直流电电化学沉积镍制备原位生长碳纳米管化学修饰电极

利用直流电电化学沉积法将生长碳纳米管(CNT)的催化剂镍均匀地附着在石墨电极(GE)表面,再通过化学气相沉积法制备得到原位生长碳纳米管化学修饰电极(GSCNT-CME).电化学沉积的金属镍和所制备的修饰电极分别用光学显微镜、扫描电子显微镜(SEM)和电子能谱(EDX)进行表征,所得修饰电极的电化学性能用[Fe(CN)6]3-/[Fe(CN)6]4-溶液进行表征.结果表明:经直流电电化学沉积,可以在石墨电极表面沉积一层致密的金属镍,能生长出管径均匀的碳纳米管,所制得的修饰电极具有良好的电化学响应灵敏性和准确性,可在电化学检测领域发挥重要的应用.     

基于碳纳米管修饰电极的胆碱电化学发光生物传感器研制

在碳纳米管(CNTs)和K3Fe(CN)6修饰的铂电极上吸附固定胆碱氧化酶,以鲁米诺为发光试剂,研制了胆碱电化学发光(ECL)生物传感器.CNTs可有效提高电极表面的电荷传输能力、提高电极表面的生物相容性和对酶分子的固载能力;K3Fe(CN)6对酶活性具有激活作用,同时对H2O2增敏的鲁米诺ECL有增强作用,均有利于提...     

基于碳纳米管修饰电极/鸟嘌呤电化学体系的固体电位型pH传感器

根据鸟嘌呤在短单壁碳纳米管修饰玻碳电极(S-SWCNT/GCE)上发生的电催化氧化特性,及其氧化电位对支持电解质溶液的pH值具有灵敏的响应,制备了以鸟嘌呤为指示剂的固体电位型pH传感器。在优化各种影响因素后,其电位在pH2.0~12.0范围内具有线性响应,回归方程为Epa(V)=-0.0497pH 0.8931。该传感器制备简单,使用方便,响应时间<20 s。在pH响应范围内待测液中离子强度对测定没有影响。酸碱滴定终点具有明显的突跃。对Na 、K 和Ca2 的选择性系数小。已成功地应用于实际样品的测定。     

基于碳纳米管修饰电极的胆碱电化学发光生物传感器研制

在碳纳米管(CNTs)和K3Fe(CN)6修饰的铂电极上吸附固定胆碱氧化酶,以鲁米诺为发光试剂,研制了胆碱电化学发光(ECL)生物传感器。CNTs可有效提高电极表面的电荷传输能力、提高电极表面的生物相容性和对酶分子的固载能力;K3Fe(CN)6对酶活性具有激活作用,同时对H2O2增敏的鲁米诺ECL有增强作用,均有利于提高传感器的检测灵敏度。研究表明,将CNTs分散液与K3Fe(CN)6混合,滴涂修饰在Pt电极上,吸附固定胆碱氧化酶,制备传感器。此传感器在含有8×10-6mol/L鲁米诺的磷酸盐缓冲液(pH7.4)、30℃条件下产生的ECL强度与胆碱浓度在1×10-7～4×10-3mol/L范围内呈线性关系,相关系数为0.994,检出限为1.2×10-8 mol/L。此生物传感器应用于鼠血样中胆碱的测定,测得结果为2.68 mg/L,平均回收率为101.1%。传感器具有快速、稳定和重现性好等特点,有望应用于常规分析。     

碳纳米管负载铂颗粒酶电极葡萄糖传感器

以碳纳米管负载纳米铂颗粒修饰玻碳电极 (CNT Pt/GCE)为基底 ,用明胶固定葡萄糖氧化酶(GOD) ,构建了电流型葡萄糖生物传感器 (GOD/CNT Pt/GCE)。在实验中 ,GOD/CNT Pt/GCE显示了良好的分析性能 ,与常规铂电极葡萄糖传感器 (GOD/Pt)相比较 ,测定葡萄糖的检出限从 6 .7× 10 -3 mol/L下降到8.3× 10 -4mol/L ;工作电位从 0 .6 5V下降至 0 .4 5V ;响应时间从 30s下降至 5s左右。实验结果表明 ,具有高度电催化活性的CNT Pt/GCE可作为酶传感器的一种新型基体电极。     

