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
Carbon Nanotube Yarn Microelectrodes Promote High Temporal Measurements of Serotonin Using Fast Scan Cyclic Voltammetry
Carbon fiber-microelectrodes (CFMEs) have been the standard for neurotransmitter detection for over forty years. However, in recent years, there have been many advances of utilizing alternative nanomaterials for neurotransmitter detection with fast scan cyclic voltammetry (FSCV). Recently, carbon nanotube (CNT) yarns have been developed as the working electrode materials for neurotransmitter sensing capabilities with fast scan cyclic voltammetry. Carbon nanotubes are ideal for neurotransmitter detection because they have higher aspect ratios enabling monoamine adsorption and lower limits of detection, faster electron transfer kinetics, and a resistance to surface fouling. Several methods to modify CFMEs with CNTs have resulted in increases in sensitivity, but have also increased noise and led to irreproducible results. In this study, we utilize commercially available CNT-yarns to make microelectrodes as enhanced neurotransmitter sensors for neurotransmitters such as serotonin. CNT-yarn microelectrodes have significantly higher sensitivities (peak oxidative currents of the cyclic voltammograms) than CFMEs and faster electron transfer kinetics as measured by peak separation (ΔEP) values. Moreover, both serotonin and dopamine are adsorption controlled to the surface of the electrode as measured by scan rate and concentration experiments. CNT yarn microelectrodes also resisted surface fouling of serotonin onto the surface of the electrode over thirty minutes and had a wave application frequency independent response to sensitivity at the surface of the electrode.
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- Award ID(s):
- 1936173
- NSF-PAR ID:
- 10156174
- Date Published:
- Journal Name:
- Sensors
- Volume:
- 20
- Issue:
- 4
- ISSN:
- 1424-8220
- Page Range / eLocation ID:
- 1173
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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μ M−1, (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 forin vivo measurements and further understanding of the physiological role of oxytocin. -
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Fast scan cyclic voltammetry (FSCV) is an analytical technique that was first developed over 30 years ago. Since then, it has been extensively used to detect dopamine using carbon fiber microelectrodes (CFMEs). More recently, electrode modifications and waveform refinement have enabled the detection of a wider variety of neurochemicals including nucleosides such as adenosine and guanosine, neurotransmitter metabolites of dopamine, and neuropeptides such as enkephalin. These alterations have facilitated the selectivity of certain biomolecules over others to enhance the measurement of the analyte of interest while excluding interferants. In this review, we detail these modifications and how specializing CFME sensors allows neuro-analytical researchers to develop tools to understand the neurochemistry of the brain in disease states and provide groundwork for translational work in clinical settings.
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Here, we developed a microfluidic electrochemical flow cell for fast-scan cyclic voltammetry which is capable of rapid on-chip dilution for efficient and cost-effective electrode calibration. Fast-scan cyclic voltammetry (FSCV) at carbon-fiber microelectrodes is a robust electroanalytical technique used to measure subsecond changes in neurotransmitter concentration over time.Traditional methods of electrode calibration for FSCV require several milliliters of a standard. Additionally, generating calibration curves can be time-consuming because separate solutions must be prepared for each concentration. Microfluidic electrochemical flow cells have been developed in the past; however, they often require incorporating the electrode in the device, making it difficult to remove for testing in biological tissues. Likewise, current microfluidic electrochemical flow cells are not capable of rapid on-chip dilution to eliminate the requirement of making multiple solutions. We designed a T-channel device, with microchannel dimensions of 100 μm × 50 μm, that delivered a standard to a 2-mm-diameter open electrode sampling well. A waste channel with the same dimensions was designed perpendicular to the well to flush and remove the standard. The dimensions of the T-microchannels and flow rates were chosen to facilitate complete mixing in the delivery channel prior to reaching the electrode. The degree of mixing was computationally modeled using COMSOL and was quantitatively assessed in the device using both colored dyes and electrochemical detection. On-chip electrode calibration for dopamine with FSCV was not significantly different than the traditional calibration method demonstrating its utility for FSCV calibration. Overall, this device improves the efficiency and ease of electrode calibration.more » « less
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Carbon-fiber microelectrodes (CFMEs) have been used for several years for the detection of neurotransmitters such as dopamine. Dopamine is a fundamentally important neurotransmitter and is also metabolized at a subsecond timescale. Recently, several metabolites of dopamine have been shown to be physiologically important such as 3-methoxytyramine (3-MT), 3,4-dihydroxyphenylacetic acid (DOPAC), and homovanillic acid (HVA). Many of these neurotransmitter metabolites are currently only detected with microdialysis coupled with liquid chromatography with relatively low temporal and spatial resolution. Current electrochemical methods such as the dopamine waveform (scanning from −0.4 to 1.3 V at 400 V s −1 ) are utilized to electrostatically repel anions such as DOPAC and promote dopamine adsorption to the surface of the electrode. Moreover, polymer coatings such as Nafion have been shown to electrostatically repel anions such as 5-hydroxyindoleacetic acid (5-HIAA). In this study, we develop novel polymer and waveform modifications for enhanced DOPAC detection. Applying the DOPAC waveform (scanning from 0 to 1.3 V at 400 V s −1 ) enhances DOPAC detection significantly because it does not include the negative holding potential of the dopamine waveform. Moreover, positively charged cationic polymers such as polyethyleneimine (PEI) allow for the preconcentration of DOPAC to the surface of the carbon fiber through an electrostatic attraction. The limit of detection for DOPAC for PEI coated CFMEs with the DOPAC waveform applied is 58.2 ± 2 nM as opposed to 291 ± 10 nM for unmodified electrodes applying the dopamine waveform ( n = 4). This work offers promise for the development of novel electrode materials and waveforms for the specific detection of several important biomolecules such as dopamine metabolite neurotransmitters.more » « less
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Serotonin (5-HT) is one of the key neurotransmitters in the human body, regulating numerous physiological functions. A disruption in 5-HT homeostasis could result in serious health problems, including neurodegenerative disorders, depression, and 5-HT syndrome. Detection of 5-HT concentrations in biological fluids, such as urine, is a potential solution for early diagnosis of these diseases. In this study, we developed a novel, simple, and low-cost electrochemical sensing platform consisting of a portable workstation with customized electrodes for 5-HT detection in artificial biological fluids. Nafion/carbon nanotubes (CNTs) and electrochemically modified carbon fiber microelectrodes (Nafion–CNT/EC CFMEs) displayed improved 5-HT sensitivity and selectivity. Together with a customized Ag/AgCl reference electrode and Pt counter electrode, the portable 5-HT sensing platform had a sensitivity of 0.074 μA μM −1 and a limit of detection (LOD) of 140 nM. This system was also assessed to measure 5-HT spiked in artificial urine samples, showing nearly full recovery rates. These satisfactory results demonstrated that the portable system exhibits outstanding performance and confirmed the feasibility of 5-HT detection, which can be used to provide point-of-care analysis in actual biological samples.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/s20041173
