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.

Reagentless Dissolution and Quantification of Particulate Lead in Tap Water via Membrane Electrolysis.

The presence of particulate Pb in tap water has been a limiting factor in the design of accurate and portable platforms for quantifying this toxic metal. Convenient and affordable electrochemical techniques are blind toward particulate species and thus require addition of reagents and additional chemical processing such as sample acidification. This study describes the fundamentals and the first use of membrane electrolysis for the reagentless sample preparation of tap water for the detection of particulate Pb contaminants. Membrane electrolysis allows for the in-situ generation of nitric acid, which, in combination with anodic stripping voltammetry, provides a powerful tool for the accurate and reagent-free detection of Pb2+. The configuration of the setup allows for its semi-autonomous operation and requires minimal attention, making electrochemical methods more suitable and accessible for continuous measurements of particulate contaminants in tap-water. The voltammetric response is linear in the range of 24.1-398 nM of Pb, which covers the action level of 48 nM suggested by the World Health Organization.

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.

Impact of physical and chemical parameters on square wave anodic stripping voltammetry for trace Pb2+ detection in water.

Exposure to lead, a toxic heavy metal, in drinking water is a worldwide problem. Lead leaching from lead service lines, the main contamination source, and other plumbing materials is controlled by the plumbosolvency of water. Square wave anodic stripping voltammetry (SWASV) has been greatly explored as a rapid and portable technique for the detection of trace Pb2+ ions in drinking water. However, the impact of water quality parameters (WQP) on the SWASV technique is not well understood. Herein, SWASV was employed to detect 10 µg L-1 Pb2+ and determine trends in the stripping peak changes in simulated water samples while individually varying the pH, conductivity, alkalinity, free chlorine, temperature, and copper levels. The pH and conductivity were controlled using the buffer 3-(N-morpholino)propanesulfonic acid (MOPS), and NaNO3, respectively and kept at pH = 7.0 and conductivity = 500 µS cm-1 when exploring other WQPs. The working electrode, a gold-nanoparticle-modified carbon nanotube fiber cross-section (AuNP-CNTf-CS) electrode provided sufficiently sharp and prominent peaks for 10 µg L-1 Pb2+ detection as well as good reproducibility, with a relative error of 5.9% in simulated water. We found that conductivity, and temperature had a proportional relationship to the peak height, and pH, alkalinity, free chlorine, and copper had an inverse relationship. In addition, increasing the copper concentration caused broadening and shifting of the Pb2+ stripping peak. At extremely low conductivities (<100 µS cm-1), the voltammograms became difficult to interpret owing to the formation of inverted and distorted peaks. These trends were then also observed within a local drinking water sample in order to validate the results.

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.

Near-electrode pH change for voltammetric detection of insoluble lead carbonate.

Lead contamination of drinking water is a concern to all inhabitants of old cities where lead pipes and soldering are still present. Simple on-site electrochemical detection methods are promising technologies that have gained attention recently. However, conventional electrochemical techniques only quantify soluble forms of lead in water without accounting for insoluble particulates. Herein, a simple voltammetric technique for quantification of insoluble lead species is reported. Lead carbonate (PbCO3) was used as a model compound to show the possibility of detecting particulate lead species directly in solution without chemical treatment. Specifically, electrochemical generation of protons was used as an alternative method to dissolve PbCO3 and thus obtain a more realistic assessment of lead contamination. Lead was detected using cathodic stripping square wave voltammetry (CSSWV). After applying a high oxidizing potential to the electrode immersed in a PbCO3 solution with solid PbCO3 particulates, a significant increase in current was observed as compared to that of a saturated PbCO3 solution. The signal was proportional to the amount of added PbCO3, even when the solubility limit was exceeded. Thus, the combination of a local pH change with CSSWV provides a simple, rapid, and reagentless method for an in-situ detection of insoluble lead species.

Functionalized carbon nanotube microfibers for chronic neural implants.

