a deployable, electrochemical MIP-based sensor. This Feature highlights the history of MIPs for PFAS detection and our group's recent advances that are essential to enable the creation of a deployable electrochemical PFAS sensor: development of rigorous analytical standards to quantify interferent effects, miniaturization of the detection platform for quantification in river water, the use of ambient O2 as the mediator molecule for detection, and the development of hardware for in-field multiplexed electrochemical sensing.

Reference electrodes must maintain a well-defined potential for long periods of time to be useful. The silver/silver chloride (Ag/AgCl) reference electrode is arguably the most widely used reference electrode, but it leaks silver and chloride ions into the sample solution through the porous frit over time. Further, the porous frit makes miniaturization to the micro- and nanoscale challenging. Here, we present an alternative, where the traditional Ag/AgCl reference electrode porous frit is replaced by a conductive wire, preventing ion leakage and allowing miniaturization to the microscale. Charge balance is maintained through a closed bipolar electrochemical mechanism, where faradaic processes occur on each end of the sealed wire. Using the above design, we demonstrate the efficacy of the leakless, bipolar reference electrode (BPRE) and miniaturize it to the microscale (μ-leakless BPRE). Importantly, we demonstrate that leakless and μ-leakless BPREs behave the same as commercial reference electrodes during potentiometric measurements and leakless BPREs perform similarly during voltammetric measurements on ultramicroelectrodes. We demonstrate that the drift during voltammetry using a leakless BPRE on a macroelectrode is slightly more appreciable compared to the drift seen with a commercial reference electrode. We detail design principles for the use of leakless BPREs in nonaqueous solvents and in sealing other conductive materials (e.g., gold and carbon). Using mass spectrometry, we show that the maximum leakage of methylene blue is 0.36 fmol/s, at least 2 orders of magnitude smaller than that of commercial reference electrodes. Finally, we demonstrate the efficacy of using leakless BPREs in potentiometric glucose sensing.

Enzymes are molecules that catalyze reactions critical to life. These catalysts are often studied in bulk water, where the influence of water volume on reactivity is neglected. Here, we demonstrate rate enhancement of up to two orders of magnitude for enzymes trapped in submicrometer water nanodroplets suspended in 1,2-dichloroethane. When single nanodroplets irreversibly adsorb onto an ultramicroelectrode surface, enzymatic activity is apparent in the amperometric current-time trace if the ultramicroelectrode generates the enzyme cofactor. Nanodroplet volume is easily accessible by integrating the current-time response and using Faraday's Law. The single nanodroplet technique allows us to plot the enzyme's activity as a function of nanodroplet size, revealing a strong inverse relationship. Finite element simulations confirm our experimental results and offer insights into parameters influencing single nanodroplet enzymology. These results provide a framework to profoundly influence the understanding of chemical reactivity at the nanoscale.

Experimental electrochemistry offers unique opportunities for interactive instruction at all levels of education; however, widespread adoption in curricula is hindered by high costs associated with...

We present a robust and facile method to produce metal nanoparticle (NP) alloys in a one-step synthesis using direct electrodeposition onto highly oriented pyrolytic graphite (HOPG). Precursor salts, H2PtCl6 and Pd(NO3)2, were dissolved in a 1 mM sodium dodecylsulfate (SDS) water droplet with 1× phosphate buffered saline solution and suspended in a dichloroethane (DCE) continuous phase. Tetrabutylammonium perchlorate was added to the DCE continuous phase to maintain charge balance during electrodeposition. NP fabrication via electrodeposition was driven by droplet collisions onto HOPG, which was biased at a potential where the metal precursor salts would reduce to their respective zero-valent atoms. Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) were used to study the size, coverage, and morphology of the NPs as well as the atomic stoichiometry. EDX mapping indicated homogeneous distribution of Pd and Pt at the single NP level. Homogeneously alloyed PdPt NPs were realized from this study with demonstrated control over metal composition, surface coverage, and NP size. Keywords: Alloy, Bimetallic, Electrodeposition, Emulsion droplet, Nanoparticle

We demonstrate quantification of porosity, nanopore tortuosity, and electrical connectivity at the single-nanoparticle (NP) level for NPs synthesized by nanodroplet-mediated electrodeposition. Focused ion beam nanoslice tomography was used to slice NPs with ca. 10 nm slice resolution followed by imaging using scanning electron microscopy (SEM), allowing measurement of these parameters on NPs not amenable to transmission electron microscopy. Slices were reconstructed in three dimensions and revealed pores with an average size of 3 ± 2 nm and relative nanopore tortuosity of 46.8 ± 24.5. We also demonstrate a new technique to evaluate electrical connectivity at the single-NP level by taking advantage of material-selective electrodeposition. The rate of Cu electrodeposition differs significantly on Pt compared to carbon, implying Cu can be selectively electrodeposited onto Pt NPs adsorbed onto a carbon support. Following the Cu electrodeposition step, NP connectivity was determined by the presence of Cu on Pt...

