基于碳纳米管的化学修饰电极及电化学生物传感器的研究进展

综述了碳纳米管的结构、合成、纯化、功能化、分散及基于碳纳米管的化学修饰电极和电化学生物传感器的研究进展。     

Carbon Nanotubes Heavy Metal Detection with Stripping Voltammetry: A Review Paper

The challenge of heavy metal detection for environmental, industrial and medical purposes has led to the development of many analytical techniques. Stripping voltammetry is a very sensitive electrochemical method and has been widely used for heavy metal detection. Carbon nanotubes, a well‐studied carbon material with physical and chemical properties suited for electrode material is commonly employed for sensitive and selective metal detection in electrochemistry. This article reviews the recent (2011–2016) applications of carbon nanotubes as an electrode or electrode surface modifier for heavy metals detection with stripping voltammetry.     

基于掺杂碳纳米管的复合体系电化学生物传感器研究

制备了含有铂纳米颗粒(NSPt)的壳聚糖(CHIT)和正硅酸四乙酯(TEOS)溶胶-凝胶溶液,将多壁碳纳米管(MWCNTs)分散于制备的CHIT和TEOS溶胶-凝胶混合物体系,并用高倍透射电镜(TEM)和扫描电子显微镜(SEM)对NSPt-CHIT表面和MWCNTs进行了表征。此种复合膜修饰玻碳电极对过氧化氢有灵敏的电化学响应。通过在此复合膜修饰的玻碳电极上固定葡萄糖氧化酶(GOx)制备了葡萄糖生物传感器。该传感器对葡萄糖在0.05~8 mmol/L范围有线性响应,相关系数为0.996,检出限(S/N=3)为10μmol/L。传感器对葡萄糖有灵敏响应,并有很好的重现性和稳定性,应用于实际样品体系的回收试验,结果良好。     

A Disposable Biosensor for Organophosphorus Nerve Agents Based on Carbon Nanotubes Modified Thick Film Strip Electrode

A disposable biosensor based on acetylcholinesterase‐functionalized acid purified multi‐wall carbon nanotubes (CNTs) modified thick film strip electrode for organophosphorus (OP) insecticides was developed. The degree of inhibition of the enzyme acteylcholinesterase (AChE) by OP compounds was determined by measuring the electrooxidation current of the thiocholine generated by the AChE catalyzed hydrolysis of acteylthiocholine (ATCh). The large surface area and electro‐catalytic activity of carbon nanotubes lowered the overpotential for thiocholine oxidation to 200 mV (vs. Ag/AgCl) without the use of mediating redox species and enzyme immobilization by physical adsorption. The biosensor detected as low as 0.5 nM (0.145 ppb) of the model organophosphate nerve agent paraoxon with good precision, electrode to electrode reproducibility and stability. Analysis of real water sample using the sensor demonstrated the feasibility of the application of the sensor for on site monitoring of OP compounds.     

Electrochemical Sensors Based on Carbon Nanotubes

Carbon nanotubes are attractive new materials. It has been about a decade since carbon nanotubes were discovered. Carbon nanotubes have many outstanding properties and have many practical or potential applications. In this short review we introduce recent advances in carbon nanotubes as potential material for electrochemical sensors. The advantages of carbon nanotubes as sensors are discussed along with future prospects.     

碳纳米管在电分析中的应用

碳纳米管因其独特的特性,自发现以来得到了广泛的关注与应用;本文着重对碳纳米管在电分析中的应用作了综述。     

Applications of Carbon Nanotubes in Electrochemical DNA Biosensors

The discovery of carbon nanotubes (CNTs) about a decade ago has brought fascinating evolutions in electronics, material industry, as well as bio-techniques for DNA analysis, gene therapy, drug delivery etc. It has also dramatically promoted the development of DNA biosensing techniques, especially electrochemical DNA biosensor. The application of CNTs in electrochemical DNA biosensors includes two main aspects: on one hand, using CNTs as a novel substrate not only enables immobilization of DNA molecules but also serves as a powerful amplifier to amplify signal transduction event of DNA hybridization. On the other hand, CNTs can also be employed as a powerful carrier to pre-concentrate enzymes or electroactive molecules for electrochemical sensing of DNA hybridization as a novel indicator. In this review, we place emphasis on recent studies of CNTs-based electrochemical DNA biosensors based on these two aspects, with advantages and disadvantages of each aspect introduced herein.     

Antibiotic Detection in Urine Using Electrochemical Sensors Based on Vertically Aligned Carbon Nanotubes

A sensitive way to determine levofloxacin using a sensor based on vertical aligned carbon nanotubes is described. The morphology and the electrochemical performance of the electrodes were characterised by atomic force microscopy, cyclic voltammetry and square wave voltammetry. A scan‐rate study and electrochemical impedance spectroscopy showed that the levofloxacin oxidation product is adsorbed on the electrode surface. Differential pulse voltammetry in phosphate‐buffer solution allowed the development of a method to determine levofloxacin levels in the range of 1.0–10.0 µmol L^?1, with a detection limit of 75.2 nmol L^?1. The proposed sensor was successfully applied in the determination of levofloxacin in urine, and the obtained results were in full agreement with those from the HPLC procedure.     