脱氢酶电化学生物传感器的研究进展

自然界中超过400种脱氢酶使用辅酶-烟酰胺腺嘌呤二核苷酸(NAD+)或烟酰胺腺嘌呤二核苷酸磷酸(NADP+)作为生物催化反应中氢和电子的传递体,因此烟酰胺型辅酶的电化学氧化对构筑此类脱氢酶电化学生物传感器具有重要的意义.本文介绍了还原型辅酶在人工电子媒介体存在下的电化学氧化,以及脱氢酶电化学生物传感器的设计和应用.     

基于碳纳米管修饰电极的脱氢酶传感器研究进展

烟酰胺腺嘌呤二核苷酸(NAD+/NADH)是目前已知300多种脱氢酶的辅酶,通过对NADH的检测,可以间接测定底物浓度或酶活力。如何利用电化学技术实现NADH的准确、快速、稳定检测,一直是电化学及生物传感领域的重要课题。碳纳米管(CNT)的发现为NADH的电化学检测注入新的生机。本文综述了近年来碳纳米管修饰电极在NADH电化学检测及脱氢酶生物传感器构建中的应用进展,并展望了其应用前景。     

碳纳米管负载铂修饰电极结合溶胶-凝胶技术制备胆固醇传感器

制作了碳纳米管和碳纳米管负载铂镶嵌修饰的浸蜡石墨电极,实验发现纳米铂的引入使修饰电极对过氧化氢的还原有更好的电催化性能。用溶胶凝胶法将胆固醇氧化酶固定在碳纳米管负载铂修饰的浸蜡石墨电极表面,构建了一种新型的胆固醇生物传感器。实现了低电位下对胆固醇的间接测定。胆固醇浓度在4.0×10-6~1×10-4mol/L范围内与其峰电流的增量呈现良好的线性关系。检出限为1.4×10-6mol/L。该传感器的灵敏度高,选择性好,可以避免样品中大量易氧化物质的干扰,且寿命长,性能稳定。     

多壁碳纳米管修饰电极上阿替洛尔电化学行为的研究及其测定

基于多壁碳纳米管修饰玻碳电极对阿替洛尔的催化作用,建立了测定阿替洛尔的电化学分析方法。多壁碳纳米管修饰玻碳电极与裸玻碳电极相比,显著提高了阿替洛尔的氧化峰电流,降低了氧化峰电位,提高了测定的灵敏度。该电极测定阿替洛尔的线性范围为4.9×10-6~6.3×10-4mol/L,检出限为2×10-6mol/L。对1.3×10-4mol/L阿替洛尔进行11次平行测定,相对标准偏差为4.4%。此法可用于阿替洛尔片剂中阿替洛尔的测定。     

多壁碳纳米管化学修饰电极测定替硝唑的研究

替硝唑(Tinidazole,TNZ)是继甲硝唑后新一代的抗厌氧菌和抗滴虫的国家级二类新药,可广泛应用于临床各种厌氧菌感染。其测定方法有紫外分光光度法、高效液相色谱法、光度法及电化学方法等。但用碳纳米管修饰电极测定TNZ还未见报道。     

Electrochemical DNA Biosensors Based on Palladium Nanoparticles Combined with Carbon Nanotubes

Palladium nanoparticles, in combination with multi‐walled carbon nanotubes (MWCNTs), were used to fabricate a sensitivity‐enhanced electrochemical DNA biosensor. MWCNTs and palladium nanoparticles were dispersed in Nafion, which were used to modify a glassy carbon electrode (GCE). Oligonucleotides with amino groups at the 5′ end were covalently linked onto carboxylic groups of MWCNTs on the electrode. The hybridization events were monitored by differential pulse voltammetry (DPV) measurement using methylene blue (MB) as an indicator. Due to the ability of carbon nanotubes to promote electron‐transfer and the high catalytic activities of palladium nanoparticles for electrochemical reaction of MB, the sensitivity of presented electrochemical DNA biosensors was remarkably improved. The detection limit of the method for target DNA was 1.2×10^?13 M.     

