Hypochlorous acid (HOCl) is a strong oxidizing agent that damages cells by interacting with lipids, nucleic acids, sulfur-containing amino acids, and membrane components. It is an endogenous substance produced by the immune system to protect mammals from pathogens. Previously, we developed an HOCl-generating electrochemical catheter (e-catheter) and demonstrated its ability to prevent central line-associated bloodstream infections. The e-catheter is an electrochemical system consisting of two parts - an e-hub and a tube. Working, counter, and reference electrodes are placed in the e-hub, which contains 0.9% NaCl as an electrolyte. Although a prototype of this device has shown activity against pathogens, it is helpful to understand the factors influencing associated electrochemical/chemical processes to optimize design and efficacy. A mathematical model could predict factors influencing HOCl generation and distribution in the catheter and could aid in optimizing these devices. Here, we developed an Electrochemical Hypochlorous Acid Production (EHAP) model to predict factors influencing electrochemical generation and distribution of HOCl in e-catheters, including polarization time, diffusion of HOCl into the e-catheter, operational voltage, working electrode length, and surface area.

Lead (Pb) has long been acknowledged as a systemic toxicant, with pronounced health impacts observed even at low exposure levels, particularly in children. Adverse effects include diminished cognitive function, altered behavior, and developmental delays. Consequently, it is imperative to conduct regular monitoring of Blood Lead Levels (BLLs). In this work, we report on an electrochemical sensor based on screen-printed carbon electrode (SPCE) coated with Nafion and mesoporous carbon (MC). The sensor system uses simple sample preparation (acidification and dilution of whole blood), minimal sample volume (a few blood drops, 200 l), and swift time-to-results (1 h). A limit of quantitation (LOQ) of 0.3 g dL Pb was achieved in whole blood. To demonstrate the practical utility of our sensor system, we evaluated its performance in the analysis of blood samples collected from children (n = 25). Comparative analysis with the laboratory-based gold standard method of inductively coupled plasma mass spectrometry (ICP-MS) demonstrated approximately 77% accuracy and 94% precision. We anticipate that our approach will serve as a valuable tool for more frequent BLL monitoring, particularly in communities where access to laboratory testing is impractical or expensive.

Thermoplastic carbon electrodes (TPEs) are an alternative form of carbon composite electrodes that have shown excellent electrochemical performance with applications in biological sensing. However, little has been done to apply TPEs to environmental sensing, specifically heavy metal analysis. The work here focuses on lead analysis and based on their electrochemical properties, TPEs are expected to outperform other carbon composite materials; however, despite testing multiple formulations, TPEs showed inferior performance. Detailed electrode characterization was conducted to examine the cause for poor lead sensing behavior. X-Ray photoelectron spectroscopy (XPS) was used to analyze the surface functional groups, indicating that acidic and alkaline functional groups impact lead electrodeposition. Further, scanning electron microscopy (SEM) and electrochemical characterization demonstrated that both the binder and graphite can influence the surface morphology, electroactive area, and electron kinetics.

In this work, we demonstrate accurate and precise measurement of manganese (Mn) concentration in human whole blood with indium tin oxide (ITO) electrode using square wave stripping voltammetry. While an essential trace metal for human health, elevated levels of Mn due to environmental or occupational exposure have been associated with severe neuromotor dysfunction characterized by parkinsonism and cognitive dysfunction making the monitoring of Mn in whole blood necessary. Pediatric populations are particularly susceptible to Mn given their developing brain and potential long-term impacts on neurodevelopment. The current gold standard for whole blood Mn measurements is by ICP-MS, which is costly and time consuming. The electrochemical detection with ITO working electrode in this work showed a limit of detection of 0.5 μg l and a linear range of 5 to 500 μg l, which encompasses the physiological Mn levels in human whole blood (5-18 μg l). Our results of Mn measurement in whole blood show an average precision of 96.5% and an average accuracy of 90.3% compared to ICP-MS for both the normal range (5-18 μg l) and the elevated levels (>36 μg l) that require medical intervention. These results demonstrate the feasibility of Mn measurements in human blood with electrochemical sensors.