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.

Traditional studies of enzymatic activity rely on the combined kinetics of millions of enzyme molecules to produce a product, an experimental approach that may wash out heterogeneities that exist between individual enzymes. Evaluating these properties on an enzyme-by-enzyme basis represents an unambiguous means of elucidating heterogeneities; however, the quantification of enzymatic activity at the single-enzyme level is fundamentally limited by the maximum catalytic rate, kcat, inherent to a given enzyme. For electrochemical methods measuring current, single enzymes must turn over greater than 107 molecules per second to produce a measurable signal on the order of 10−12 A. Enzymes with this capability are extremely rare in nature, with typical kcat values for biologically relevant enzymes falling between 1 and 10 000 s−1. Thus, clever amplification strategies are necessary to electrochemically detect the vast majority of enzymes. This review details the progress toward the electroanalytical detection and evaluation of single enzyme kinetics largely focused on the nanoimpact method, a chronoamperometric detection strategy that monitors the change in the current-time profile associated with stochastic collisions of freely diffusing entities (e.g., enzymes) onto a microelectrode or nanoelectrode surface. We discuss the experimental setups and methods developed in the last decade toward the quantification of single molecule enzymatic rates. Special emphasis is given to the limitations of measurement science in the observation of single enzyme activity and feasible methods of signal amplification with reasonable bandwidth.

Single-entity electrochemistry has emerged as a powerful tool to study the adsorption behavior of single nanoscale entities one-at-a-time on an ultramicroelectrode surface. Classical single-entity collision studies have focused on the behavior of spherical nanoparticles or entities where the orientation of the colliding entity does not impact the electrochemical response. Here, we report a detailed study of the collision of asymmetric single graphene nanoplatelets onto ultramicroelectrodes. The collision of conductive graphene nanoplatelets on biased ultramicroelectrode surfaces can be observed in an amperometric i-t trace, revealing a variety of current transients (both positive and negative steps). To elucidate the dynamics of nanoplatelet adsorption processes and probe response heterogeneity, we correlated the collision events with optical microscopy. We show that positive steps are due to nanoplatelets coming into contact with the ultramicroelectrode, making an electrical connection, and adsorbing partly on the glass surrounding the ultramicroelectrode. Negative steps occur when nanoplatelets adsorb onto the glass without an electrical connection, effectively blocking flux of ferrocenemethanol to the ultramicroelectrode surface. These measurements allow rigorous quantification of current transients and detailed insights into the adsorption dynamics of asymmetric objects at the nanoscale.

International audience; Nanoparticles interact with a variety of interfaces, from cell walls for medicinal applications to conductive interfaces for energy storage and conversion applications. Unfortunately, quantifying dynamic changes of nanoparticles near interfaces is difficult. While optical techniques exist to study nanoparticle dynamics, motions smaller than the diffraction limit are difficult to quantify. Single-entity electrochemistry has high sensitivity, but the technique suffers from ambiguity in the entity’s size, morphology, and collision location. Here, we combine optical microscopy, single-entity electrochemistry, and numerical simulations to elucidate the dynamic motion of graphene nanoplatelets at a gold ultramicroelectrode (radius ∼5 μm). The approach of conductive graphene nanoplatelets, suspended in 10 μM NaOH, to an ultramicroelectrode surface was tracked optically during the continuous oxidation of ferrocenemethanol. Optical microscopy confirmed the nanoplatelet size, morphology, and collision location on the ultramicroelectrode. Nanoplatelets collided on the ultramicroelectrode at an angle, θ, enhancing the electroactive area, resulting in a sharp increase in current. After the collision, the nanoplatelets reoriented to lay flat on the electrode surface, which manifested as a return to the baseline current in the amperometric current–time response. Through correlated finite element simulations, we extracted single nanoplatelet angular velocities on the order of 0.5–2°/ms. These results are a necessary step forward in understanding nanoparticle dynamics at the nanoscale