Partially Oxidized Graphene/Metallic Single‐Walled Carbon Nanotubes Film‐Coated Electrode for Nanomolar Detection of Dopamine

Enriched metallic single‐walled carbon nanotubes (mSWCNTs) were dispersed in aqueous solution of partially oxidized graphene (po‐Gr). As‐prepared po‐Gr/mSWCNTs suspension was used to modify glassy carbon electrode (GCE) surface, which showed high electrocatalytic activity for dopamine (DA) oxidation in pH 7.0 phosphate buffered saline (PBS) solution. Using po‐Gr/mSWCNTs/GCE we could detect DA from 350 to 3600 nM, with a detection limit down to 25 nM in physiological condition (in pH 7.0 PBS); whereas, po‐Gr/GCE (without mSWCNTs) and bare GCE produced measurable signals only at or above 200 nM DA. Thus, the po‐Gr/mSWCNTs film we fabricated is a promising nanomaterial for fabrication of biosensors for nanomolar detection of DA.     

多巴胺在电沉积石墨烯修饰碳分子线电极上的电化学测定

以分子线二苯乙炔为修饰剂和粘合剂制备了一种新型的碳糊电极-碳分子线电极(CMWE),并以其为基底电极采用电化学还原法将石墨烯(GR)沉积到CMWE表面得到电沉积石墨烯修饰碳分子线电极(GR/CMWE)。考察了多巴胺(DA)在该修饰电极上的电化学行为。实验结果显示DA在GR/CMWE上出现了1对峰形良好的氧化还原峰,与裸电极相比,该氧化还原峰的电流增大,峰电位差减小,表明修饰电极对DA的电化学反应有催化作用。在最佳实验条件下峰电流与DA浓度在8.0×10-7~2.0×10-3mol/L范围内呈良好的线性关系,检出限(3σ)为2.55×10-7mol/L。将该电极用于多巴胺注射液样品的检测,结果满意。     

Electrochemical Sensor for the Quantification of Dopamine Using Glassy Carbon Electrodes Modified with Single‐Wall Carbon Nanotubes Covalently Functionalized with Polylysine

We report a dopamine electrochemical sensor based on the modification of glassy carbon electrodes (GCE) with polylysine‐functionalized single‐wall carbon nanotubes (SWCNT‐PLys). The resulting electrodes (GCE/SWCNT‐PLys) showed a significant improvement in the electrooxidation of dopamine with drastic decrease in the peak potentials separation and important enhancement in the associated currents. Dopamine was detected by differential pulse voltammetry‐adsorptive stripping with medium exchange at nanomolar levels even in the presence of high excess of ascorbic and uric acids. The sensor was successfully used for the quantification of dopamine in urine samples enriched with the neurotransmitter.     

Electrochemical Pretreatment of Amino‐Carbon Nanotubes on Graphene Support as a Novel Platform for Bilirubin Oxidase with Improved Bioelectrocatalytic Activity towards Oxygen Reduction

The electrochemical conditioning of amino‐carbon nanotubes (CNTs) on a graphene support in an alkaline solution is used to produce ?NHOH as hydrophilic functional groups for the efficient immobilization of bilirubin oxidase enzyme. The application of the immobilized enzyme for the direct electrocatalytic reduction of O₂ is investigated. The onset potential of 0.81 V versus NHE and peak current density of 2.3 mA cm^?2 for rotating modified electrode at 1250 rpm, indicate improved biocatalytic activity of the proposed system for O₂ reduction.     

纳米碳管电极的制备与电化学检测性能研究

纳米碳管由于其独特的物理和化学性能及广阔的应用前景而备受关注,其相关研究涉及到众多领域[1￣3]。在电化学分析领域,与其它碳电极材料相比,纳米碳管电极具有较大的电极表面积和较高的电子传递速率,其使用能增大响应电流、降低检出限,是目前电化学分析电极中一个十分引人注目     

Electrochemical Detection of Human Interleukin-15 using a Graphene Oxide-Modified Screen-Printed Carbon Electrode

Biofunctionalizing a simple and disposable graphene oxide-modified screen-printed carbon electrode with anti-interleukin-15 antibodies has been successfully demonstrated for the first time for the label-free electrochemical detection of interleukin-15, a biomarker of early HIV infection. To improve the electrochemical reactivity and introduce carboxylic groups on the surface of screen-printed carbon electrode, high-quality graphene oxide was used for the modification of screen-printed carbon electrode. With simple modification of the screen-printed carbon electrode, the device exhibited satisfactory sensitivity, selectivity, stability, reproducibility, and regenerability. The immunosensor provided a detection limit of 3.51?ng?mL^?1 and a sensitivity of 0.5655?µA cm^?2?mL?ng^?1. The simply constructed immunosensor thus rendered promising device for immunoreactions on the surface of the electrode.     

