Surface-Roughened Graphene Oxide Microfibers Enhance Electrochemical Reversibility.

Here, we provide an optimized method for fabricating surface-roughened graphene oxide disk microelectrodes (GFMEs) with enhanced defect density to generate a more suitable electrode surface for dopamine detection with fast-scan cyclic voltammetry (FSCV). FSCV detection, which is often influenced by adsorption-based surface interactions, is commonly impacted by the chemical and geometric structure of the electrode's surface, and graphene oxide is a tunable carbon-based nanomaterial capable of enhancing these two key characteristics. Synthesized GFMEs possess exquisite electronic and mechanical properties. We have optimized an applied inert argon (Ar) plasma treatment to increase defect density, with minimal changes in chemical functionality, for enhanced surface crevices to momentarily trap dopamine during detection. Optimal Ar plasma treatment (100 sccm, 60 s, 100 W) generates crevice depths of 33.4 ± 2.3 nm with high edge plane character enhancing dopamine interfacial interactions. Increases in GFME surface roughness improve electron transfer rates and limit diffusional rates out of the crevices to create nearly reversible dopamine electrochemical redox interactions. The utility of surface-roughened disk GFMEs provides comparable detection sensitivities to traditional cylindrical carbon fiber microelectrodes while improving temporal resolution ten-fold with amplified oxidation current due to dopamine cyclization. Overall, surface-roughened GFMEs enable improved adsorption interactions, momentary trapping, and current amplification, expanding the utility of GO microelectrodes for FSCV detection.

Creating covalent bonds between Cu and C at the interface of metal/open-ended carbon nanotubes.

The unique electrical properties of carbon nanotubes (CNTs) are highly desired in many technological applications. Unfortunately, in practice, the electrical conductivity of most CNTs and their assemblies has fallen short of expectations. One reason for this poor performance is that electrical resistance develops at the interface between carbon nanomaterials and metal surfaces when traditional metal-metal type contacts are employed. Here, a method for overcoming this resistance using covalent bond formation between open-ended CNTs and Cu surfaces is investigated experimentally and supported by theoretical calculations. The open-ended CNTs are vertically oriented compared to the substrate and have carboxylic functional groups that react with aminophenyl groups (linkers) grafted on metal surfaces. The covalent bond formation, crosslinking carboxylic and amine, via amide bond formation occurs at 120 °C. The covalent bonding nature of the aminophenyl linker is demonstrated theoretically using (100), (110), and (111) Cu surfaces, and bridge-like bond formation between carbon and two adjacent Cu atoms is revealed. The electrical conductivity calculated for a single intramolecular-type junction supports covalent bond formation between Cu and CNTs. Experimentally, the robustness of the covalent bonding between vertically oriented CNTs is tested by exposing CNTs on Cu to sonication, which reveals that CNTs remain fixed to the Cu supports. Since bonding CNTs to metals was performed at low temperatures, the reported method of covalent bond formation is expected to facilitate the application of CNTs in multiple fields, including electronics.

Evaluation of Polymer-Coated Carbon Nanotube Flexible Microelectrodes for Biomedical Applications.

The demand for electrically insulated microwires and microfibers in biomedical applications is rapidly increasing. Polymer protective coatings with high electrical resistivity, good chemical resistance, and a long shelf-life are critical to ensure continuous device operation during chronic applications. As soft and flexible electrodes can minimize mechanical mismatch between tissues and electronics, designs based on flexible conductive microfibers, such as carbon nanotube (CNT) fibers, and soft polymer insulation have been proposed. In this study, a continuous dip-coating approach was adopted to insulate meters-long CNT fibers with hydrogenated nitrile butadiene rubber (HNBR), a soft and rubbery insulating polymer. Using this method, 4.8 m long CNT fibers with diameters of 25-66 µm were continuously coated with HNBR without defects or interruptions. The coated CNT fibers were found to be uniform, pinhole free, and biocompatible. Furthermore, the HNBR coating had better high-temperature tolerance than conventional insulating materials. Microelectrodes prepared using the HNBR-coated CNT fibers exhibited stable electrochemical properties, with a specific impedance of 27.0 ± 9.4 MΩ µm2 at 1.0 kHz and a cathodal charge storage capacity of 487.6 ± 49.8 mC cm-2. Thus, the developed electrodes express characteristics that made them suitable for use in implantable medical devices for chronic in vivo applications.

Hydrophilic Micro- and Macroelectrodes with Antibiofouling Properties for Biomedical Applications.

Implantable neural electrodes are generally used to record the electrical activity of neurons and to stimulate neurons in the nervous system. Biofouling triggered by inflammatory responses can dramatically affect the performance of neural electrodes, resulting in decreased signal sensitivity and consistency over time. Thus, long-term clinical applications require electrically conducting electrode materials with reduced dimensions, high flexibility, and antibiofouling properties that can reduce the degree of inflammatory reactions and increase the lifetime of neural electrodes. Carbon nanotubes (CNTs) are well known to form flexible assemblies such as CNT fibers. Herein, we report the covalent functionalization of predefined CNT fiber and film surfaces with hydrophilic, antibiofouling phosphorylcholine (PC) molecules. The electrochemical and spectroscopic characteristics, impedance properties, hydrophilicity, and in vitro antifouling nature of the functionalized CNT surfaces were evaluated. The hydrophilicity of the functionalized CNT films was demonstrated by a decrease in the static contact angle from 134.4° ± 3.9° before to 15.7° ± 1.5° after one and fully wetting after three functionalization cycles, respectively. In addition, the extent of protein absorption on the functionalized CNT films was significantly lower than that on the nonfunctionalized CNT film. Surprisingly, the faradic charge-transfer properties and impedance of the CNT assemblies were preserved after functionalization with PC molecules. These functionalized CNT assemblies are promising for the development of low-impedance neural electrodes with higher hydrophilicity and protein-fouling resistance to inhibit inflammatory responses.