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The development of integrated analytical devices is crucial for advancing next-generation point-of-care platforms. Herein, we describe a facile synthesis of a strongly catalytic and durable Nitrogen-doped graphene oxide decorated platinum cobalt (NGO-PtCo) nanocomposite that is conjugated with target-specific DNA aptamer (i-e. MUC1) and grown on carbon fiber. Benefitting from the combined features of the high electrochemical surface area of N-doped GO, high capacitance and stabilization by Co, and high kinetic performance by Pt, a robust, multifunctional, and flexible nanotransducer surface was created. The designed platform was applied for the specific detection of a blood-based oncomarker, CA15-3. The electrochemical characterization proved that nanosurface provides a highly conductive and proficient immobilization support with a strong bio-affinity towards MUC1 aptamer. The specific interaction between CA15-3 and the aptamer alters the surface properties of the aptasensor and the electroactive signal probe generated a remarkable increase in signal intensity. The sensor exhibited a wide dynamic range of 5.0 × 10-2 -200 U mL-1, a low limit of detection (LOD) of 4.1 × 10-2 U mL-1, and good reproducibility. The analysis of spiked serum samples revealed outstanding recoveries of up to 100.03 %, by the proposed aptasensor. The aptasensor design opens new revelations in the reliable detection of tumor biomarkers for timely cancer diagnosis.
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Accurate detection of ascorbic acid (AA) plays a significant role in food and human physiological processes. Herein, a three-dimensional flexible leaf-like nitrogen-doped hierarchical carbon nanoarrays with high-density carbon nanotube "tentacle" architecture (NC/CNT-Co), which possesses high specific surface area, plenty of active defect sites, and various pore size distributions, was synthesized by the pyrolysis of zeolitic imidazolate framework (ZIF(Co)), while g-C3N4 acted as carbon source and heteroatom doping agent. Benefiting from its unique structure and surface properties, a selective and highly sensitive AA sensor was developed using this material. Compared to powder materials, NC/CNT-Co modified CF (CF@NC/CNT-Co) which don't be extra decorated, exhibits lower detection limit (1 µM), a wider linear range (20-1400 µM), and better stability, showing higher performance in electrocatalysis and detection of AA. Furthermore, CF@NC/CNT-Co also demonstrates high resistance to interference and fouling in AA detection. Particularly, the prepared CF@NC/CNT-Co electrode could determine AA in beverage samples with a recovery rate of 96.3-103.5 %. Therefore, the three-dimensional NC/CNT-Co hierarchical structure can be provided as an original electrode nanomaterial suitable for the selective and sensitive detection of AA, with a wide range of practical applications from food analysis to the pharmaceutical industry.
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Structural supercapacitors (SSCs) are multifunctional energy storage composites (MESCs) that combine the mechanical properties of fiber-reinforced polymers and the electrochemical performance of supercapacitors to reduce the overall mass in lightweight applications with electrical energy consumption. These novel MESCs have huge potentials, and their properties have improved dramatically since their introduction in the early 2000's. However, the current properties of SSCs are not sufficient for complete energy supply of electrically driven devices. To overcome this drawback, the aim of the current study is to identify key areas for enhancement of the multifunctional performance of SSCs. Critical modification paths for the SSC constituents are systematically analyzed. Special focus is given to the improvement of carbon fiber-based electrodes, the selection of structural electrolytes and the implementation of separators for the development of more efficient SSCs. Finally, current SSCs are compared in terms of their multifunctionality including material combinations and modifications.