The catalytic reduction of ethyl chloroacetate (ECA) by hydroxocobalamin (HOCbl) in dimethylformamide was studied electrochemically and spectroelectrochemically to identify initial steps in the reaction between the electrogenerated Co(I) center of cobalamin (cob(I)alamin) and ECA. Cyclic voltammograms of HOCbl in the presence of ECA show a small increase in current related to reduction of Co(II) to Co(I), and a new peak at more negative potentials related to reduction of an ethyl carboxymethyl-Cbl intermediate. The oxidation state of HOCbl during catalysis was monitored by means of spectroelectrochemical controlled-potential bulk electrolysis. Addition of ECA to electrogenerated cob(I)alamin initially generates the Co(II) form (cob(II)alamin) followed by a gradual formation of an ethyl carboxymethyl-Cbl intermediate. Controlled-potential bulk electrolysis was performed to identify products formed from catalytic reduction of ECA by electrogenerated cob(I)alamin and quantify the number of electrons transferred per molecule of ECA. Product distributions and coulometric results, together with the results of voltammograms and spectroelectrochemical controlled-potential bulk electrolysis, were interpreted to propose a reaction mechanism.

DNAs have been used as probes for nanopore sensing of noncharged biomacromolecules due to its negative phosphate backbone. Inspired by this, we explored the potential of diblock synthetic polyelectrolytes as more flexible and inexpensive nanopore sensing probes by investigating translocation behaviors of PEO-b-PSS and PEO-b-PVBTMA through commonly used alpha-hemolysin (α-HL) and porin A (MspA) nanopores. Translocation recordings in different configurations of pore orientation and testing voltage indicated efficient PEO-b-PSS translocations through α-HL and PEO-b-PVBTMA translocations through MspA. This work provides insight into synthetic polyelectrolyte-based probes to expand probe selection and flexibility for nanopore sensing.

Selective serotonin reuptake inhibitors (SSRIs) have been used for decades to treat disorders linked to serotonin dysregulation in the brain. Moreover, SSRIs are often used in studies aimed at measuring serotonin with fast-scan cyclic voltammetry (FSCV) in living tissues. Here, we show that three different SSRIs - fluoxetine, escitalopram, and sertraline - significantly diminish the faradaic oxidation current of serotonin when employing the commonly used Jackson waveform. Coating carbon-fiber microelectrodes (CFMs) with Nafion resulted in further degradation of peak current, increased response times, and decreased background charging currents compared to bare CFMs. To decrease fouling, we employed a recently published extended serotonin waveform, which scans to a maximum positive potential of +1.3 V, rather than +1.0 V used in the Jackson waveform. Use of this waveform with bare CFMs alleviated the decrease in faradaic current, indicating decreased electrode fouling. Collectively, our results suggest that fouling considerations are important when designing FSCV experiments that employ SSRIs and that they can be overcome by using the appropriate waveform.

We demonstrate the density and shape of platinum nanoparticles (PtNP) on carbon-fiber microelectrodes with fast-scan cyclic voltammetry (FSCV) directly impacts detection of adenosine. Previously, we showed that metal nanoparticle-modified carbon significantly improves adenine-based purine detection; however, how the size and shape of the particles impact electrochemical detection was not investigated. Electrochemical investigations of how the surface topology and morphology impacts detection is necessary for designing ultrasensitive electrodes and for expanding fundamental knowledge of electrode-analyte interactions. To change the density and shape of the PtNP's on the surface, we varied the concentration of KPtCl and electrodeposition time. We show that increasing the concentration of KPtCl increases the density of PtNP's while increasing the electrodeposition time impacts both the density and size. These changes manipulate the adsorption behavior which impacts sensitivity. Based on these results, an optimal electrodeposition procedure was determined to be 1.0 mg/mL of KPtCl deposited for 45 s and this results in an average increase in adenosine detection by 3.5 ±0.3-fold. Interestingly, increasing the size and density of PtNPs negatively impacts dopamine detection. Overall, this work provides fundamental insights into the differences between adenosine and dopamine interaction at electrode surfaces.

