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Prof. Cory Rusinek
University of Nevada, Las Vegas

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0 Analytical Chemistry
0 Electrochemical Engineering
0 Electrochemistry
0 Sensors
0 Electrochemical oxidation

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Review
Published: 26 January 2021 in Micromachines
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Carbon-based electrodes combined with fast-scan cyclic voltammetry (FSCV) enable neurochemical sensing with high spatiotemporal resolution and sensitivity. While their attractive electrochemical and conductive properties have established a long history of use in the detection of neurotransmitters both in vitro and in vivo, carbon fiber microelectrodes (CFMEs) also have limitations in their fabrication, flexibility, and chronic stability. Diamond is a form of carbon with a more rigid bonding structure (sp 3-hybridized) which can become conductive when boron-doped. Boron-doped diamond (BDD) is characterized by an extremely wide potential window, low background current, and good biocompatibility. Additionally, methods for processing and patterning diamond allow for high-throughput batch fabrication and customization of electrode arrays with unique architectures. While tradeoffs in sensitivity can undermine the advantages of BDD as a neurochemical sensor, there are numerous untapped opportunities to further improve performance, including anodic pretreatment, or optimization of the FSCV waveform, instrumentation, sp 2/sp 3 character, doping, surface characteristics, and signal processing. Here, we review the state-of-the-art in diamond electrodes for neurochemical sensing and discuss potential opportunities for future advancements of the technology. We highlight our team’s progress with the development of an all-diamond fiber ultramicroelectrode as a novel approach to advance the performance and applications of diamond-based neurochemical sensors.

ACS Style

Erin Purcell; Michael Becker; Yue Guo; Seth Hara; Kip Ludwig; Collin McKinney; Elizabeth Monroe; Robert Rechenberg; Cory Rusinek; Akash Saxena; James Siegenthaler; Caryl Sortwell; Cort Thompson; James Trevathan; Suzanne Witt; Wen Li. Next-Generation Diamond Electrodes for Neurochemical Sensing: Challenges and Opportunities. Micromachines 2021, 12, 128 .

AMA Style

Erin Purcell, Michael Becker, Yue Guo, Seth Hara, Kip Ludwig, Collin McKinney, Elizabeth Monroe, Robert Rechenberg, Cory Rusinek, Akash Saxena, James Siegenthaler, Caryl Sortwell, Cort Thompson, James Trevathan, Suzanne Witt, Wen Li. Next-Generation Diamond Electrodes for Neurochemical Sensing: Challenges and Opportunities. Micromachines. 2021; 12 (2):128.

Chicago/Turabian Style

Erin Purcell; Michael Becker; Yue Guo; Seth Hara; Kip Ludwig; Collin McKinney; Elizabeth Monroe; Robert Rechenberg; Cory Rusinek; Akash Saxena; James Siegenthaler; Caryl Sortwell; Cort Thompson; James Trevathan; Suzanne Witt; Wen Li. 2021. "Next-Generation Diamond Electrodes for Neurochemical Sensing: Challenges and Opportunities." Micromachines 12, no. 2: 128.

Full length original research paper
Published: 19 June 2020 in Water and Environment Journal
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Perfluoroalkyl substances (PFAS) have unique properties that limit their degradability in the environment. One of these PFAS is an acid (PFOA). Electrochemical oxidation is a promising method for remediation, but energy costs are high. To limit the energy consumption, this study used a boron‐doped diamond (BDD) electrode stack and a combined current density technique that employed 50 mA/cm2 for the first 0.25 hours then lowered the current density to 1, 5, or 10 mA/cm2. This technique is similar to one developed previously; however, that method was only developed for compounds comprising of carbon, oxygen and nitrogen, whereas PFAS have the addition of fluorine. For the degradation of PFOA, the combined current density of 50 and 5 mA/cm2 (50&5) allowed for a 37% reduction in energy usage to obtain 75% defluorination compared to using 50 mA/cm2 alone. Further investigation into remediating an ion‐exchange regeneration solution shows great promise.

ACS Style

Mary Ensch; Cory A. Rusinek; Michael F. Becker; Thomas Schuelke. A combined current density technique for the electrochemical oxidation of perfluorooctanoic acid (PFOA) with boron‐doped diamond. Water and Environment Journal 2020, 35, 158 -165.

AMA Style

Mary Ensch, Cory A. Rusinek, Michael F. Becker, Thomas Schuelke. A combined current density technique for the electrochemical oxidation of perfluorooctanoic acid (PFOA) with boron‐doped diamond. Water and Environment Journal. 2020; 35 (1):158-165.