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Objective.Carbon fiber (CF) is good for chronic neural recording due to the small diameter (7µm), high Young's modulus, and low electrical resistance, but most high-density carbon fiber (HDCF) arrays are manually assembled with labor-intensive procedures and limited by the accuracy and repeatability of the operator handling. A machine to automate the assembly is desired.Approach.The HDCF array assembly machine contains: (1) a roller-based CF extruder, (2) a motion system with three linear and one rotary stages, (3) an imaging system with two digital microscope cameras, and (4) a laser cutter. The roller-based extruder automatically feeds single CF as raw material. The motion system aligns the CF with the array backend then places it. The imaging system observes the relative position between the CF and the backend. The laser cutter cuts off the CF. Two image processing algorithms are implemented to align the CF with the support shanks and circuit connection pads.Main results.The machine was capable of precisely handling 6.8µm carbon fiber electrodes (CFEs). Each electrode was placed into a 12µm wide trenches in a silicon support shank. Two HDCF arrays with 16 CFEs populated on 3 mm shanks (with 80µm pitch) were fully assembled. Impedance measurements were found to be in good agreement with manual assembled arrays. One HDCF array was implanted in the motor cortex in an anesthetized rat and was able to detect single unit activity.Significance.This machine can eliminate the manual labor-intensive handling, alignment and placement of single CF during assembly, providing a proof-of-concepts towards fully automated HDCF array assembly and batch production.
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Fenômenos Eletrofisiológicos , Ratos , Animais , Fibra de Carbono , Microeletrodos , Eletrodos Implantados , Impedância ElétricaRESUMO
Dopamine (DA) is an essential type of neurotransmitter in the central nervous system. DA neurons usually exist as nuclei which are mainly found in the ventral tegmental area (VTN) and substantia nigra pars compacta (SNc). Parkinson's disease, epilepsy, schizophrenia and other diseases are all related to the abnormal metabolism of DA. Compared with traditional DA detection methods such as spectrophotometry and electrophoresis, electrochemical sensing technology has high detection efficiency, high sensitivity, fast and convenient real-time detection, which is recognized as the most effective method for measuring neurotransmitters in vivo. The working electrode of an electrochemical sensor can be generally divided into the conventional electrode and the microelectrode according to its size. The microelectrode shows excellent properties such as high sensitivity, high temporal resolution, and high spatial resolution while detecting DA, which makes it possible to detect neurotransmitters in vivo. In order to further investigate the role of DA in regulating action, emotion, and cognition, and to further clarify the relationship between DA abnormalities or lack and neurological diseases such as Parkinson, more and more researchers apply microelectrode-based electrochemistry sensing technology to detect DA in vivo. This article reviews recent applications of microelectrodes and the latest researches in DA detection in vivo, focusing on the following three types of microelectrodes: (1) non-nanomaterial-modified carbon fiber microelectrodes (CFE); (2) nanomaterial-modified microelectrodes; (3) microelectrode arrays (MEA).
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Dopamina , Neurotransmissores , Dopamina/análise , Eletroquímica , Microeletrodos , TecnologiaRESUMO
Many psychiatric drugs are weak bases that accumulate in and are released from synaptic vesicles, but the functional impact of vesicular drug release is largely unknown. Here, we examine the effect of vesicular release of the anxiolytic antipsychotic drug cyamemazine on electrically evoked striatal dopamine responses with fast scan cyclic voltammetry. Remarkably, in the presence of nanomolar extracellular cyamemazine, vesicular cyamemazine release in the brain slice can increase dopamine responses 30-fold. Kinetic analysis and multiple stimulation experiments show that this occurs by inducing delayed emptying of the releasable dopamine pool. Also consistent with increased dopamine release, an antagonist (dihydro-ß-erythroidine) implicates nicotinic acetylcholine receptors, which can directly cause dopamine release, in the vesicular cyamemazine effect. Therefore, vesicular release of cyamemazine can dramatically enhance dopaminergic synaptic transmission, possibly by recruiting an excitatory cholinergic input to induce an extra phase of release. More generally, this study suggests that synaptic drug release following vesicular accumulation by acidic trapping can expand psychiatric drug pharmacodynamics.
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Antipsicóticos/farmacocinética , Corpo Estriado/efeitos dos fármacos , Corpo Estriado/metabolismo , Dopamina/metabolismo , Fenotiazinas/farmacocinética , Transmissão Sináptica/efeitos dos fármacos , Vesículas Sinápticas , Animais , Liberação Controlada de Fármacos , Masculino , Ratos , Ratos Sprague-DawleyRESUMO
Enrichment of cadmium ion (Cd2+) from the environment may lead to kidney disease and weakened immunity in the body. Current techniques are not convenient enough to measure Cd2+ concentration in the environment due to low sensitivity and poor linear range. In this paper, a new measurement technique is proposed using a new sensing electrode made of nano-copper-enhanced carbon fiber. Nano-copper was deposited onto the surface of carbon fiber to enhance the current concentration and mass transfer rate of Cd2+ during measurement, which improved the electrochemical detection sensitivity significantly (by up to 3.7 × 108 nA/nM) and broadened the linear range to 10~105 nM. This device provides a low-cost solution for measuring Cd2+ concentration in the environment.