Therapeutic monitoring of neurotransmitters (NTs) and psychiatric medications is essential for the diagnosis and treatment of mental illness. However, in-vivo monitoring of NTs in humans as well as continuous physiological monitoring of psychiatrics have yet to be realized. In pursuit of this goal, there has been a plethora of work to develop electrochemical sensors for both in-vivo NT monitoring as well as in-vitro detection of psychiatric medications. We review these sensors here while discussing next steps needed to achieve concurrent, continuous physiological monitoring of NTs and psychiatric medications as part of a closed-loop feedback system that guides medication administration.

Carbon nanotube yarn microelectrodes (CNTYMEs) have micron-scale surface crevices that momentarily trap molecules. CNTYMEs improve selectivity among cationic catecholamines because secondary reactions are enhanced, but no anions have been studied. Here, we compared fast-scan cyclic voltammetry (FSCV) of dopamine and anionic interferents 3,4 dihydroxyphenylacetic acid (DOPAC) and L-ascorbic acid (AA) at CNTYMEs and carbon fiber microelectrodes (CFMEs). At CFMEs, dopamine current decreases with increasing FSCV repetition frequency at pH 7.4, whereas DOPAC and AA have increasing currents with increasing frequency, because of less repulsion at the negative holding potential. Both DOPAC and AA have side reactions after being oxidized, which are enhanced by trapping. At pH 4, the current increases for DOPAC and AA because they are not repelled. In addition, AA has a different oxidation pathway at pH 4, and an extra peak in the CV is enhanced by trapping effects at CNTYMEs. At pH 8.5, co-detection of dopamine in the presence of DOPAC and AA is enhanced at 100 Hz frequency because of differences in secondary peaks. Thus, the trapping effects at CNTYMEs affects anions differently than cations and secondary peaks can be used to identify dopamine in mixture of AA and DOPAC with FSCV.

Electrochemical sensors that utilize enzymes are a sensitive, inexpensive means of detecting biologically relevant analytes. These sensors are categorized based on their construction and method of signal transport. Type I sensors consist of a crosslinked enzyme on an electrode surface and are potentially subject to interference from byproducts and other biological analytes. However, type II sensors help alleviate this problem with the addition of a redox polymer layer that assists in signal transduction, thus minimizing interferences. An osmium-loaded poly(vinylimidazole) polymer (Os-PVI) is commonly used with successful results, and when combined with an enzyme yields a type II sensor. Our initial attempts at the synthesis of this polymer resulted in an unexpected osmium precursor, which had fluorescent and redox properties that did not match with the desired Os-PVI polymer. Careful exclusion of oxygen during the Os complex precursor synthesis was necessary to avoid this unexpected oxygen containing Os-precursor, which had been seen previously in mass spectrometry studies. All precursors and osmium polymers were characterized with H NMR, fluorescence, mass spectrometry, and cyclic voltammetry to provide a better understanding of these compounds and assist in the building of new sensors.

Carbon fiber microelectrodes (CFMEs) have been used to detect neurotransmitters and other biomolecules using fast-scan cyclic voltammetry (FSCV) for the past few decades. This technique measures neurotransmitters such as dopamine and, more recently, physiologically relevant neuropeptides. Oxytocin, a pleiotropic peptide hormone, is physiologically important for adaptation, development, reproduction, and social behavior. This neuropeptide functions as a stress-coping molecule, an anti-inflammatory agent, and serves as an antioxidant with protective effects especially during adversity or trauma. Here, we measure tyrosine using the Modified Sawhorse Waveform (MSW), enabling enhanced electrode sensitivity for the amino acid and oxytocin peptide. Applying the MSW, decreased surface fouling and enabled codetection with other monoamines. As oxytocin contains tyrosine, the MSW was also used to detect oxytocin. The sensitivity of oxytocin detection was found to be 3.99 ± 0.49 nA/μM, (n=5). Additionally, we demonstrate that applying the MSW on CFMEs allows for real time measurements of exogenously applied oxytocin on rat brain slices. These studies may serve as novel assays for oxytocin detection in a fast, sub-second timescale with possible implications for measurements and further understanding of the physiological role of oxytocin.

