Cory A. Rusinek

Electrospun carbon nanofiber modified electrodes for stripping voltammetry.

Electrospun polyacrylonitrile (PAN) based carbon nanofibers (CNFs) have attracted intense attention due to their easy processing, high carbon yield, and robust mechanical properties. In this work, a CNF modified glassy carbon (GC) electrode that was coated with Nafion polymer was evaluated as a new electrode material for the simultaneous determination of trace levels of heavy metal ions by anodic stripping voltammetry (ASV). Pb(2+) and Cd(2+) were used as a representative system for this initial study. Well-defined stripping voltammograms were obtained when Pb(2+) and Cd(2+) were determined individually and then simultaneously in a mixture. Compared to a bare GC electrode, the CNF/Nafion modified GC (CNF/Nafion/GC) electrode improved the sensitivity for lead detection by 8-fold. The interface properties of the CNF/Nafion/GC were characterized by electrochemical impedance spectroscopy (EIS), which showed the importance of the ratio of CNF/Nafion on electrode performance. Under optimized conditions, the detection limits are 0.9 and 1.5 nM for Pb(2+) and Cd(2+), respectively.

Cloud Point Extraction for Electroanalysis: Anodic Stripping Voltammetry of Cadmium

Cloud point extraction (CPE) is a well-established technique for the preconcentration of hydrophobic species from water without the use of organic solvents. Subsequent analysis is then typically performed via atomic absorption spectroscopy (AAS), UV-vis spectroscopy, or high performance liquid chromatography (HPLC). However, the suitability of CPE for electroanalytical methods such as stripping voltammetry has not been reported. We demonstrate the use of CPE for electroanalysis using the determination of cadmium (Cd(2+)) by anodic stripping voltammetry (ASV). Rather than using the chelating agents which are commonly used in CPE to form a hydrophobic, extractable metal complex, we used iodide and sulfuric acid to neutralize the charge on Cd(2+) to form an extractable ion pair. This offers good selectivity for Cd(2+) as no interferences were observed from other heavy metal ions. Triton X-114 was chosen as the surfactant for the extraction because its cloud point temperature is near room temperature (22-25 °C). Bare glassy carbon (GC), bismuth-coated glassy carbon (Bi-GC), and mercury-coated glassy carbon (Hg-GC) electrodes were compared for the CPE-ASV. A detection limit for Cd(2+) of 1.7 nM (0.2 ppb) was obtained with the Hg-GC electrode. ASV with CPE gave a 20x decrease (4.0 ppb) in the detection limit compared to ASV without CPE. The suitability of this procedure for the analysis of tap and river water samples was demonstrated. This simple, versatile, environmentally friendly, and cost-effective extraction method is potentially applicable to a wide variety of transition metals and organic compounds that are amenable to detection by electroanalytical methods.

Determination of Lead with a Copper-Based Electrochemical Sensor

This work demonstrates determination of lead (Pb) in surface water samples using a low-cost copper (Cu)-based electrochemical sensor. Heavy metals require careful monitoring due to their toxicity, yet current methods are too complex or bulky for point-of-care (POC) use. Electrochemistry offers a convenient alternative for metal determination, but the traditional electrodes, such as carbon or gold/platinum, are costly and difficult to microfabricate. Our copper-based sensor features a low-cost electrode material-copper-that offers simple fabrication and competitive performance in electrochemical detection. For anodic stripping voltammetry (ASV) of Pb, our sensor shows 21 nM (4.4 ppb) limit of detection, resistance to interfering metals such as cadmium (Cd) and zinc (Zn), and stable response in natural water samples with minimum sample pretreatment. These results suggest this electrochemical sensor is suitable for environmental and potentially biological applications, where accurate and rapid, yet inexpensive, on-site monitoring is necessary.