BACKGROUND: Much progress has been made at the interface between neural tissue and electrodes for neurophysiology. However, there continues to be a need for novel materials that integrate well with the nervous system and facilitate neural recordings with longer-term sustainability and stability. Such materials have the potential to improve clinical approaches and provide important tools for basic neuroscience research. NEW METHOD: In this paper, we explore the use of dry-spun untreated or functionalized carbon nanotube fibers as implantable electrodes for neural recordings from insects over extended time periods. RESULTS: Measurements of fly eyes responding to light flashes illustrate the suitability of these materials for recording both the low- and high-frequency components of neural signals. Repeated recordings show good sustainability, especially with functionalized carbon nanotube fibers. In particular, recordings from the optic lobes of Madagascar hissing cockroaches last for at least 8 weeks. COMPARISON WITH EXISTING METHOD(S): Electrophysiological research continues to rely heavily on metal electrodes that are good for short-lived preparations but less suitable for longer-term recordings, as scar tissue formation and cytotoxicity tend to cause a gradual reduction in signals. CONCLUSIONS: Functionalized carbon nanotubes are a promising novel material that can be used to obtain long-term or repeated stable recordings, which are necessary for longitudinal studies, or to maintain other neural tissue interfaces such as those in insect-machine hybrid robots. The introduced insect preparation can also be used for the relatively rapid and cost-efficient testing of novel electrode materials.

Carbon Nanotube Microelectrode Set: Detection of Biomolecules to Heavy Metals.

An ultrasensitive electrochemical microelectrode set (µ-ES), where all three electrodes are made of highly densified carbon nanotube fiber (HD-CNTf) cross sections (length ∼40 µm), embedded in an inert polymer matrix, and exposed open-ended CNTs at the interface, is presented here. Bare open ends of HD-CNTf rods were used as the working (∼40 µm diameter) and counter (∼94 µm diameter) electrodes, while the cross section of a ∼94 µm diameter was electroplated with Ag/AgCl and coated with Nafion to employ as a quasi-reference electrode. The Ag/AgCl/Nafion-coated HD-CNTf rod quasi-reference electrode provided a very stable potential comparable to the commercial porous-junction Ag/AgCl reference electrode. The HD-CNTf rod µ-ES has been evaluated by electrochemical determination of biologically important analytes, i.e., dopamine (DA), ß-nicotinamide adenine dinucleotide (NADH), a diuretic drug, i.e., furosemide, and a heavy metal, i.e., lead ions (Pb2+). Different voltammetric techniques were employed during the study, i.e., cyclic voltammetry (CV), square wave voltammetry (SWV), amperometry, and square wave anodic stripping voltammetry (SWASV). The direct metallic connection to CNTs gives access to the exceptional properties of highly ordered open-ended CNTs as electrochemical sensors. The distinct structural and electronic properties of aligned HD-CNTf rods in the µ-ES demonstrate fast electron transfer kinetics and offer excellent detection performance during testing for different analytes with wide linear ranges, excellent sensitivity, and very low limits of detection.

Hydrogen Nanometrology in Advanced Carbon Nanomaterial Electrodes.

A comparative experimental study between advanced carbon nanostructured electrodes, in similar hydrogen uptake/desorption conditions, is investigated making use of the recent molecular beam-thermal desorption spectrometry. This technique is used for monitoring hydrogen uptake and release from different carbon electrocatalysts: 3D-graphene, single-walled carbon nanotube networks, multi-walled carbon nanotube networks, and carbon nanotube thread. It allows an accurate determination of the hydrogen mass absorbed in electrodes made from these materials, with significant enhancement in the signal-to-noise ratio for trace hydrogen avoiding recourse to ultra-high vacuum procedures. The hydrogen mass spectra account for the enhanced surface capability for hydrogen adsorption in the different types of electrode in similar uptake conditions, and confirm their enhanced hydrogen storage capacity, pointing to a great potential of carbon nanotube threads in replacing the heavier metals or metal alloys as hydrogen storage media.

Parts per trillion detection of heavy metals in as-is tap water using carbon nanotube microelectrodes.