In efforts to increase the energy density of lithium-ion batteries, researchers have attempted to both increase the thickness of battery electrodes and increase the relative fractions of active material. One system that has both of these attributes are sintered thick electrodes comprised of only active material. Such electrodes have high areal capacities, however, detailed understanding is needed of their transport properties, both electronic and ionic, to better quantify their limitations to cycling at higher current densities. In this report, efforts to improve models of the electrochemical cycling of sintered electrodes are described, in particular incorporation of matrix electronic conductivity which is dependent on the extent of lithiation of the active material and accounting for initial gradients in lithiation of active material in the electrode that develop as a consequence of transport limitations during charging cycles. Adding in these additional considerations to a model of sintered electrode discharge resulted in improved matching of experimental cell measurements.

Catalysis of Cu deposition from a near-neutral Cu complexed electrolyte is examined using Bi, Pb and Tl additives that were selected based on their known ability to accelerate Au deposition in near neutral pH gold sulfite electrolytes. Where appropriate, the ability of these electrolytes to yield superconformal filling of recessed features is also briefly examined. Voltammetry reveals strong acceleration of Cu deposition by Bi additions while indication of superconformal filling accompanied by unusual microstructural transitions are evident in cross-sectioned specimens examined by scanning electron microscopy. Results are discussed in the context of behaviors observed for the same heavy metal additives in gold sulfite electrolytes.

The mechanism underlying -stimulated bottom-up Au filling and self-passivation in trenches and vias in slightly alkaline ( ) + electrolytes is explored. The impacts of electrolyte components ( ), and and potential-dependent kinetic factors on the rate of Au electrodeposition are quantified experimentally. Derived parameters are applied within the surfactant conservation Curvature Enhanced Accelerator Coverage model to simulate the filling of high aspect ratio trenches. It is observed that Bi adsorption accelerates the Au deposition rate with a non-linear dependence occurring around a critical coverage. Further, the impact of electrolyte composition is such that gradients of and derived from reduction of during deposition accentuate deposition farther from the feature opening. These factors and surface area reduction at the bottoms of filling features localize active deposition to feature bottoms. Ultimately, weakening of the concentration gradients and associated kinetics as bottom-up feature filling progresses reduces the Bi coverage on the growth front below the critical value and bottom-up growth terminates. Good agreement is observed with key experimental features including the incubation period of conformal deposition, transition to bottom-up growth, subsequent bottom-up filling and finally self-passivation as the growth front nears the field.

The microstructure and crystallographic texture of copper electrodeposits in millimeter scale through silicon vias are characterized using electron backscatter diffraction. The deposits obtained from additive-containing CuSO-HSO electrolytes are characteristic of the superconformal deposition process, with growth textures and columnar grains consistent with previous findings in smaller TSV. The microstructure, like the filling evolution it records, changes substantially with chloride concentration for the concentrations of polymer suppressor used. With chloride concentrations of 80 μmol·L and less, columnar grains of Cu capture the linear motion of the local growth front during filling with a strong <110> orientation along the elongated grain axes typical of deposition in chloride-containing Cu electrolytes. In the mid- and upper- via locations these columnar grains are angled upward from the sidewalls toward the center of the v-shaped growth front. In a limited region adjacent to the via bottom they extend vertically from the bottom surface. With millimolar chloride concentration, deposition also exhibits columnar grains with preferred <110> growth orientation in the lower region of the via and adjacent to the sidewalls. However, separation of the central deposit from the sidewalls results in a convex geometry of the growth front and spatially varying texture in most of the deposit.

This work extends an extreme variant of superconformal Au electrodeposition to deeper device architectures while exploring factors that constrain its function and the robustness of void-free processing. The unconventional bottom-up process is used to fill diffraction gratings with trenches 94 μm deep and 305 μm deep, with aspect ratios (height/width) of just below 20 and 15, respectively, in near-neutral 0.16 mol·L NaAu(SO) + 0.64 mol·L NaSO electrolyte containing 50 μmol·L Bi. Although the aspect ratios are modest compared to previously demonstrated void-free filling beyond AR = 60, the deepest trenches filled exceed those in previous work by 100 μm - a nearly 50 % increase in depth. Processes that substantially accelerate the start of bottom-up deposition demonstrate a linkage between transport and void-free filling. Final profiles are highly uniform across 65 mm square gratings because of self-passivation inherent in the process. Electron microscopy and electron backscatter diffraction confirm the fully dense Au and void-free filling suggested by the electrochemical measurements. X-ray transmission "fringe visibility" average more than 80 % at 50 kV X-ray tube voltage across the deeper gratings and 70 % at 40 kV across the shallower gratings, also consistent with uniformly dense, void-free fill across the gratings.

