Adam Bange

Disposable Copper-Based Electrochemical Sensor for Anodic Stripping Voltammetry

In this work, we report the first copper-based point-of-care sensor for electrochemical measurements demonstrated by zinc determination in blood serum. Heavy metals require careful monitoring, yet current methods are too complex for a point-of-care system. Electrochemistry offers a simple approach to metal detection on the microscale, but traditional carbon, gold (Au), or platinum (Pt) electrodes are difficult or expensive to microfabricate, preventing widespread use. Our sensor features a new low-cost electrode material, copper, which offers simple fabrication and compatibility with microfabrication and PCB processing, while maintaining competitive performance in electrochemical detection. Anodic stripping voltammetry of zinc using our new copper-based sensors exhibited a 140 nM (9.0 ppb) limit of detection (calculated) and sensitivity greater than 1 μA/μM in the acetate buffer. The sensor was also able to determine zinc in a bovine serum extract, and the results were verified with independent sensor measurements. These results demonstrate the advantageous qualities of this lab-on-a-chip electrochemical sensor for clinical applications, which include a small sample volume (μL scale), reduced cost, short response time, and high accuracy at low concentrations of analyte.

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.

Manganese Detection with a Metal Catalyst Free Carbon Nanotube Electrode: Anodic versus Cathodic Stripping Voltammetry

Anodic stripping voltammetry (ASV) and cathodic stripping voltammetry (CSV) were used to determine Mn concentration using metal catalyst free carbon nanotube (MCFCNT) electrodes and square wave stripping voltammetry (SWSV). The MCFCNTs are synthesized using a Carbo Thermal Carbide Conversion method which results in a material that does not contain residual transition metals. Detection limits of 120 nM and 93 nM were achieved for ASV and CSV, respectively, with a deposition time of 60 s. CSV was found to be better than ASV in Mn detection in many aspects, such as limit of detection and sensitivity. The CSV method was used in pond water matrix addition measurements.

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.

Copper-based electrochemical sensor with palladium electrode for cathodic stripping voltammetry of manganese.

In this work, we report on the development of a palladium-based, microfabricated point-of-care electrochemical sensor for the determination of manganese using square wave cathodic stripping voltammetry. Heavy metals require careful monitoring, yet current methods are too complex for a point-of-care system. Voltammetry offers an attractive approach to metal detection on the microscale, but traditional carbon, gold, or platinum electrodes are difficult or expensive to microfabricate, preventing widespread use. Our sensor uses palladium working and auxiliary electrodes and integrates them with a copper-based reference electrode for simple fabrication and compatibility with microfabrication and printed circuit board processing, while maintaining competitive performance in electrochemical detection. Copper electrodes were prepared on glass substrate using a combination of microfabrication procedures followed by electrodeposition of palladium. The disposable sensor system was formed by bonding a poly(dimethylsiloxane) (PDMS) well to the glass substrate. Cathodic stripping voltammetry of manganese using our new disposable palladium-based sensors exhibited 334 nM (18.3 ppb) limit of detection in borate buffer. The sensor was used to demonstrate manganese determination in natural water samples from a pond in Burnet Woods, located in Cincinnati, OH, and the Ohio River.

Adsorption of fluorescently labeled microbeads on PDMS surfaces

Fluorescently labeled beads may be utilized in transparent microfluidic devices to facilitate a variety of immunoassay based chemical measurements. We investigate the ability to visualize, quantitate, and reduce undesirable adsorption of beads within a polydimethylsiloxane (PDMS) microchannel device. These methods are prerequisites to the design of practical bead-based microfluidic sensing devices. The PDMS microchannels were shown to be transparent enough to make accurate quantitative optical measurements, although significant adsorption was observed. Epifluorescence microscopy was employed in an attempt to quantitatively evaluate microbead adsorption to PDMS microchannel walls and bulk surfaces after different agitation, solution, and surface treatments. This microscopy method provides reproducible imaging of individual beads and allows for characterization of adsorption to PDMS microchannel walls. Solution composition seemed to play a more important role in the ability to reduce the number of adsorbed beads to the PDMS surface than agitation. The most significant reduction in bead adsorption was seen in surface treatment. The most effective surface treatment examined in this study was Teflon AF.

A nanotube composite microelectrode for monitoring dopamine levels using cyclic voltammetry and differential pulse voltammetry

Needle-type nanotube composite microelectrodes were fabricated by injecting a carbon nanotube epoxy solution into pulled-glass tubes. Electrochemical impedance spectroscopy was used to study the complex impedance of the electrode and showed that the electron transfer resistance of the electrode decreases with an increase in the percentage of nanotubes in the epoxy. Cyclic voltammetry was performed under reducing conditions in 6.0mM K3Fe(CN)6 to examine the surface properties of the microelectrodes. The results showed a steady-state response up to 0.5 V/s attributable to radial diffusion with a high steady-state current density. Cyclic voltammetry and differential pulse voltammetry were then used to detect dopamine. The results showed a linear response with a sensitivity of 100nA/mM. Based on the cyclic voltammetry and differential pulse voltammetry results, needle-type nanotube composite microelectrodes are promising sensors for detecting neurotransmitters.

Carbon nanotube array smart materials

Highly aligned multi-wall carbon nanotube arrays up to 4 mm tall were synthesized on Si wafers using a chemical vapor deposition process with water delivery. Based on the long nanotube arrays, several prototype smart materials were developed including a biosensor, electrochemical actuator, and nanotube probes. The biosensor was formed by casting epoxy into a nanotube array and polishing the ends of the nanotubes. This electrode produced a near ideal sigmoidal cyclic voltammogram. Nanotube electrodes were then used to form a label-free immunosensor based on electrochemical impedance spectroscopy. The nanotube array immunosensor has good sensitivity, but decreasing the array size and improving the biofunctionalization is expected to dramatically increase the reproducibility and sensitivity. The electrochemical actuator was formed by bonding an electrode to a 1mm square by 4 mm long as-grown nanotube array post. The nanotube array actuator operated up to 10 Hz in a 2 M NaCl solution. With a driving voltage of 2 volts, the actuator produced 0.15% strain. Finally, nanotube bundles are being welded to tungsten tips and put inside glass needles for use as probes for biosensors and electrophysiology applications. All the smart materials applications discussed are recent, and further development is expected to yield improved performance and commodity level practical devices.

Lab-on-a-chip sensor for measuring Zn by stripping voltammetry

This work reports on continuing development of a lab-on-a-chip sensor for electrochemical detection of heavy metal zinc in blood serum. The sensor consists of a three electrode system, including an environmentally-friendly bismuth working electrode, a Ag/AgCl reference electrode, and a gold auxiliary electrode. By optimizing the electrodeposition of bismuth film, better control of fabrication steps and improving interface between the sensor and potentiostat, repeatability and sensitivity of the lab-on-a-chip sensor has been improved. Through optimization of electrolyte and stripping voltammetry parameters, limits of detection were greatly improved. The optimized sensor was able to measure zinc in in the physiological range of 65-95 μg/dL. Ultimately, with further development and integrated sample preparation sensor system will permit rapid (min) measurements of zinc from a sub-mL sample (a few drops of blood) for bedside monitoring.