Polymer Modified Carbon Fiber Microelectrodes for Precision Neurotransmitter Metabolite Measurements.
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ABSTRACT:
SUBMITTER: Wonnenberg P
PROVIDER: S-EPMC8081299 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description: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/sec) 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/sec) 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.
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Project description:Carbon nanohorns (CNHs), closed cone-shaped cages of sp 2-hybridized carbons, are a promising nanomaterial to improve carbon-fiber microelectrode (CFME) dues to their high specific surface area and edge planes, but few studies have tested their electrochemical properties. Here, we tested the dopamine detection at electrodeposited CNHs on CFME (CNH/CFME). The optimized concentration of CNHs in the deposition solution is 0.5 mg/mL, and the optimized electrodeposition waveform is 10 cycles of triangular waveform scanned from -1.0 V and +1.0 V at 50 mV/s. Using fast-scan cyclic voltammetry, the optimized CNH/CFME enhances dopamine peak current to 2.3 ± 0.2 times that of the CFME. To further increase the current, CNH/CFMEs were oxidized in NaOH (ox-CNH/CFME), which creates more defects and surface oxide groups to adsorb dopamine. The oxidative etching further increases the peak current to 3.5 ± 0.2 times of the CFME, and ox-CNH/CFME had a limit of detection of 6 ± 2 nM. The dopamine anodic current at ox-CNH/CFME was stable for 8 h of continuous scanning. The ox-CNH/CFME enhanced the anodic peak current for other cationic neurotransmitters including epinephrine, norepinephrine, and serotonin, but less enhancement was found for ascorbic acid, showing higher selectivity for cationic molecules. CNHs also decreased tissue biofouling at CFME. Thus, electrodeposited CNHs are a promising new method for increasing the surface area and current of CFMEs for dopamine detection.
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Project description:The mechanisms that control extracellular serotonin levels in vivo are not well-defined. This shortcoming makes it very challenging to diagnose and treat the many psychiatric disorders in which serotonin is implicated. Fast-scan cyclic voltammetry (FSCV) can measure rapid serotonin release and reuptake events but cannot report critically important ambient serotonin levels. In this Article, we use fast-scan controlled adsorption voltammetry (FSCAV), to measure serotonin's steady-state, extracellular chemistry. We characterize the "Jackson" voltammetric waveform for FSCAV and show highly stable, selective, and sensitive ambient serotonin measurements in vitro. In vivo, we report basal serotonin levels in the CA2 region of the hippocampus as 64.9 ± 2.3 nM (n = 15 mice, weighted average ± standard error). We electrochemically and pharmacologically verify the selectivity of the serotonin signal. Finally, we develop a statistical model that incorporates the uncertainty in in vivo measurements, in addition to electrode variability, to more critically analyze the time course of pharmacological data. Our novel method is a uniquely powerful analysis tool that can provide deeper insights into the mechanisms that control serotonin's extracellular levels.
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Project description:Fibers made of CNTs are attractive microelectrode sensors because they can be directly fabricated into microelectrodes. Different protocols for making CNT fibers have been developed, but differences in surface structure and therefore electrochemical properties that result have not been studied. In this study, we correlated the surface and electrochemical properties for neurochemical detection at 3 types of materials: CNT fibers produced by wet spinning with (1) polyethylenimine (PEI/CNT) or (2) chlorosulfonic acid (CA/CNT), and (3) CNT yarns made by solid-based CNT drawing. CNT yarns had well-aligned, high purity CNTs, abundant oxygen functional groups, and moderate surface roughness which led to the highest dopamine current density (290 ± 65 pA/cm2) and fastest electron transfer kinetics. The crevices of the CNT yarn and PEI/CNT fiber microelectrodes allow dopamine to be momentarily trapped during fast-scan cyclic voltammetry detection, leading to thin-layer cell conditions and a response that was independent of applied waveform frequency. The larger crevices on the PEI/CNT fibers led to a slower time response, showing too much roughness is detrimental to fast detection. CA/CNT fibers have a smoother surface and lower currents, but their negative surface charge results in high selectivity for dopamine over uric acid or ascorbic acid. Overall, small crevices, high conductivity, and abundant oxygen groups led to high sensitivity for amine neurotransmitters, such as dopamine and serotonin. Thus, different surfaces of CNT fibers result in altered electrochemical properties and could be used in the future to predict and control electrochemical performance.