The influence of polymer overlayers on the catalytic activity of Ag for electrochemical CO reduction to CO is explored. Polystyrene and poly(4-vinylpyridine) films of varying thicknesses are applied as catalysis-directing overlayers atop Ag electrodes. For polystyrene, substantial suppression of CO reduction activity is observed while the hydrogen evolution reaction (HER) increases. The addition of a nitrogen heteroatom into the phenyl groups of polystyrene (e.g., a pyridine ring) results in an increase in the conversion of CO to CO and suppression of HER. Block copolymer variants containing both phenyl and pyridyl functionalities exhibit similar activity for CO evolution but appear to suppress HER further than the polymer layer containing only pyridine groups. The size of the blocks for the copolymer influences the catalytic output of the Ag electrode, suggesting that the hierarchical structure that forms in the block copolymer layer plays a role in catalytic activity at the electrode surface. Analysis of the polymer overlayers suggests that polystyrene significantly inhibits all ion transport to the metal electrode, while poly(4-vinylpyridine) enables CO transport while modifying the electronics of the Ag active site. Therefore, the engineered application of polymer overlayers, especially those containing heteroatoms, enables new avenues of electrochemical CO reduction to be explored.

The persistent achievements of ionic liquids in various fields, including medicine and energy necessitate the efficient development of novel functional ionic liquids that exhibit favorable characteristics, alongside the development of practical and scalable synthetic methodologies. Ionic liquids are fundamentally understood as materials in which structure begets function, and the function and applicability of ILs is of utmost concern. It was recently reported that "full fluorosulfonyl" electrolyte is compatible with both the Li metal anode and the metal-oxide cathode that is crucial for the development of high-voltage rechargeable lithium-metal batteries. Inspired by these results, for the first time, we reported the synthesis of a series of ionic liquids with a sulfonyl fluoride motif using an highly effective and modular fluorosulfonylethylation procedure. Herein, we present a detailed analysis of novel sulfonyl fluoride-based ionic liquids paired with the hexafluorophosphate anion. We employed a combination of computational modeling and X-ray crystallographic studies to gain an in-depth understanding of their structure-property correlations.

Single nanopores in silicon nitride membranes are asymmetrically modified with Nafion and investigated with scanning ion conductance microscopy, where Nafion alters local ion concentrations at the nanopore. Effects of applied transmembrane potentials on local ion concentrations are examined, with the Nafion film providing a reservoir of cations in close proximity to the nanopore. Fluidic diodes based on ion concentration polarization are observed in the current-voltage response of the nanopore and in approach curves of SICM nanopipette in the vicinity of the nanopore. Experimental results are supported with finite element method simulations that detail ion depletion and enrichment of the nanopore/Nafion/nanopipette environment.

Seven acetylacetonate (acac) metal complexes ranging from early transition metals to post-transition metals were examined by cyclic voltammetry in acetonitrile (MeCN), dichloromethane (DCM), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and dimethylformamide (DMF). The electronic potential of any observed redox events is reported along with an analysis of the reversibility of those events across a range of scan rates. Group 8 compounds Fe(acac) Ru(acac) showed at least quasi-reversible reductions across all solvents while Ru(acac) also featured a reversible oxidation. The early and post-transition compounds VO(acac), Ga(acac) and In(acac) exhibited irreversible reductions, while TiO(acac) showed no redox activity within the examined potential ranges. Mn(acac) featured an oxidation that showed solvent-dependent reversibility, and a reduction that was irreversible in all examined solvents. DFT calculations indicated minimal solvent effects on the HOMO-LUMO gap for the majority of compounds, but a significant effect was observed for Ru(acac). This study serves as a valuable initial step for further examination of acetylacetonate metal complexes for applications as electrochemical internal standards, nanoparticle precursors, and electrocatalysts.