Glassy Carbon Electrodes Modified with Multiwall Carbon Nanotubes Dispersed in Polylysine

We report the analytical performance of glassy carbon electrodes (GCE) modified with a dispersion of multiwall carbon nanotubes (MWCNT) in polylysine (Plys) (GCE/MWCNT‐Plys). The resulting electrodes show an excellent electrocatalytic activity towards different bioanalytes like ascorbic acid, uric acid and hydrogen peroxide, with important decrease in their oxidation overvoltages. The dispersion of 1.0 mg/mL MWCNT in 1.0 mg/mL polylysine is highly stable, since after 2 weeks the sensitivity for hydrogen peroxide at GCE modified with this dispersion remained in a 90% of the original value. The MWCNT‐Plys layer immobilized on glassy carbon electrodes has been also used as a platform to build supramolecular architectures by self‐assembling of polyelectrolytes based on the polycationic nature of the polylysine used to disperse the nanotubes. The self‐assembling of glucose oxidase has allowed us to obtain a supramolecular multistructure for glucose biosensing. The influence of glucose oxidase concentration and adsorption time as well as the effect of using polylysine or MWCNT‐Plys as polycationic layers for further adsorption of GOx is also evaluated.     

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.     

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.     

Comparison of the Electrochemical Reactivity of Electrodes Modified with Carbon Nanotubes from Different Sources

The electrochemical activity of five different commercial carbon nanotubes (CNT), prepared by the ARC discharge and chemical vapor deposition (CVD) methods, has been assessed and compared. The various multi‐walled CNT were immobilized onto a glassy carbon electrode using three different dispersing agents (Nafion, concentrated nitric acid and dimethylformamide (DMF)) and their voltammetric response to ferricyanide, NADH and hydrogen peroxide examined. SEM was used to characterize the surface morphology. The corresponding cyclic voltammetry and amperometric data showed that the electrocatalytic activity, the background current and the electroanalytical performance are strongly depended on the preparation of the CNT and on the dispersing agent used. The most favorable amperometric detection of NADH and hydrogen peroxide is observed at the NanoLab CVD‐produced CNT in connection to a DMF‐surface dispersion. ARC‐produced CNT display a smaller capacitance, particularly in connection to the DMF dispersion. Such differences in the electrochemical reactivity are attributed to the different surface chemistries (primarily defect densities) of the corresponding CNT layers, associated with the different production and dispersion protocols.     

Use of Cationic Surfactants Film Carbon Paste Electrodes Modified with Multiwalled Carbon Nanotubes in Electrochemical Analysis of dsDNA

Direct electrochemistry of dsDNA based on the enhancement effect of cationic surfactants such as dodecyltrimethylammonium bromide (DTAB) and tetradecyltrimethylammonium bromide (TTAB) was achieved by using a carbon paste electrode modified with multiwalled carbon nanotubes (MWCNTs/CPE) as the basal electrode. The results indicated that the dsDNA molecules have been adsorbed quite strongly on the cationic surfactants’ film and very well developed peaks which were attributed to the oxidation of guanine residues on the dsDNA molecule structure were obtained from both electrodes. The electrochemical behavior of dsDNA at the surface of the modified electrodes was also evaluated. Based on the signal of guanine, under the optimal conditions, very low levels of dsDNA were detected following short accumulation times with detection limits of 0.650 mg L^?1 and 0.119 mg L^?1 for DTAB/MWCNTs/CPE and TTAB/MWCNTs/CPE, respectively.     