Chicago/Turabian Style

Mary Ensch; Cory A. Rusinek; Michael F. Becker; Thomas Schuelke. 2020. "A combined current density technique for the electrochemical oxidation of perfluorooctanoic acid (PFOA) with boron‐doped diamond." Water and Environment Journal 35, no. 1: 158-165.

Journal article
Published: 30 March 2020 in Sustainability
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This study investigated the use of iron and aluminum and their combinations as electrodes to determine the technically sound and economically feasible electrochemical approach for the treatment of anaerobic digestion effluent. The results indicated that the use of iron as anode and cathode is the most suitable solution among different electrode combinations. The reduction of turbidity, total chemical oxygen demand, total phosphorus, total coliforms, Escherichia coli, Enterococci, and phages in the reclaimed water were 99%, 91%, 100%, 1.5 log, 1.7 log, 1.0 log, and 2.0 log, respectively. The economic assessment further concluded that the average treatment cost is $3 per 1000 L for a small-scale operation handling 3000 L wastewater/day. This study demonstrated that the electrocoagulation (EC) is a promising technique for the recovery and reclamation of water from anaerobic digestion effluent. Even though its energy consumption is higher and the nitrogen removal is insufficient compared to some conventional wastewater treatment technologies, there are several advantages of the EC treatment, such as short retention time, small footprint, no mixing, and gradual addition of coagulants. These features make EC technology applicable to be used alone or combined with other technologies for a wide range of wastewater treatment applications.

ACS Style

Sibel Uludag-Demirer; Nathan Olson; Rebecca Ives; Jean Pierre Nshimyimana; Cory A. Rusinek; Joan B. Rose; Wei Liao. Techno-Economic Analysis of Electrocoagulation on Water Reclamation and Bacterial/Viral Indicator Reductions of a High-Strength Organic Wastewater—Anaerobic Digestion Effluent. Sustainability 2020, 12, 2697 .

AMA Style

Sibel Uludag-Demirer, Nathan Olson, Rebecca Ives, Jean Pierre Nshimyimana, Cory A. Rusinek, Joan B. Rose, Wei Liao. Techno-Economic Analysis of Electrocoagulation on Water Reclamation and Bacterial/Viral Indicator Reductions of a High-Strength Organic Wastewater—Anaerobic Digestion Effluent. Sustainability. 2020; 12 (7):2697.

Chicago/Turabian Style

Sibel Uludag-Demirer; Nathan Olson; Rebecca Ives; Jean Pierre Nshimyimana; Cory A. Rusinek; Joan B. Rose; Wei Liao. 2020. "Techno-Economic Analysis of Electrocoagulation on Water Reclamation and Bacterial/Viral Indicator Reductions of a High-Strength Organic Wastewater—Anaerobic Digestion Effluent." Sustainability 12, no. 7: 2697.

Research article
Published: 03 December 2019 in Environmental Science & Technology
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This research investigated mechanisms for biofouling control at boron-doped diamond (BDD) electrode surfaces polarized at low applied potentials (e.g., -0.2 to 1 V versus Ag/AgCl), using Pseudomonas aeruginosa as a model organism. Results indicated that electrostatic interactions between bacteria and ionic electrode functional groups facilitated bacteria attachment at the open circuit potential (OCP). However, under polarization the applied potential governed these electrostatic interactions and electrochemical reactions resulted in surface bubble formation and near-surface pH modulation that decreased surface attachment under anodic conditions. The poration of the attached bacteria occurred at OCP conditions and increased with the applied potential. Scanning electrochemical microscopy (SECM) provided near-surface pH and oxidant formation measurements under anodic and cathodic polarizations. The near-surface pH was 3.1 at 1.0 V vs. Ag/AgCl and 8.0 at -0.2 V vs. Ag/AgCl and was possibly a contributor to bacteria poration. Interpretation of SECM data using a reactive transport model allowed for a better understanding of the near-electrode chemistry. Under cathodic conditions, the primary oxidant formed was H2O2 and under anodic conditions a combination of H2O2, Cl•, HO2•, Cl2•-, and Cl2 formation likely contributed to bacteria poration at potentials as low as 0.5 V vs. Ag/AgCl.

ACS Style

Meng-Hsuan Lin; Shafigh Mehraeen; Gang Cheng; Cory A. Rusinek; Brian P. Chaplin. Role of Near-Electrode Solution Chemistry on Bacteria Attachment and Poration at Low Applied Potentials. Environmental Science & Technology 2019, 54, 446 -455.