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Here, we describe the utility of a carbon fiber (CF) electrode that is inexpensive, simple, and flexible and can be embedded with elastomeric nanocomposite piezo-resistive sensors fabricated from silicone rubber (Ecoflex) blended with carbon nanotubes (CNTs) and various wt % of silicone thinner to tune the sensitivity and softness range. The performance of the CF electrode was evaluated on the basis of piezo-resistive responses from the sensors subjected to dynamic sinusoidal compressive strains at different levels and frequencies. The responses were positive-pressure effects with rate-dependent asymmetric nonlinear hysteresis characteristics. Developing a mathematical model to describe the rate-dependent asymmetric nonlinear hysteresis behavior is technically impossible; therefore, we employed artificial intelligence-based hysteresis modeling, long short-term memory recurrent neural network, to describe the hysteresis nonlinearity. The debonding strength of the CF electrode was determined in the pull-off testing and was found to be much higher than that of a copper wire electrode. The debonding mechanism was further elucidated via an in situ resistance profile. The importance of a robust conductive interface between a CF electrode and a nanocomposite was experimentally demonstrated. It was found that the inherent piezo-resistance of the CF was negligible compared with the piezo-resistance of the sensor; therefore, the signals from the sensor were free of interference. We believe CF-embedded tunable piezo-resistive sensors could be used in biomedical devices, artificial e-skins, robotic touch applications, and flexible keyboards where the required stretchability of the electrode can be introduced via an appropriate geometrical design.
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Even though large number of individually addressable electrodes can be effectively assembled in a small area, electrochemical detection methods have a relatively limited ability to detect multiple analytes compared to microdialysis probes and other analytic techniques. Here, we report a facile method for the electro-addressable functionalization of a probe comprising of closely spaced three individually addressable carbon fiber electrodes (CFEs) for the detection of nucleic acids. First, a multi electrode array probe comprising three adjacent CFEs was fabricated through pulling a three-barrel glass capillary with a single carbon fiber in each barrel. Second, electropolymerization based doping was used for the electro-addressable functionalization of the multi-electrode array probe. To demonstrate that the current strategy works, anti-miR-34a was electrografted on only one of three electrodes by the electropolymerization of pyrrole on a specific electrode. A second electrode was coated only with polypyrrole (PPy) and the third was left unmodified. The results demonstrate that the present strategy has great potential for constructing multiplex nucleic acid micro/nano biosensors for local and in situ detection of multiple nucleic acid molecules, such as miRNAs at a time.
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Técnicas Eletroquímicas , MicroRNAs/análise , Eletrodos , Humanos , Polímeros/química , Pirróis/químicaRESUMO
A method for simultaneous electrochemical detection of brain tissue PO2 (PtO2) and pH changes together with neuronal activity using a modified form of fast cyclic voltammetry with carbon fiber electrodes is described. This technique has been developed for in vivo applications and recordings from discrete brain nuclei in experimental animals. The small size of the carbon fiber electrode (â7 µm, length <100 µm) ensures minimal disruption of the brain tissue and allows recordings from small brain areas. Sample rate (up to 4 Hz) is sufficient to resolve rapid changes in PtO2 and pH that follow changes in neuronal activity and metabolism. Rapid switching between current and voltage recordings allows combined electrochemical detection and monitoring of extracellular action potentials. For simultaneous electrochemical detection of PtO2 and pH, two consecutive trapezoidal voltage ramps are applied with double differential-subtraction of the background current. This enables changes in current caused by protons and oxygen to be detected separately with minimal interference between the two. The profile of PtO2 changes evoked by increases in local neuronal activity recorded using the described technique was very similar to that of blood-oxygen-level-dependent responses recorded using fMRI. This voltammetric technique can be combined with fMRI and brain vessel imaging to study the metabolic mechanisms underlying neurovascular coupling response with much greater spatial and temporal resolution than is currently possible.