Bare and Polymer-Coated Indium Tin Oxide as Working Electrodes for Manganese Cathodic Stripping Voltammetry

Though an essential metal in the body, manganese (Mn) has a number of health implications when found in excess that are magnified by chronic exposure. These health complications include neurotoxicity, memory loss, infertility in males, and development of a neurologic psychiatric disorder, manganism. Thus, trace detection in environmental samples is increasingly important. Few electrode materials are able to reach the negative reductive potential of Mn required for anodic stripping voltammetry (ASV), so cathodic stripping voltammetry (CSV) has been shown to be a viable alternative. We demonstrate Mn CSV using an indium tin oxide (ITO) working electrode both bare and coated with a sulfonated charge selective polymer film, polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene-sulfonate (SSEBS). ITO itself proved to be an excellent electrode material for Mn CSV, achieving a calculated detection limit of 5 nM (0.3 ppb) with a deposition time of 3 min. Coating the ITO with the SSEBS polymer was found to increase the sensitivity and lower the detection limit to 1 nM (0.06 ppb). This polymer modified electrode offers excellent selectivity for Mn as no interferences were observed from other metal ions tested (Zn(2+), Cd(2+), Pb(2+), In(3+), Sb(3+), Al(3+), Ba(2+), Co(2+), Cu(2+), Ni(3+), Bi(3+), and Sn(2+)) except Fe(2+), which was found to interfere with the analytical signal for Mn(2+) at a ratio 20:1 (Fe(2+)/Mn(2+)). The applicability of this procedure to the analysis of tap, river, and pond water samples was demonstrated. This simple, sensitive analytical method using ITO and SSEBS-ITO could be applied to a number of electroactive transition metals detectable by CSV.

Analysis of Ag(I) Biocide in Water Samples Using Anodic Stripping Voltammetry with a Boron-Doped Diamond Disk Electrode

The electroanalytical performance of a new commercial boron-doped diamond disk and a traditional nanocrystalline thin-film electrode were compared for the anodic stripping voltammetric determination of Ag(I). The diamond disk electrode is more flexible than the planar film as the former is compatible with most electrochemical cell designs including those incorporating magnetic stirring. Additionally, mechanical polishing and surface cleaning are simpler to execute. Differential pulse anodic stripping voltammetry (DPASV) was used to detect Ag(I) in standard solutions after optimization of the deposition potential, deposition time and scan rate. The optimized conditions were used to determine the concentration of Ag(I) in a NASA simulated potable water sample and a NIST standard reference solution. The electrochemical results were validated by ICP-OES measurements of the same solutions. The detection figures of merit for the disk electrode were as good or superior to those for the thin-film electrode. Detection limits were ≤5 μg L-1 (S/N = 3) for a 120 s deposition period, and response variabilities were <5% RSD. The polished disk electrode presented a more limited linear dynamic range presumably because of the reduced surface area available for metal phase formation. The concentrations of Ag(I) in the two water samples, as determined by DPASV, were in good agreement with the concentrations determined by ICP-OES.

Isatin Detection Using a Boron-Doped Diamond 3-in-1 Sensing Platform

Boron-doped diamond (BDD) is a promising electrochemical tool that exhibits excellent chemical sensitivity and stability. These intrinsic advantages coupled with the materials vast microfabrication flexibility make BDD an attractive sensing device. In this study, two different 3-in-1 BDD electrode sensors were fabricated, characterized, and investigated for their capability to detect isatin, an anxiogenic indole that possesses anticonvulsant activity. Each device was comprised of a working, reference, and auxiliary electrode, all made of BDD. Two different working electrode geometries were studied, a 2 mm diameter macroelectrode (MAC) and a microelectrode array (MEA). The BDD quasi-reference electrode was studied by measuring its potential against a traditional Ag/AgCl reference electrode. While the potential shifted as a function of solution pH, a miniscule potential drift was observed when holding the solution pH constant. Specifically, the BDD quasi-reference electrode had a potential of -0.2 V (vs Ag/AgCl) in a pH 7 solution, and this remained stable for a 30-h time period. For the detection of isatin, solutions were analyzed using both sensors in pH 7.4 phosphate buffered saline (PBS). Using the MEA sensor, the limit of detection (LOD, (3σ)/m) for isatin was found to be 0.04 μM; an increase to 0.22 μM was observed with the MAC sensor. These results were compared to those obtained from UV-vis spectrophotometry, where a 0.57 μM LOD was observed. The feasibility for use in a complex sample matrix was also examined by completing measurements in urine simulant. The results presented herein indicate that both 3-in-1 BDD sensors are applicable at low limits of detection with potential application as an electrochemical detector for chromatographic methods.