AMA Style

Meng-Hsuan Lin, Shafigh Mehraeen, Gang Cheng, Cory A. Rusinek, Brian P. Chaplin. Role of Near-Electrode Solution Chemistry on Bacteria Attachment and Poration at Low Applied Potentials. Environmental Science & Technology. 2019; 54 (1):446-455.

Chicago/Turabian Style

Meng-Hsuan Lin; Shafigh Mehraeen; Gang Cheng; Cory A. Rusinek; Brian P. Chaplin. 2019. "Role of Near-Electrode Solution Chemistry on Bacteria Attachment and Poration at Low Applied Potentials." Environmental Science & Technology 54, no. 1: 446-455.

Research article
Published: 01 April 2019 in ACS Applied Materials & Interfaces
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The combination of conductivity, optical transparency, and wide anodic potential window has driven significant interest in indium tin oxide (ITO) as an electrode material for electrochemical measurements. More recently, ITO has been applied to the detection of trace metals using cathodic stripping voltammetry (CSV), specifically manganese (Mn). However, the optimization of ITO fabrication for a voltammetric method such as CSV has yet to be reported, nor have the microstructural properties of ITO been investigated for CSV. Furthermore, CSV does not require optical transparency, thereby allowing non-transparent substrates to be used for deposition. This enables microfabrication procedures to be expanded and simplified compared to glass or quartz. Combining this with the profound importance of sensitive, selective detection of toxic metal ions in environmentally- and biologically-relevant samples, makes ITO especially attractive. In this work, we report a thorough investigation of ITO deposition and processing on silicon (Si) substrates for CSV analysis using Mn as the model analyte. Several ITO process parameters were examined such as heated deposition and post-process annealing. Each ITO film was characterized using a variety of surface, bulk (x-ray diffraction), and electrochemical measurements. While each ITO film type showed electrochemical activity, the heated and annealed (HA) ITO fabrication process yielded superior results for Mn CSV where a limit of detection (LOD) of 0.1 ppb (1.8 nM) was obtained. This work exemplifies new applications of ITO as an electrode material while providing a baseline for trace detection of toxic metals and other contaminants amenable to detection by CSV.

ACS Style

Mary Ensch; Bettina Wehring; Greg D. Landis; Elias Garratt; Michael F. Becker; Thomas Schuelke; Cory A. Rusinek. Indium Tin Oxide Film Characteristics for Cathodic Stripping Voltammetry. ACS Applied Materials & Interfaces 2019, 11, 16991 -17000.

AMA Style

Mary Ensch, Bettina Wehring, Greg D. Landis, Elias Garratt, Michael F. Becker, Thomas Schuelke, Cory A. Rusinek. Indium Tin Oxide Film Characteristics for Cathodic Stripping Voltammetry. ACS Applied Materials & Interfaces. 2019; 11 (18):16991-17000.

Chicago/Turabian Style

Mary Ensch; Bettina Wehring; Greg D. Landis; Elias Garratt; Michael F. Becker; Thomas Schuelke; Cory A. Rusinek. 2019. "Indium Tin Oxide Film Characteristics for Cathodic Stripping Voltammetry." ACS Applied Materials & Interfaces 11, no. 18: 16991-17000.

Journal article
Published: 31 July 2018 in Journal of The Electrochemical Society
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Neurochemical sensing with implantable microelectrodes has created multiple research opportunities in the field of neuroscience. The ability to record extracellular biopotentials and detect neurotransmitters with high sensitivity has enabled deeper understanding of brain and nervous system function. Diamond has many advantages over other electrode materials such as good biocompatibility, wide potential window, low double-layer capacitance, long-term stability, resistance to corrosion/fouling, and fabrication flexibility. In this work, we present a micromachined, implantable, all-diamond microfiber capable of reliable, precise neurochemical sensing. The all-diamond fiber consists of a conductive boron-doped polycrystalline diamond (BDD) core encapsulated in layers of insulating polycrystalline diamond (PCD) cladding. The PCD serves as a biocompatible and hermetic package while also acting as a dielectric barrier to prevent signal cross-talking. The all-diamond microelectrodes were thoroughly characterized using topographical and electrochemical methods. The capability for neurotransmitter sensing was completed using dopamine (DA) as the model analyte. Fast-scan cyclic voltammetry (FSCV) of DA was also completed to demonstrate the practicality for in vivo sensing at rapid rates. The fabrication is described in great detail and the capability for batch-scale process is demonstrated. These novel all-diamond microelectrodes have commercial-scale potential, generating a powerful tool for neurochemical analysis.