Heavy metal contamination of drinking water is a major global issue. Research reports across the globe show contamination of heavy metals higher than the set standards of the World Health Organization (WHO) and US Environmental Protection Agency (EPA). To our knowledge, no electrochemical sensor for heavy metals with parts per trillion (PPT) limits of detection (LOD) in as-is tap water has been reported or developed. Here, we report a microelectrode that consists of six highly densified carbon nanotube fiber (HD-CNTf) cross sections called rods (diameter ∼69 µm and length ∼40 µm) in a single platform for the ultra-sensitive detection of heavy metals in tap water and simulated drinking water. The HD-CNTf rods microelectrode was evaluated for the individual and simultaneous determination of trace level of heavy metal ions i.e. Cu2+, Pb2+ and Cd2+ in Cincinnati tap water (without supporting electrolyte) and simulated drinking water using square wave stripping voltammetry (SWSV). The microsensor exhibited a broad linear detection range with an excellent limit of detection for individual Cu2+, Pb2+ and Cd2+ of 6.0 nM, (376 ppt), 0.45 nM (92 ppt) and 0.24 nM (27 ppt) in tap water and 0.32 nM (20 ppt), 0.26 nM (55 ppt) and 0.25 nM (28 ppt) in simulated drinking water, respectively. The microelectrode was shown to detect Pb2+ ions well below the WHO and EPA limits in a broad range of water quality conditions reported for temperature and conductivity in the range of 5 °C-45 °C and 55 to 600 µS/cm, respectively.

True Picomolar Neurotransmitter Sensor Based on Open-Ended Carbon Nanotubes.

Neurotransmitters are important chemicals in human physiological systems for initiating neuronal signaling pathways and in various critical health illnesses. However, concentration of neurotransmitters in the human body is very low (nM or pM level) and it is extremely difficult to detect the fluctuation of their concentrations in patients using existing electrochemical biosensors. In this work, we report the performance of highly densified carbon nanotubes fiber (HD-CNTf) cross-sections called rods (diameter ∼ 69 µm, and length ∼ 40 µm) as an ultrasensitive platform for detection of common neurotransmitters. HD-CNTf rods microelectrodes have open-ended CNTs exposed at the interface with electrolytes and cells and display a low impedance value, i.e., 1050 Ω. Their fabrication starts with dry spun CNT fibers that are encapsulated in an insulating polymer to preserve their structure and alignment. Arrays of HD-CNTf rods microelectrodes were applied to detect neurotransmitters, i.e., dopamine (DA), serotonin (5-HT), epinephrine (Epn), and norepinephrine (Norepn), using square wave voltammetry (SWV) and cyclic voltammetry (CV). They demonstrate good linearity in a broad linear range (1 nM to 100 µM) with an excellent limit of detection, i.e., 32 pM, 31 pM, 64 pM, and 9 pM for DA, 5-HT, Epn, and Norepn, respectively. To demonstrate practical application of HD-CNTf rod arrays, detection of DA in human biological fluids and real time monitoring of DA release from living pheochromocytoma (PC12) cells were performed.

Carbon Nanotube Fibers for Neural Recording and Stimulation.

Recordings and stimulations of neuronal electrical activity are topics of great interest in neuroscience. Many recording techniques, and even treatment of neurological disorders, can benefit from a microelectrode that is flexible, chemically inert, and electrically conducting and preferentially transfers electrons via capacitive charge injection. Commercial electrodes that currently exist and other electrodes that are being tested with the purpose of facilitating and improving the electron transport between solid materials and biological tissues still have some limitations. This paper discusses carbon nanotube (CNT)-based microelectrodes to record and stimulate neurons and compares their electron transport capabilities to noble metals such as Au and Ag. The recording ability of electrodes is tested through electroretinography on Sarcophaga bullata fly eyes by using Au and Ag wires and CNT fibers as electrodes. Stimulation is demonstrated through the implantation of Au wire and CNT fibers into the antennas of the Madagascar hissing cockroach (Gromphadorhina portentosa) to control their locomotion. Our results demonstrate that a particular property of the CNT fiber is its high rate of electron transfer, leading to an order of magnitude lower impedance compared to Au and Ag and an impressive 15.09 charge injection capacity. We also established that this carbon nanomaterial assembly performs well for in vivo electrophysiology, rendering it a promising prospect for neurophysiological applications.

Defect Sites Modulate Fouling Resistance on Carbon-Nanotube Fiber Electrodes.

