Carbon nanotube (CNT)-based microelectrodes have been investigated as alternatives to carbon-fiber microelectrodes for the detection of neurotransmitters because they are sensitive, exhibit fast electron transfer kinetics, and are more resistant to surface fouling. Wet spinning CNTs into fibers using a coagulating polymer produces a thin, uniform fiber that can be fabricated into an electrode. CNT fibers formed in poly(vinyl alcohol) (PVA) have been used as microelectrodes to detect dopamine, serotonin, and hydrogen peroxide. In this study, we characterize microelectrodes with CNT fibers made in polyethylenimine (PEI), which have much higher conductivity than PVA-CNT fibers. PEI-CNT fibers have lower overpotentials and higher sensitivities than PVA-CNT fiber microelectrodes, with a limit of detection of 5 nM for dopamine. The currents for dopamine were adsorption controlled at PEI-CNT fiber microelectrodes, independent of scan repetition frequency, and stable for over 10 h. PEI-CNT fiber microelectrodes were resistant to surface fouling by serotonin and the metabolite interferant 5-hydroxyindoleacetic acid (5-HIAA). No change in sensitivity was observed for detection of serotonin after 30 flow injection experiments or after 2 h in 5-HIAA for PEI-CNT electrodes. The antifouling properties were maintained in brain slices when serotonin was exogenously applied multiple times or after bathing the slice in 5-HIAA. Thus, PEI-CNT fiber electrodes could be useful for the in vivo monitoring of neurochemicals.

Carbon nanotube yarn microelectrodes (CNTYMEs) exhibit rapid and selective detection of dopamine with fast-scan cyclic voltammetry (FSCV); however, the sensitivity limits their application in vivo. In this study, we introduce laser treatment as a simple, reliable, and efficient approach to improve the sensitivity of CNTYMEs by three fold while maintaining high temporal resolution. The effect of laser treatment on the microelectrode surface was characterized by scanning electron microscopy, Raman spectroscopy, energy dispersion spectroscopy, and laser confocal microscopy. Laser treatment increases the surface area and oxygen containing functional groups on the surface, which provides more adsorption sites for dopamine than at unmodified CNTYMEs. Moreover, similar to unmodified CNTYMEs, the dopamine signal at laser treated CNTYMEs is not dependent on scan repetition frequency, unlike the current at carbon fiber microelectrodes (CFMEs) which decreases with increasing scan repetition frequency. This frequency independence is caused by the significantly larger surface roughness which would trap dopamine-o-quinone and amplify the dopamine signal. CNTYMEs were applied as an in vivo sensor with FSCV for the first time and laser treated CNTYMEs maintained high dopamine sensitivity compared to CFMEs with an increased scan repetition frequency of 50 Hz, which is five-fold faster than the conventional frequency. CNTYMEs with laser treatment are advantageous because of their easy fabrication, high reproducibility, fast electron transfer kinetics, high sensitivity, and rapid in vivo measurement of dopamine and could be a potential alternative to CFMEs in the future.

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 get 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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Glass insulated carbon-fiber microelectrodes (CFMEs) are standard tools for the measurement of neurotransmitters. However, electrodes are fabricated individually and the glass can shatter, limiting application in higher order mammals. Here, we developed a novel microelectrode batch fabrication method using a 3D-printed mold and polyimide resin insulating agent. The 3D-printed mold is low cost, customizable to change the electrode shape, and allows 40 electrodes to be made simultaneously. The polyimide resin is biocompatible, quick to cure, and does not adhere to the plastic mold. The electrodes were tested for the response to dopamine with fast-scan cyclic voltammetry both in vitro and in vivo and performed similarly to traditional glass-insulated electrodes, but with lower background currents. Thus, polyimide-insulated electrodes can be mass-produced using a 3D-printed mold and are an attractive alternative for making cheap, biocompatible microelectrodes.