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Project description:Adenosine triphosphate (ATP) is an important rapid signaling molecule involved in a host of pathologies in the body. Historically, ATP is difficult to directly detect electrochemically with fast-scan cyclic voltammetry (FSCV) due to limited interactions at bare carbon-fibers. Systematic investigations of how ATP interacts at electrode surfaces is necessary for developing more sensitive electrochemical detection methods. Here, we have developed gold nanoparticle (AuNP), and platinum nanoparticle (PtNP) modified carbon-fiber microelectrodes coupled to FSCV to measure the extent to which ATP interacts at metal nanoparticle-modified surfaces and to improve the sensitivity of direct electrochemical detection. AuNP and PtNPs were electrodeposited on the carbon-fiber surface by scanning from -1.2 to 1.5 V for 30 s in 0.5 mg/mL HAuCl4 or 0.5 mg/mLK2PtCl6. Overall, we demonstrate an average 4.1 ± 1.0-fold increase in oxidative ATP current at AuNP-modified and a 3.5 ± 0.3-fold increase at PtNP-modified electrodes. Metal nanoparticle-modified surfaces promoted improved electrocatalytic conversion of ATP oxidation products at the surface, facilitated enhanced adsorption strength and surface coverage, and significantly improved sensitivity. ATP was successfully detected within living murine lymph node tissue following exogenous application. Overall, this study demonstrates a detailed characterization of ATP oxidation at metal nanoparticle surfaces and a significantly improved method for direct electrochemical detection of ATP in tissue.
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Project description:We have compared the properties and resistance to DA fouling of a carbon nanotube fiber (CNTF) microelectrode to a traditional carbon fiber (CF) microelectrode. These two materials show comparable electrochemical activities for outer-sphere and inner-sphere redox reactions. Although the CNTF might have a higher intrinsic RC constant, thus limiting its high-frequency behavior, the CNTF shows a significantly higher durability than the CF in terms of electrode stability. During constant oxidation of 100 ?M DA, the signal measured by the CNTF microelectrode shows a 2-h window over which no decrease in current is observed. Under the same conditions, the current obtained at the CF microelectrode decreases by almost 50%. A model of the fouling process, assuming the formation of growing patches of insulator on the surface, has been compared to the data. This model is found to be in good agreement with our results and indicates a growth rate of the patches in the 0.1-2 nm s(-1) range.
| S-EPMC4276597 | biostudies-literature
Project description:Adenosine is a neuromodulator that regulates neurotransmission. Adenosine can be monitored using fast-scan cyclic voltammetry at carbon-fiber microelectrodes and ATP is a possible interferent in vivo because the electroactive moiety, adenine, is the same for both molecules. In this study, we investigated carbon-fiber microelectrodes coated with Nafion and carbon nanotubes (CNTs) to enhance the sensitivity of adenosine and decrease interference by ATP. Electrodes coated in 0.05 mg mL(-1) CNTs in Nafion had a 4.2 ± 0.2 fold increase in current for adenosine, twice as large as for Nafion alone. Nafion-CNT electrodes were 6 times more sensitive to adenosine than ATP. The Nafion-CNT coating did not slow the temporal response of the electrode. Comparing different purine bases shows that the presence of an amine group enhances sensitivity and that purines with carbonyl groups, such as guanine and hypoxanthine, do not have as great an enhancement after Nafion-CNT coating. The ribose group provides additional sensitivity enhancement for adenosine over adenine. The Nafion-CNT modified electrodes exhibited significantly more current for adenosine than ATP in brain slices. Therefore, Nafion-CNT modified electrodes are useful for sensitive, selective detection of adenosine in biological samples.
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Project description:Fast-scan cyclic voltammetry (FSCV) can detect small changes in dopamine concentration; however, measurements are typically limited to scan repetition frequencies of 10 Hz. Dopamine oxidation at carbon-fiber microelectrodes (CFMEs) is dependent on dopamine adsorption, and increasing the frequency of FSCV scan repetitions decreases the oxidation current, because the time for adsorption is decreased. Using a commercially available carbon nanotube yarn, we characterized carbon nanotube yarn microelectrodes (CNTYMEs) for high-speed measurements with FSCV. For dopamine, CNTYMEs have a significantly lower ΔEp than CFMEs, a limit of detection of 10 ± 0.8 nM, and a linear response to 25 μM. Unlike CFMEs, the oxidation current of dopamine at CNTYMEs is independent of scan repetition frequency. At a scan rate of 2000 V/s, dopamine can be detected, without any loss in sensitivity, with scan frequencies up to 500 Hz, resulting in a temporal response that is four times faster than CFMEs. While the oxidation current is adsorption-controlled at both CFMEs and CNTYMEs, the adsorption and desorption kinetics differ. The desorption coefficient of dopamine-o-quinone (DOQ), the oxidation product of dopamine, is an order of magnitude larger than that of dopamine at CFMEs; thus, DOQ desorbs from the electrode and can diffuse away. At CNTYMEs, the rates of desorption for dopamine and dopamine-o-quinone are about equal, resulting in current that is independent of scan repetition frequency. Thus, there is no compromise with CNTYMEs: high sensitivity, high sampling frequency, and high temporal resolution can be achieved simultaneously. Therefore, CNTYMEs are attractive for high-speed applications.