有序介孔碳/石墨烯/镍泡沫的制备及其对多巴胺的高灵敏度和高选择性检测

柔性生物传感器在可穿戴电子设备中有着广泛的应用前景. 为了获得柔性电化学多巴胺传感器,作者在本工作中首先在镍泡沫表面通过化学气相沉积生长石墨烯,随后通过高温碳化嵌段共聚物与酚醛树脂在石墨烯表面共组装形成的薄膜制备了有序介孔碳/石墨烯/镍泡沫（OMC/G/Ni）复合材料. 其中,镍泡沫可以为复合材料提供具有高导电性和良好柔韧性的金属骨架,而具有垂直排列介孔阵列的有序介孔碳层为复合材料提供了高的电活性表面积,且有利于活性位点的暴露. 值得注意的是,夹在有序介孔碳层和镍泡沫之间的石墨烯极大地增强了各组分之间的相容性,有利于进一步提升复合材料的电化学性能. 作为电化学传感器中的工作电极,OMC/G/Ni体现出优异的多巴胺检测能力. 不但具有宽的线性检测范围（0.05 ~ 58.75 μmol·L^-1）和低检测限（0.019 μmol·L^-1）,还具有良好的选择性、重现性和稳定性. 此外,OMC/G/Ni在弯曲状态下依旧能够保持对多巴胺的高检测能力,证明了其在柔性生物传感器中的应用潜力.     

Recent Applications of Carbon Nanomaterials for microRNA Electrochemical Sensing

MicroRNA (miRNA) is an important tumor marker in the human body, and its early detection has a great influence on the survival rate of patients. Although there are many detection methods for miRNA at present such as northern blotting, real-time quantitative polymerase chain reaction, microarrays, and others, electrochemical biosensors have the advantages of low detection cost, small instrument size, simple operation, non-invasive detection and low consumption of reagents and solvents, and thus they play an important role in the early detection of cancer. In addition, with the development of nanotechnology, nano-biosensors show great potential. The application of various nanomaterials in the development of electrochemical biosensor has greatly improved the detection sensitivity of electrochemical biosensor. Among them, carbon nanomaterials which have unique electrical, optical, physical and chemical properties have attracted increasing attention. In particular, they have a large surface area, good biocompatibility and conductivity. Therefore, carbon nanomaterials combined with electrochemical methods can be used to detect miRNA quickly, easily and sensitively. In this review, we systematically review recent applications of different carbon nanomaterials (carbon nanotubes, graphene and its derivatives, graphitic carbon nitride, carbon dots, graphene quantum dots and other carbon nanomaterials) for miRNA electrochemical detection. In addition, we demonstrate the future prospects of electrochemical biosensors modified by carbon nanomaterials for the detection of miRNAs, and some suggestions for their development in the near future.     

碳纳米管基复合材料研究进展

碳纳米管基复合材料具有优良的性能,已在化学、化工、材料、生物、医学等领域受到广泛关注.本文主要综述了功能材料包覆碳纳米管的制备方法及其力学、磁学、光学、电化学等性质,以及当前研究的焦点和存在的问题.     

Application of Different Carbon Materials for Carbon Paste Electrodes to Simultaneous Electrochemical Detection of four DNA Bases with High Simpleness

Three different carbon materials, graphite, graphene and multiwalled carbon nanotubes (MWCNTs), were applied to fabricate carbon paste electrodes and used directly as working electrodes without any further modification in a simple electrochemical system for simultaneous detection of four DNA bases, guanine, adenine, thymine and cytosine. EIS and SEM were used to characterize the formed carbon paste electrodes made from different carbon nanomaterials and silicon oil, respectively. Conditions for bases detection were studied, such as ratio of carbon nanomaterials to silicon oil, types of buffer saline and pH. An unexpected result was discovered that compared with graphite and graphene, MWCNTs in carbon paste electrodes were not able to obtain admirable electrochemical behavior, the possible reason of which was preliminary discussed. Individual and simultaneous detection of four bases were successfully carried out, with acceptable linear ranges and low detection limits. Furthermore, this facile method had admirable reproducibility, stability and acceptable recovery in real urine sample (97.62 % ∼103.36 %), indicating certain practical potential.     