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Pure N mono- and N/P dual-doped cotton-stalk-derived activated carbon fibers (CSCFs) were synthesized by steam, HNO3(CSCF-N), NH3(CSCF-A), and (NH4)3PO4(CSCF-N/P) treatments. This study investigated how three different N/P modifiers affected the pore structure, chemical property, H2O2 generation ability, and electrocatalytic activity of methylene blue (MB) degradation of CSCFs in an electric-Fenton system. Results confirmed that the three employed treatments effectively doped N/P in the carbon lattice and slightly changed the pore structures. NH3 and (NH4)3PO4 were the most effective modifiers for the N mono-doping and N/P dual-doping of CSCFs, respectively. Among the fabricated CSCFs, the N/P dual-doped CSCF-N/P demonstrated the highest electrochemical activity in an electro-Fenton system, followed by the N mono-doped CSCF-A, the CSCF-N, and the raw CSCF. In contrast to the CSCF electrode, the CSCF-N/P electrode exhibited enhanced H2O2, OH generation, and MB degradation efficiency by 42%, 41%, and 35%, respectively. Under optimum conditions, the electrochemical decolorization efficiency of MB (initial concentration, 100 mg L-1) of the CSCF-N/P reached 93% after 150 min and was 24.1% higher than that of the CSCF. By the tenth cycle, 82.2% of the MB could still be decomposed, suggesting the excellent stability and reusability of the N/P co-doped CSCF electrode. The outstanding electrocatalytic performance of the CSCF-N/P electrode is primarily due to the simultaneous doping of active N/P sites with low activation energy and introduction of mesopores with strong trapping forces for MB. The MB reduction catalyzed by CSCF electrodes followed pseudo-first-order kinetics, and the reaction rate depended on the modifiers.
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Carbono/química , Peróxido de Hidrogênio/química , Azul de Metileno/química , Poluentes Químicos da Água/química , Fibra de Carbono , EletrodosRESUMO
Dopamine plays crucial roles in a broad spectrum of brain functions, and neural circuit mechanisms underlying dopaminergic regulation have been intensively studied in the past decade. As larval zebrafish have relatively simple and highly conserved dopaminergic systems, it can serve as an ideal vertebrate animal model to tackle this issue at a whole-brain scale. For this purpose, it is important to develop methods for monitoring endogenous dopamine release in intact larval zebrafish. Here, we developed a real-time method to monitor dopamine release at high spatiotemporal resolution in the brain of awake larval zebrafish using carbon fiber microelectrodes. As an example for application, we combined this method with genetic tools and in vivo calcium imaging and found that food extract can activate pretectal dopaminergic neurons, which in turn release dopamine at the visual center through their projection, providing a dopaminergic circuit mechanism for olfactory modulation of visual functions. Thus, our study demonstrates, for the first time, the utility of carbon fiber microelectrodes for monitoring sensory-evoked dopamine release in the brain of an awake small organism. SIGNIFICANCE STATEMENT: With carbon fiber microelectrodes, we have succeeded in monitoring sensory-evoked dopamine release in the brain of an awake small organism for the first time. By elucidating the circuitry origin of the dopamine release, we illustrated the potential application of this method in dissection of the neural circuitry mechanisms underlying dopaminergic neuromodulation.