Carbon nanotube (CNT) fiber electrodes have become increasingly popular electrode materials for neurotransmitter detection with fast-scan cyclic voltammetry (FSCV). The unique properties of CNT fiber electrodes like increased electron transfer, sensitivity, waveform application frequency independence, and resistance to fouling make them ideal biological sensors for FSCV. In particular, their resistance to fouling has been observed for several years, but the specific physical properties which aid in fouling resistance have been debated. Here, we investigate the extent to which the presence of defect sites on the surface attenuate both chemical and biological fouling with FSCV. We compared traditional carbon-fiber microelectrodes (CFMEs) to pristine CNTs and functionalized CNTs. CFMEs and functionalized CNTs are highly disordered with a great deal of defect sites on the surface. The pristine CNTs have fewer defects compared to the purposefully functionalized CNTs and CFMEs. All electrode surfaces were characterized by a combination of scanning electron microscopy (SEM), Raman spectroscopy, and energy dispersive spectroscopy (EDS). Chemical fouling was studied using serotonin, a popular neurotransmitter notoriously known for electrode fouling. To assess biological fouling, electrodes were implanted in brain tissue for 2 h. Defect sites on the carbon were shown to resist biofouling compared to pristine CNTs but were detrimental for serotonin detection. Overall, we provide insight into the extent to which the electrode surface dictates fouling resistance with FSCV. This work provides evidence that careful considerations of the surface of the CNT material are needed when designing sensors for fouling resistance.

Heatable carbon nanotube composite membranes for sustainable recovery from biofouling.

Membrane filtration is one of the most reliable methods for water treatment. However, wider application is limited due to biofouling caused by accumulation of microorganisms on the membrane surface. This report details a heatable carbon nanotube composite membrane with self-cleaning properties for sustainable recovery from biofouling. Microfiltration polycarbonate/carbon-nanotubes hybrid membranes were fabricated using drawable nanotubes that maintained the porosity and provided electrical conductivity to the membrane. Less than 25 V potential and 2-3 W power increase membrane temperature to 100°C in ~10 s. This temperature is above what most microbial life, bacteria and viruses can handle. When this membrane was employed, filtered Escherichia coli collected on its surface were successfully annihilated within 1 min. Ohmic heating of this membrane could be an effective solution to combat biofouling and complications associated with membrane-based filtration. This is a novel and highly desirable approach to combat biofouling, due to its simplicity and economic advantage.

Carbon Nanotube Fiber Ionization Mass Spectrometry: A Fundamental Study of a Multi-Walled Carbon Nanotube Functionalized Corona Discharge Pin for Polycyclic Aromatic Hydrocarbons Analysis.

Mass spectrometry continues to tackle many complicated tasks, and ongoing research seeks to simplify its instrumentation as well as sampling. The desorption electrospray ionization (DESI) source was the first ambient ionization source to function without extensive gas requirements and chromatography. Electrospray techniques generally have low efficiency for ionization of nonpolar analytes and some researchers have resorted to methods such as direct analysis in real time (DART) or desorption atmospheric pressure chemical ionization (DAPCI) for their analysis. In this work, a carbon nanotube fiber ionization (nanoCFI) source was developed and was found to be capable of solid phase microextraction (SPME) of nonpolar analytes as well as ionization and sampling similar to that of direct probe atmospheric pressure chemical ionization (DP-APCI). Conductivity and adsorption were maintained by utilizing a corona pin functionalized with a multi-walled carbon nanotube (MWCNT) thread. Quantitative work with the nanoCFI source with a designed corona discharge pin insert demonstrated linearity up to 0.97 (R2) of three target PAHs with phenanthrene internal standard. Graphical Abstract ᅟ.

Carbon Nanotube Thread Electrochemical Cell: Detection of Heavy Metals.

In this work, all three electrodes in an electrochemical cell were fabricated based on carbon nanotube (CNT) thread. CNT thread partially insulated with a thin polystyrene coating to define the microelectrode area was used as the working electrode; bare CNT thread was used as the auxiliary electrode; and a micro quasi-reference electrode was fabricated by electroplating CNT thread with Ag and then anodizing it in chloride solution to form a layer of AgCl. The Ag|AgCl coated CNT thread electrode provided a stable potential comparable to the conventional liquid-junction type Ag|AgCl reference electrode. The CNT thread auxiliary electrode provided a stable current, which is comparable to a Pt wire auxiliary electrode. This all-CNT thread three electrode cell has been evaluated as a microsensor for the simultaneous determination of trace levels of heavy metal ions by anodic stripping voltammetry (ASV). Hg2+, Cu2+, and Pb2+ were used as a representative system for this study. The calculated detection limits (based on the 3σ method) with a 120 s deposition time are 1.05, 0.53, and 0.57 nM for Hg2+, Cu2+, and Pb2+, respectively. These electrodes significantly reduce the dimensions of the conventional three electrode electrochemical cell to the microscale.