碳纳米管修饰电极对多巴胺和肾上腺素的电分离及同时测定

研究了多巴胺 (DA)和肾上腺素 (EP)在多壁碳纳米管 (MWNT)修饰电极上的电化学性质 ,发现该修饰电极对神经递质DA和EP有显著的增敏和电分离作用。还原峰电位差达ΔEp=390mV ,可同时测定DA和EP。DA和EP的还原峰电流与其浓度分别在 2 .0× 10 -6～ 1.0× 10 -3 mol/L和 1.0× 10 -6～ 1.0× 10 -3 mol/L浓度范围内呈良好的线性关系 ;方法的检出限分别为 1× 10 -6mol/L和 5× 10 -7mol/L。由于抗坏血酸 (AA)在MWNT修饰电极上的氧化是不可逆的 ,因此利用还原峰进行测定 ,消除了AA对DA和EP的干扰     

DNA Induced FePt Bimetallic Nanoparticles on Reduced Graphene Oxide for Electrochemical Determination of Dopamine

FePt bimetallic nanoparticles were formed on reduced graphene oxide(rGO) with the help of double-stranded DNA(dsDNA) via a simple and universal route to obtain a FePt/DNA-rGO composite. The FePt nanoparticles with an average size of about 5 nm were well dispersed on rGO. FePt/DNA-rGO modified glassy carbon electrode(GCE) exhibited excellent electrocatalytic activity for the oxidation of dopamine(DA) with a detection limit of 100 nmol/L(S/N = 3). In addition, the FePt/DNA-rGO based electrochemical sensor showed an excellent selectivity for DA in the presence of ascorbic acid(AA), uric acid(UA) and other interference reagents. The as-prepared electrochemical biosensor shows great promise in the application of clinical diagnostics.     

Electrochemical Determination of Dopamine with Ruthenium(III)-Modified Glassy Carbon and Screen-Printed Electrodes

Here is reported for the first time the application of sodium bis[N-2-oxyphenyl-5-bromosalicylideneiminato-ONO]ruthenate(III) as a mediator with multiwalled carbon nanotubes and Nafion at glassy carbon and screen-printed electrodes for the determination of dopamine in the presence of ascorbic acid. Electrochemical studies were performed using cyclic voltammetry, differential pulse voltammetry, and flow injection amperometry. In flow injection mode, the flow rate was 0.4?mL?min^?1, the injection volume 250?µL, and the operation potential 0.05?V vs. Ag/AgCl. In 0.1M pH 7.5 phosphate buffer, the sensor provided a linear dynamic range up to 50?mg?L^?1 dopamine with a detection limit of 0.11?±?0.04?mg?L^?1. The sensor was used for the determination of dopamine in ampoules of dopamine hydrochloride by cyclic voltammetry, differential pulse voltammetry, and flow injection amperometry.     

A Nanocomposite Containing Carbon Nano-onions and Polyaniline Nanotubes as a Novel Electrode Material for Electrochemical Sensing of Daidzein

Glassy carbon electrode (GCE) were modified with nanocomposites containing conductive polyaniline nanotubes (PANI_nt) and carbon nano-onions (CNOs). Herein we report a simple and sensitive way for daidzein (DA) determination at concentrations between 1 and 10 μM by linear sweep voltammetry using GCE/PANI_nt/CNOs system. The DA electrochemical behavior was examined in two buffer environments (pH 7.5 and 4.5) using electrodes modified with the oxidized CNOs or their derivatives containing carboxyl and benzylamino functional groups. The direct electrooxidation of DA was observed at +0.65 V and +0.8 V at pH 7.5 and at +0.7 V and +1.1 V vs. Ag/AgCl at pH 4.5.     

Zirconium Molybdate Nanocomposites’ Sensing Platform for the Sensitive and Selective Electrochemical Detection of Adefovir