Control of the Properties of Carbon Nanotubes Synthesized by CVD for Application in Electrochemical Biosensors

Interest in carbon nanotubes (CNT) has grown at a very rapid rate in the last decade. Their interesting physical and chemical properties open attractive possibilities in many application areas. These properties depend on the process conditions during synthesis and on subsequent purification steps. Recent studies have demonstrated that CNT can promote the electron transfer of biomolecules. These exceptional properties make them attractive for use in electrochemical biosensors. Multi walled nanotubes have been synthesized by the Chemical Vapor Deposition (CVD) method using methane as a carbon source and Ni–Al₂O₃–SiO₂ as the catalyst. The influence of the variation of certain reaction parameters such as feed gas composition, catalyst mass, temperature and reaction time in the yield of the CVD process has been established. In addition, the structural and chemical characteristics of the CNTs have been studied and a purification process to eliminate the catalyst and amorphous carbon has been developed that involves a gaseous oxidative process and acid treatment. The efficiency of the purification step has been determined by analytical techniques. Atomic force microscopy, Raman scattering, thermogravimetric analysis, inductively coupled plasma atomic spectroscopy are the characterization techniques employed in this work.     

Comparison of the Electrochemical Reactivity of Carbon Nanotubes Paste Electrodes with Different Types of Multiwalled Carbon Nanotubes

Carbon nanotubes (CNTs) are widely used in electrochemical studies. It is reported that CNTs with different source and dispersed in different agents [1] yield significant difference of electrochemical reactivity. Here we report on the electrochemical performance of CNTs paste electrodes (CNTPEs) prepared by multiwalled carbon nanotubes (MWNTs) with different diameters, lengths and functional groups. The resulting electrodes exhibit remarkable different electrochemical reactivity towards redox molecules such as NADH and K₃[Fe(CN)₆]. It is found that CNTPEs prepared by MWNTs with 20–30 nm diameter show highest catalysis to NADH oxidation, while CNTPEs prepared by MWNTs with carboxylate groups have best electron‐transfer rate (The peak‐peak separation (ΔE_p) is +0.108 V for MWNTs with carboxylate groups, +0.155 V for normal MWNTs, and +0.174 V for short MWNTs) but weak catalysis towards oxidation of NADH owing to the hydrophilicity of carboxylate groups. The electrochemical reactivity depends on the lengths of CNTs to some extent. The ‘long’ CNTs perform better in our study (The oxidation signals of NADH appear below +0.39 V for ‘long’ CNTs and above +0.46 V for the ‘short’ one totally). Readers may get some directions from this article while choose CNTs for electrochemical study.     

碳纳米管在样品前处理中的应用

碳纳米管是一维碳基纳米材料,具有独特的管状结构、良好的化学稳定性、热稳定性和高比表面积.近年来,碳纳米管在有机小分子、金属离子和生物大分子分离富集方面得到了广泛的应用.本文综述了碳纳米管及功能化碳纳米管在固相萃取、固相微萃取、中空纤维膜保护固相微萃取和液膜萃取等样品前处理技术中的应用.     

氮掺杂碳纳米管的制备及其电化学性能

采用弱反应性含氮有机物水合肼、二乙烯三胺对碳纳米管进行氮掺杂处理. 结合X射线光电子谱(XPS)分析和扫描电镜(SEM)观察, 发现两种含氮有机物处理均可使碳纳米管表面成功连接上含氮基团, 并保持了碳纳米管的本征形貌和结构. 水合肼处理的碳纳米管的氮含量(碳/氮原子比为95/2)明显高于二乙烯三胺处理的碳纳米管(碳/氮原子比为96/0.5). 氮掺杂后碳纳米管在水溶液中分散性明显改善, 且分散性随着氮含量增加进一步增强, 因此水合肼处理的碳纳米管分散性明显优于二乙烯三胺处理的碳纳米管. 作为电化学电容器电极材料, 碳纳米管含氮官能团贡献了赝电容, 但其循环性仍需进一步改进. 氮掺杂碳纳米管较好的亲水性, 改善了电解液的浸润, 循环后氮掺杂碳纳米管电极的比容量仍略高于纯碳纳米管电极的比容量.     

碳纳米管的电化学贮氢性能研究

研究了碳纳米管电极的电化学性能 ,其电化学储氢量达到 2 0 0mAh·g 1且具有高的电化学活性和良好的循环寿命 .采用循环伏安法研究了氢在碳纳米管电极上吸附 /氧化机理 .     

Electrochemical Biosensing Systems Based on Carbon Nanotubes and Carbon Nanofibers

Abstract

Carbon nanomaterials are in the forefront of research in a variety of chemical and physical disciplines. Of these, certain nanostructures seem to be suitable for the development of electrochemical biosensors. In particular carbon nanotubes, and carbon nanofibers have specific chemical and physical characteristics that lent them ideal for the development of biosensors with unique analytical characteristics. In particular, their conductivity, surface area, inherent and induced chemical functionalities, and biocompatibility provide the grounds for the development of a new era of electrochemical biosensors. In this review, we will examine the recent developments of biosensor design based on these new nanostructures.     