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Project description:Neurotoxic heavy metals, such as Cd2+, pose a significant global health concern due to their increased environmental contamination and subsequent detrimental health hazards they pose to human beings. These metal ions can breach the blood-brain barrierblood-brain barrier, leading to severe and often irreversible damage to the central nervous system and other vital organs. Therefore, developing a highly sensitive, robust, and rapid in vivo detection method for these hazardous heavy metal ions is of the utmost importance for early detection, thus initiating timely therapeutics. Detecting ultra-low levels of toxic metal ions in vivo and obtaining accurate speciation information remains a challenge with conventional analytical techniques. In this study, we fabricated a novel carbon carbon-fiber microelectrode (CFM)-based sensor that can detect Cd2+ ions using fast-scan cyclic voltammetry by electrodepositing gold nanoparticles (AuNP). We optimized electrochemical parameters that generate a unique cyclic voltammogram (CV) of Cd2+ at a temporal resolution of 100 ms with our novel sensor. All our experiments were performed in tris buffer that mimics the artificial cerebellum fluid. We established a calibration curve resulting in a limit of detection (LOD) of 0.01 µM with a corresponding sensitivity of 418.02 nA/ µM. The sensor's selectivity was evaluated in the presence of other metal ions, and it was noteworthy to observe that the sensor retained its ability to produce the distinctive Cd2+ CV, even when the concentration of other metal ions was 200 times higher than that of Cd2+. We also found that our sensor could detect free Cd2+ ions in the presence of complexing agents. Furthermore, we analyzed the solution chemistry of each of those Cd2+-ligand solutions using a geochemical model, PHREEQC. The concentrations of free Cd2+ ions determined through our electrochemical data align well with geochemical modeling data, thus validating the response of our novel sensor. Furthermore, we reassessed our sensor's LOD in tris buffer based on the concentration of free Cd2+ ions determined through PHREEQC analysis, revealing an LOD of 0.00132 µM. We also demonstrated the capability of our sensor to detect Cd2+ ions in artificial urine samples, showcasing its potential for application in actual biological samples. To the best of our knowledge, this is the first AuNP-modified, CFM-based Cd2+ sensor capable of detecting ultra-low concentrations of free Cd2+ ions in different complex matrices, including artificial urine at a temporal resolution of 100 ms, making it an excellent analytical tool for future real-time, in vivo detection, particularly in the brain.
| S-EPMC10971841 | biostudies-literature
Project description:Nanodiamonds (NDs) are carbon nanomaterials with a core diamond crystalline structure and crystal defects, such as graphitic carbon and heteroatoms, on their surface. For electrochemistry, NDs are promising to increase active sites and decrease fouling, but NDs have not been studied for neurotransmitter electrochemistry. Here, we optimized ND coatings on microelectrodes and found that ND increases the sensitivity for neurotransmitters with fast-scan cyclic voltammetry detection and decreases electrochemical and biofouling. Different sizes and functionalizations of NDs were tested, and ND suspensions were drop-casted onto carbon-fiber microelectrodes (CFMEs). The 5 nm ND-H and 5 nm ND-COOH formed thick coatings, while the 15 and 60 nm ND-COOH formed more sparse coatings. With electrochemical impedance spectroscopy, 5 nm ND-H and 5 nm ND-COOH had high charge-transfer resistance, while 15 and 60 nm ND-COOH had low charge-transfer resistance. ND-COOH (15 nm) was optimal, with the best electrocatalytic properties and current for dopamine. Sensitivity was enhanced 2.1 ± 0.2 times and the limit of detection for dopamine improved to 3 ± 1 nM. ND coating increased current for other cations such as serotonin, norepinephrine, and epinephrine, but not for the anion ascorbic acid. Moreover, NDs decreased electrochemical fouling from serotonin and 5-hydroxyindoleacetic acid, and they also decreased biofouling in brain slice tissue by 50%. The current at biofouled ND-coated electrodes is similar to the signal of pristine, unfouled CFMEs. The carboxylated ND-modified CFMEs are beneficial for neurotransmitter detection because of easy fabrication, improved limit of detection, and antifouling properties.
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