Flexible Micro-Supercapacitor Based on Graphene with 3D Structure.

Flexible micro-supercapacitors (MSCs) are constructed by 3D graphene from chemical vapor deposition. Without using any binder or metal current collector, the as-prepared 3D graphene MSC exhibits good flexibility, excellent cyclic life, and high areal capacitance of 1.5 mF cm-2 at a scan rate of 10 V s-1 . The electrochemical performance is further improved by oxygen plasma functionalization.

Mechanical Strength Improvements of Carbon Nanotube Threads through Epoxy Cross-Linking.

Individual Carbon Nanotubes (CNTs) have a great mechanical strength that needs to be transferred into macroscopic fiber assemblies. One approach to improve the mechanical strength of the CNT assemblies is by creating covalent bonding among their individual CNT building blocks. Chemical cross-linking of multiwall CNTs (MWCNTs) within the fiber has significantly improved the strength of MWCNT thread. Results reported in this work show that the cross-linked thread had a tensile strength six times greater than the strength of its control counterpart, a pristine MWCNT thread (1192 MPa and 194 MPa, respectively). Additionally, electrical conductivity changes were observed, revealing 2123.40 S·cm-1 for cross-linked thread, and 3984.26 S·cm-1 for pristine CNT thread. Characterization suggests that the obtained high tensile strength is due to the cross-linking reaction of amine groups from ethylenediamine plasma-functionalized CNT with the epoxy groups of the cross-linking agent, 4,4-methylenebis(N,N-diglycidylaniline).

Optically transparent carbon nanotube film electrode for thin layer spectroelectrochemistry.

Carbon nanotube (CNT) film was evaluated as an optically transparent electrode (OTE) for thin layer spectroelectrochemistry. Chemically inert CNT arrays were synthesized by chemical vapor deposition (CVD) using thin films of Fe and Co as catalysts. Vertically aligned CNT arrays were drawn onto a quartz slide to form CNT films that constituted the OTE. Adequate conductivity and transparency make this material a good OTE for spectroelectrochemistry. These properties could be varied by the number of layers of CNTs used to form the OTE. Detection in the UV/near UV region down to 200 nm can be achieved using these transparent CNT films on quartz. The OTE was characterized by transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, UV-visible spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and thin layer spectroelectrochemistry. Ferricyanide, tris(2,2'-bipyridine) ruthenium(II) chloride, and cytochrome c were used as representative redox probes for thin layer spectroelectrochemistry using the CNT film OTE, and the results correlated well with their known properties. Direct electron transfer of cytochrome c was achieved on the CNT film electrode.

Free-standing carbon nanotube-titania photoactive sheets.

We report on the development of a new photoactive material via titania (TiO2) nanoparticle deposition on free-standing aligned carbon nanotube (CNT) sheets. Controlling homogeneous dispersion of negatively charged TiO2 nanoparticles, achieved by adjusting pH higher than the point of zero charge (PZC), influenced electrochemical deposition of TiO2 on CNT sheets substrate. Varying deposition time with constant voltage, 5 V allowed different thickness of TiO2 to be deposited layer on the CNT sheets. The thickness and morphology of CNT-TiO2 sheets was verified by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). Electrochemical experiments show that diffusion coefficient of Fe(CN)6(3-) was 5.56×10(-6) cm(2) s(-1) at pristine CNT sheets and 2.19×10(-6) cm(2) s(-1) at the CNT-TiO2 sheets. Photocatalytic activity for CNT-TiO2 sheets exhibits high photocurrent density (when deposition time=30 min, 4.3 µA cm(-2) in N2, 13.4 µA cm(-2) in CO2). This paper proved a possibility to use CNT-TiO2 sheets based on highly-aligned CNT sheets substrate as new photoactive material.