基于离子液体修饰碳纳米管电极的碱性磷酸酶电化学检测

利用自制的离子液体修饰碳纳米管电极(CNTs-ILE),在对CNTs-ILE的特性及对碱性磷酸酶(AP)酶促反应的底物磷酸对硝基苯酯(PNPP)和产物对硝基苯酚(PNP)进行电化学研究的基础上,采用安培法对酶促反应进程实现了持续动态的检测.实验表明,CNTs-ILE的循环伏安特性优于传统玻碳电极,且它在检测PNP时呈现出良好的抗钝化特性.当AP浓度范围在1.0～100 U/L时,电流大小与AP的浓度呈良好的线性关系.本方法可快速检测AP浓度,检测时间在20 min内.CNTs-ILE具有良好的抗钝化、操作简单及制作成本低等特点,在碱性磷酸酶的检测领域中有望得到进一步发展.在传统ELISA基础上,利用CNTs-ILE对具体样本最终的AP酶促反应产物进行电化学检测,通过峰值电流大小确定抗原浓度,为检测以AP为标记酶的抗原和抗体提供了理论依据.     

A Review on the Effects of Introducing CNTs in the Modification Process of Electrochemical Sensors

This review summarizes some developments in the fabrication of modified sensors and biosensors through the incorporating the carbon nanotubes (CNTs) in their modification ingredients. A large number of papers have paid attention towards the application of carbon nanotubes (CNTs) as electrode constituents and studied its electrochemical behavior. Here, we survey the achievements in the detection of various substances with high selectivity and sensitivity provided using CNTs based electrodes. Moreover, modified electrodes by CNTs have demonstrated the electrocatalytic features and higher sensitivity in detection of analytes. The improved characteristics arises from the large surface area and good conductivity of CNTs. However, it should be considered that the use of single walled carbon nanotubes (SWCNTs) or multi‐walled carbon nanotubes (MWCNTs), the presence of impurities, and the chemical procedures adopted are effective on the performance of the modified sensors.     

Electrochemical Characteristics of Glucose Oxidase Adsorbed at Carbon Nanotubes Modified Electrode with Ionic Liquid as Binder

Multiwall carbon nanotubes (CNTs)‐modified electrode has been prepared by using ionic liquid (IL) as the binder. The as‐prepared CNTs‐IL composite modified electrode has good biocompatibility and is a suitable matrix to immobilize biomolecules. Glucose oxidase (GOx), containing flavin adenine dinucleotide as active site, stably adsorbed on modified electrode surface has resulted in the direct electron transfer. The electron transfer rate of 9.08 s^?1 obtained is much higher than that of GOx adsorbed on the CNTs papers (1.7 s^?1), and the process is more reversible with small redox peak separation of 23 mV. This may be due to the synergetic promotion of CNTs and IL to electron transfer of the protein, especially the IL as the binder, showing better electrochemical properties than that of chitosan and Nafion. Furthermore, GOx adsorbed at the modified electrode exhibits good stability and keeps good electrocatalytic activity to glucose with broad linear range up to 20 mM. Besides, the simple preparation procedure and easy renewability make the system a basis to investigate the electron transfer kinetics and biocatalytic performance of GOx and provide a promising platform for the development of biosensors.     

二氧化锡填充多壁碳纳米管材料的制备及电化学性能

用硝酸氧化法处理多壁碳纳米管(MWCNTs), 使得MWCNTs端口打开, 长度变短, 表面得到改性. 通过二氯化锡与硝酸银反应, 过滤后的溶液在浓硝酸环境中, Sn2+在毛细作用下扩散进入碳纳米管管腔, 吸附、成核并在热处理作用下沉积, 从而制备出SnO2/MWCNTs纳米复合材料. XRD和TEM测试表明, 部分SnO2填充到MWCNTs管腔, 形成不连续的纳米颗粒. 电化学测试表明, SnO2填充的MWCNTs可以结合两者的优势, 使得复合材料的循环性能和比容量均有所改善.     

Single‐Walled Carbon Nanotube Based Real‐Time Organophosphate Detector

A novel single‐walled carbon nanotube (SWNT) based biosensor for real‐time detection of organophosphate has been developed. Horizontally aligned SWNTs are assembled to desirable electrodes using AC dielectrophoresis technique. Organophosphorus hydrolase (OPH) immobilized on the SWNTs by nonspecific binding triggers enzymatic hydrolysis of organophosphates (OPs), such as paraoxon, consequently causing a detectable change in the conductance of the SWNTs. The conductance change is found to be correlated to the concentration of organophosphate. Our results suggest the novel biosensor has great potential to serve as a simple and reusable platform of sensing organophosphate on a real‐time basis.     

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