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Dopamina/metabolismo , Olfato/fisiologia , Vigília/fisiologia , Animais , Animais Geneticamente Modificados , Cálcio/metabolismo , Proteínas da Membrana Plasmática de Transporte de Dopamina/genética , Proteínas da Membrana Plasmática de Transporte de Dopamina/metabolismo , Neurônios Dopaminérgicos/fisiologia , Eletroquímica , Equidae , Proteínas de Fluorescência Verde/genética , Proteínas de Fluorescência Verde/metabolismo , Larva , Terapia a Laser , Microeletrodos , OptogenéticaRESUMO
Locus coeruleus (LC) has noradrenergic nerve terminals projecting to hypothalamus that modulating cardiovascular activity. To study the dynamic characteristics of norepinephrine (NE) release in hypothalamus followed by electrical stimulation in the locus coeruleus in the stress-induced hypertension (SIH) rats, we established the hypertension model rats by stimulations combining noise and foot-shock stress. After the end of modeling, NE release in the hypothalamus by electrical stimulation in LC was studied and NE signal was recorded by carbon fiber electrode. The peak value, the time to peak and half-life period of NE signal in both group rats were analyzed. Furthermore, to clarify the role of angiotensin II type 2 receptors (AT2) in norepinephrine (NE) release and the blood pressure of rat model of stress-induced hypertension, we intraperitoneally administered the AT2 receptor antagonist PD123319 (AT2 receptor antagonist, 0.3mg/kg, i.p.) and intracerebroventricularly injection of CGP42112 (AT2 receptor agonist, 6µg/5µl, i.c.v.) to adult male rats. We found the peak value of NE signal in the hypothalamus followed by electrical stimulation in the LC in SIH rats were higher than that in controls (P<0.01). Intraperitoneal injection of PD123319 (AT2 receptor antagonist) potentiated electrical stimulation in the LC induced NE release in the hypothalamus in SIH rats and elevated blood pressure (P<0.05), whereas intracerebroventricular injection of CGP42112 (AT2 receptor agonist) inhibited the NE release and reduced the heart rate (P<0.05). These results suggest that combining noise and foot-shock stresses increased the blood pressure and the secretion of NE in the hypothalamus followed by electrical stimulation in the LC in rats. AT2 receptors can inhibit the secretion of NE from the LC to the hypothalamus. The attenuation of presynaptic action of AT2 receptor may play a role in the pathophysiological mechanism of SIH in rats.
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Hipertensão/fisiopatologia , Locus Cerúleo/metabolismo , Locus Cerúleo/fisiopatologia , Norepinefrina/metabolismo , Receptor Tipo 2 de Angiotensina/fisiologia , Estresse Psicológico/fisiopatologia , Bloqueadores do Receptor Tipo 2 de Angiotensina II/farmacologia , Animais , Pressão Sanguínea/efeitos dos fármacos , Pressão Sanguínea/fisiologia , Modelos Animais de Doenças , Hipotálamo/metabolismo , Imidazóis/farmacologia , Masculino , Oligopeptídeos/farmacologia , Piridinas/farmacologia , Ratos , Ratos Sprague-Dawley , Receptor Tipo 2 de Angiotensina/agonistasRESUMO
This study was aimed to develop a simultaneous determination of zinc and cadmium with carbon fiber electrode by linear sweep stripping voltammetry. Effects of analytical base solution, accumulation potential, ac-cumulation time and scanning velocity were also investigated on the determination. The results showed that in 1 mol·L-1 H2SO4 medium solution, zinc and cadmium had good electrochemical response on the carbon fiber electrode and appeared sensitive anodic stripping peaks at-0.97 V and-0.77 V, respectively. The anodic stripping peak cur-rents and concentrations of zinc and cadmium showed good linear relationships, with correlation coefficients R2 of 0.996 5 and 0.995 4, respectively. The detection limits of zinc and cadmium (S/N=3) were 1.5×10-9 mol·L-1 and 1.0×10-10 mol·L-1, respectively. The average recoveries of zinc and cadmium were 98.9%and 98.1%with the rela-tive standard deviations (RSD) of 2.72%and 2.45%(n=6), respectively. It was concluded that the method of simul-taneous determination of zinc and cadmium with carbon fiber electrode was simple, sensitive and accurate.
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A flow-electrolytical cell containing a strand of micro Au modified carbon fiber electrodes (CFE) has been designedand characterized for use in a voltammatric detector for detecting cysteine using high-performance liquid chromatography. Cysteine is more efficiently electrochemical oxidized on a Au /CFE than a bare gold and carbon fiber electrode. The possible reaction mechanism of the oxidation process is described from the relations to scan rate, peak potentials and currents. For the pulse mode, and measurements with suitable experimental parameters, a linear concentration from 0.5 to 5.0 mg·L(-1) was found. The limit of quantification for cysteine was below 60 ng·mL(-1).