Carbon Nanotubes Modified Graphite Electrodes for Monitoring of Biointeraction Between 6‐Thioguanine and DNA

In this present study, single‐walled carbon nanotubes (SWCNT) modified disposable pencil graphite electrodes (SWCNT‐PGEs) were developed for the electrochemical monitoring of anticancer drug, and its interaction with double stranded DNA (dsDNA). Under this aim, SWCNT‐PGEs were applied for the first time in the literature to analyse of 6‐Thioguanine (6‐TG), and also to investigate its interaction with DNA by voltammetric and impedimetric methods. The surface morphologies of PGE and SWCNT‐PGE were explored using scanning electron microscopy (SEM) and electrochemical characterization of unmodified/modified electrodes was performed by cyclic voltammetry (CV). Experimental parameters; such as, the concentration of 6‐TG and its interaction time with dsDNA were optimized by using differential pulse voltammetry (DPV). Additionally, the interaction of 6‐TG with dsDNA was studied in case of different interaction times by electrochemical impedance spectroscopy (EIS) in contrast to voltammetric results. The detection limit of 6‐TG was found to be 0.25 μM by SWCNT‐PGE.     

Enzymatic Biosensors Based on Carbon Nanotubes Paste Electrodes

The performance of enzymatic biosensors based on the immobilization of different enzymes within a carbon nanotubes paste electrode (CNTPE) prepared by dispersion of multi‐wall carbon nanotubes (MWNT) and mineral oil is reported in this work. The strong electrocatalytic activity of carbon nanotubes towards the reduction of hydrogen peroxide and quinones and the oxidation of NADH have allowed an effective low‐potential amperometric determination of lactate, phenols, catechols and ethanol, in connection with the incorporation of lactate oxidase, polyphenol oxidase and alcohol dehydrogenase/NAD⁺, respectively, within the composite matrix. Compared to the analogous enzymatic CPEs, a great enhancement in the response is observed at the enzymatic CNTPEs. Therefore, highly sensitive lactate, phenols, catechols and alcohols biosensors without using any metal or redox mediator can be obtained with this new composite material.     

维生素C在多壁碳纳米管/壳聚糖复合膜修饰玻碳电极上的电化学行为及测定

研究了维生素C在多壁碳纳米管/壳聚糖复合膜修饰玻碳电极上的电化学行为及测定。实验结果表明,在0.2 mol/L PBS(pH6.0)缓冲溶液中,修饰电极对抗坏血酸的氧化具有明显的催化和增敏效应,其氧化峰电位由 0.5 V负移至 0.1 V(vs.AgCl/Ag)。对修饰剂碳纳米管的用量、支持电解质、富集电位和富集时间等进行了优化。采用半微分伏安法进行定量测定,其线性范围为4.0×10-6~2.0×10-3mol/L,r=-0.998 3,检出限为1.0μmol/L。对抗坏血酸在修饰电极上的电化学行为进行了探讨,其电极反应为具有吸附特性和不可逆的电极过程,测得参加反应的质子数为2,电极反应的电子转移系数为0.59。测定了维生素C药片中抗坏血酸的含量,回收率在93%~105%。     

碳纳米管阵列电极的构建及电化学研究

本文提出一种改进的氧化铝模板法制备碳纳米管阵列电极:首先结合气相化学沉积和磁控溅射在氧化铝模板中制得碳纳米管阵列电极,然后用HF溶液将沉积了碳纳米管的氧化铝模板阻挡层除去,控制溶出时间即可得到不同溶出长度的碳纳米管阵列电极.循环伏安测试表明,锂离子在该阵列电极中的嵌入脱出反应主要发生在碳纳米管的端口处.此外,还应用固定频率交流阻抗法,研究了不同溶出时间的碳纳米管阵列电极的电容性质.