Adefovir (ADV) is an anti-retroviral drug, which can be used to treat acquired immune deficiency syndrome (AIDS) and chronic hepatitis B (CHB), so its quantitative analysis is of great significance. In this work, zirconium molybdate (ZrMo₂O₈) was synthesized by a wet chemical method, and a composite with multi-walled carbon nanotubes (MWCNTs) was made. ZrMo₂O₈-MWCNTs composite was dropped onto the surface of a glassy carbon electrode (GCE) to prepare ZrMo₂O₈-MWCNTs/GCE, and ZrMo₂O₈-MWCNTs/GCE was used in the electrochemical detection of ADV for the first time. The preparation method is fast and simple. The materials were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and cyclic voltammetry (CV). It was electrochemically analysed by differential pulse voltammetry (DPV). Compared with single-material modified electrodes, ZrMo₂O₈-MWCNTs/GCE showed a vastly improved electrochemical response to ADV. Moreover, the sensor complements the study of the electrochemical detection of ADV. Under optimal conditions, the proposed electrochemical method showed a wide linear range (from 1 to 100 μM) and a low detection limit (0.253 μM). It was successfully tested in serum and urine. In addition, the sensor has the advantages of a simple preparation, fast response, good reproducibility and repeatability. It may be helpful in the potential applications of other substances with similar structures.     

Disposable Multiwalled Carbon Nanotube Printed Film Electrochemical Determination of Acetaminophen,Dopamine, and Uric Acid

A novel printed film consisting of multiwalled carbon nanotubes was fabricated on a polyethylene terephthalate substrate by means of a mass flexographic printing process. Potential applications of this film for electrochemical biosensing were examined through the oxidation of acetaminophen, dopamine, and uric acid in phosphate buffer (pH 7.0). The results demonstrate that the printed carbon nanotube film exhibits an enhanced electrochemical response toward these molecules. Dopamine and uric acid did not interfere with each other and, thus, their simultaneous determination may be performed. The results suggest the mass flexographic printing technique has potential application for the construction of low-cost, precise, and disposable multiwalled carbon nanotube films.     

一种估算多壁碳纳米管电化学容量的方法

Five kinds of multi-walled carbon nanotubes were prepared by CVD(Chemical Vapour Deposition) and purified under the same conditions, then were used as electrodes for super capacitors in order to compare their performance. The differences measured in terms of specific capacitance by galvanostatic cycling were presented, porosity measurements using nitrogen at 77 K made on carbon nanotubes allowd a better understanding of the electrochemical behavior of these carbon nanotubes. The experiment results show that pore diameter in the range of more than 3nm is required to maximize the capacitance in the electrolyte of 1.0 mol·L^-1 LiClO₄/EC+DEC(V_EC∶V_DEC=1∶1), and the BET surface area contributed by this extent is almost linear with the specific capacitance, in which an average value is about 0.11 F·m^-2, and the specific capacitance estimated from above is very close to the value by experiment.     

8-羟基脱氧鸟苷在壳聚糖/石墨烯修饰电极上的电化学及DNA氧化损伤检测

采用循环伏安(CV)、线性扫描伏安(LSV)和示差脉冲伏安(DPV)等方法研究了8-羟基脱氧鸟苷(8-OHdG)在壳聚糖(Chi)/石墨烯(GR)修饰的玻碳电极(GCE)上的电化学行为,8-OHdG在该修饰电极上氧化峰电流与其浓度在3.5×10-7~1.4×10-4 mol/L范围内呈良好的线性关系,检测限为6.4×10-8 mol/L(S/N=3)。 将Chi/GR/GCE用于检测DNA氧化损伤,8-OHdG在修饰电极上的氧化峰电流与损伤的DNA质量浓度在10~300 mg/L范围内呈良好的线性关系,损伤DNA检出限为0.026 mg/L(S/N=3)。     

石墨烯修饰玻碳电极对多巴胺的电催化氧化

通过3-巯丙基三乙氧基硅烷(METMS)将氧化石墨烯(GO)固载到玻碳电极(GCE)表面, 用电化学方法还原GO制备石墨烯修饰玻碳电极(rGO-METMS-GCE). 利用傅里叶变换红外光谱(FTIR)、 拉曼光谱(Raman)、 扫描电子显微镜(SEM)和原子力显微镜(AFM)等技术对GO和rGO-METMS-GCE的结构和表面形貌进行表征. 采用循环伏安(CV)和差分脉冲溶出伏安(DPV)法研究了rGO-METMS-GCE对多巴胺(DA)的电催化氧化性能及反应机理. 结果表明, 与裸GCE相比, DA在rGO-METMS-GCE电极上的氧化还原峰电流(i_pa和i_pc) 增大4倍, 氧化峰电位负移106 mV, 氧化峰与还原峰电位差(ΔE_p)从202 mV降低至66 mV, DA电化学氧化可逆性明显改善, 表明rGO-METMS-GCE对DA电化学氧化具有显著电催化作用. DA在rGO-METMS-GCE上的反应机理为单电子转移过程.