ACS Style

Cory A. Rusinek; Yue Guo; Robert Rechenberg; Michael F. Becker; Erin Purcell; Matthew Verber; Collin McKinney; Wen Li. All-Diamond Microfiber Electrodes for Neurochemical Analysis. Journal of The Electrochemical Society 2018, 165, G3087 -G3092.

AMA Style

Cory A. Rusinek, Yue Guo, Robert Rechenberg, Michael F. Becker, Erin Purcell, Matthew Verber, Collin McKinney, Wen Li. All-Diamond Microfiber Electrodes for Neurochemical Analysis. Journal of The Electrochemical Society. 2018; 165 (12):G3087-G3092.

Chicago/Turabian Style

Cory A. Rusinek; Yue Guo; Robert Rechenberg; Michael F. Becker; Erin Purcell; Matthew Verber; Collin McKinney; Wen Li. 2018. "All-Diamond Microfiber Electrodes for Neurochemical Analysis." Journal of The Electrochemical Society 165, no. 12: G3087-G3092.

Research article
Published: 29 April 2018 in Analytical Chemistry
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The performance of a boron-doped diamond disk and a planar diamond thin-film electrode was compared for the anodic stripping voltammetric determination of Ag(I). The polished diamond disk electrode is more flexible than the planar diamond 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. In addition, the concentration of Ag(I) in two water samples, a NASA simulated potable water and a NIST standard reference solution, was determined. The electrochemical results were validated by measurements of the same solutions using ICP-OES. The disk electrode exhibited lower background current and noise. The detection figures of merit for the disk electrode were generally as good or superior to those for the planar film electrode. Detection limits were ≤ 5 ppb (S/N=3) for the modest deposition conditions, and response variabilities were < 5% RSD. However, the disk electrode presented a more limited linear dynamic range because of the reduced surface area available for metal phase formation. The concentration of Ag (I) in the two real samples, as determined by DPASV, was in good agreement with the concentration determined by ICP-OES.

ACS Style

Vanessa Y. Maldonado; Patricio Javier Espinoza-Montero; Cory A. Rusinek; Greg M. Swain. Analysis of Ag(I) Biocide in Water Samples Using Anodic Stripping Voltammetry with a Boron-Doped Diamond Disk Electrode. Analytical Chemistry 2018, 90, 6477 -6485.

AMA Style

Vanessa Y. Maldonado, Patricio Javier Espinoza-Montero, Cory A. Rusinek, Greg M. Swain. Analysis of Ag(I) Biocide in Water Samples Using Anodic Stripping Voltammetry with a Boron-Doped Diamond Disk Electrode. Analytical Chemistry. 2018; 90 (11):6477-6485.

Chicago/Turabian Style

Vanessa Y. Maldonado; Patricio Javier Espinoza-Montero; Cory A. Rusinek; Greg M. Swain. 2018. "Analysis of Ag(I) Biocide in Water Samples Using Anodic Stripping Voltammetry with a Boron-Doped Diamond Disk Electrode." Analytical Chemistry 90, no. 11: 6477-6485.

Research article
Published: 23 January 2018 in Analytical Chemistry
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Boron-doped diamond (BDD) is a promising electrochemical tool that exhibits excellent chemical sensitivity and stability. These intrinsic advantages coupled with the material’s 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 is comprised of a working, reference, and auxiliary electrode, all made of BDD. Two different working electrode geometries were studied, a 2 mm diameter macro electrode (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-hour 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.

ACS Style

Mary Ensch; Vanessa Y. Maldonado; Greg M. Swain; Robert Rechenberg; Michael F. Becker; Thomas Schuelke; Cory A. Rusinek. Isatin Detection Using a Boron-Doped Diamond 3-in-1 Sensing Platform. Analytical Chemistry 2018, 90, 1951 -1958.

AMA Style

Mary Ensch, Vanessa Y. Maldonado, Greg M. Swain, Robert Rechenberg, Michael F. Becker, Thomas Schuelke, Cory A. Rusinek. Isatin Detection Using a Boron-Doped Diamond 3-in-1 Sensing Platform. Analytical Chemistry. 2018; 90 (3):1951-1958.

Chicago/Turabian Style

Mary Ensch; Vanessa Y. Maldonado; Greg M. Swain; Robert Rechenberg; Michael F. Becker; Thomas Schuelke; Cory A. Rusinek. 2018. "Isatin Detection Using a Boron-Doped Diamond 3-in-1 Sensing Platform." Analytical Chemistry 90, no. 3: 1951-1958.