碳纳米管在生物传感器中的应用

碳纳米管是一种新型的纳米材料,将其用于修饰电极,可以降低化学物质氧化还原反应的过电位,改善生物分子氧化还原可逆性,其大比表面积有利于酶的固定化,还能促进酶活性中心与电极表面的电子传递.碳纳米管的这些特性对于提高生物检测的灵敏度和稳定性具有重大意义,为生物传感器领域开辟了广阔的前景.     

基于碳纳米管固定葡萄糖氧化酶的ECL葡萄糖传感器的制备

将葡萄糖氧化酶(GOD)固定在多壁碳纳米管(MWCNTs)修饰电极(ME)上,GOD催化氧化葡萄糖生成过氧化氢,并使鲁米诺产生电致化学发光(ECL),据此构建了一种新型ECL葡萄糖传感器.结果表明:CNTs修饰的电极对鲁米诺和H2O2反应具有显著的电催化活性和增敏效果.该传感器对葡萄糖检测的线性范围为0.01～10.0...     

辣根过氧化酶在纳米银修饰玻碳电极上的直接电化学研究1

通过自组装依次将纳米银粒子和辣根过氧化酶(HRP)固定到巯基乙胺(Cys)修饰的玻碳电极上,制备了HRP/Ag/Cys膜修饰电极.用交流阻抗技术表征了电极的自组装过程.用循环伏安法和计时电流法考察了HRP与电极之间的直接电化学行为及酶对过氧化氢电催化特性.电极响应对过氧化氢有良好的电催化还原性质,性能稳定,响应时间小于5 s.有望应用于制备第三代生物传感器     

一种新的多层碳纳米管复合膜修饰的葡萄糖生物传感器制备

将碳纳米管(CNT)分散在壳聚糖(CHIT)溶液中固定到玻碳电极表面,用戊二醛交联甲苯胺蓝(TB)得到复合膜(TB-CNT-CHIT)修饰电极.由于碳纳米管具有良好的电子传递性能,与碱性生物染料甲苯胺蓝之间表现出协同作用,使甲苯胺蓝的电化学活性得到了较大的提高.此TB-CNT-CHIT复合膜修饰的玻碳电极在较低电位下对过氧化氢具有良好的电催化性能,与TB-CHIT膜比较,测定H2O2的灵敏度增大了近20倍.将复合组份多层修饰到电极上,通过戊二醛固定葡萄糖氧化酶,制备了一种新的葡萄生物传感器,该传感器在-0.2 V下对葡萄糖响应的线性范围为0.05～10 mM,检测下限为10μM.传感器的灵敏度较高,响应快,性能稳定.     

基于铂纳米颗粒修饰碳纳米管Nafion膜电极的葡萄糖传感器

将分散在Nafion溶液中的多壁碳纳米管(MWNT)修饰玻碳电极(GCE),再在该膜上电沉积一层铂纳米粒子,制成铂纳米颗粒修饰的碳纳米管Nafion膜电极(Nafion-MWNT-Pt/GCE),并吸附固定葡萄糖氧化酶(GOD),构建电流型葡萄糖生物传感器。考察了Nafion-MWNT-Pt/GCE的电化学特性,发现沉积铂纳米粒子后,Fe(CN)6-3/-4电对在Nafion-MWNT-Pt/GCE上的氧化峰和还原蜂之间的电势差(ΔE)为179mV,小于未修饰铂纳米粒子的碳纳米管Nafion膜电极的ΔE(190mV),表明碳纳米管上电沉积的铂纳米粒子可加速电极的电子传递,电化学反应具有良好的可逆性。此外,铂纳米粒子尚具有良好的催化H2O2氧化的特性,H2O2在Nafion-MWNT-Pt/GCE上的计时电流响应明显增大。基于Nafion-MWNT-Pt/GCE的葡萄糖生物传感器显示了良好的传感性能,其检测线性范围为2.1×10-5～7.6×10-3mol/L,检测下限为1.0×10-6mol/L。     

多孔阳极氧化铝的化学修饰及其应用于过氧化氢的测定

多孔阳极氧化铝经化学修饰后吸附细胞色素C,制备了过氧化氢生物传感器电极。多孔阳极氧化铝通过电化学和化学腐蚀阻挡层后,用两步无电沉积方法制备了纳米金修饰的多孔阳极氧化铝电极,再在含有L-半胱氨酸的细胞色素C的溶液中通过吸附制备细胞色素C电极。用循环伏安法和计时电流法测试细胞色素C电极的电化学性能及催化对过氧化氢的还原。结果表明,包覆的细胞色素C电极显示较好的稳定性,在扫描速度为80 mV/s时于-50 mV、-190 mV附近出现一对稳定的氧化还原峰。该电极对过氧化氢具有良好的电催化还原性能,在1.5×10-5 mol/L～4.8×10-4 mol/L浓度范围内,电流与浓度呈良好的线性关系。多孔阳极氧化铝经化学修饰后,可应用于生物传感器。     

普鲁士蓝膜修饰铂电极对过氧化氢的电催化还原研究

在循环伏安法制备ＰＢ膜修饰铂电极的基础上,研究了其对过氧化氢的电催化还原特性,并讨论了催化机理。结果表明ＰＢ膜修饰电极对过氧化氢有很好的催化作用,过氧化氢浓度在０．０５￣５ｍｍｏｌ·Ｌ＾－１范围内,浓度与电流响应呈线性关系。有望在氧化酶生物传感器开发中获得进一步的应用。     

纳米银/ds-DNA/聚（3,4-乙烯基二氧噻吩）复合膜修饰电极的制备及应用于过氧化氢无酶传感器

在室温水相中,通过电化学方法在玻碳电极上先聚合了聚（3, 4-乙烯基二氧）噻吩（PEDOT）,然后又电沉积了双链DNA（ds-DNA）和银纳米粒子（Nano-Ag）,制备了Nano-Ag/ds-DNA/PEDOT复合膜修饰玻碳电极（GCE）。对该复合膜进行了表征,并研究了该复合膜修饰电极的电化学行为以及对过氧化氢（H2O2）的电催化还原。结果显示,施加工作电位为-0.3 V时,修饰电极对H2O2有着很好的电催化还原能力,达到稳态电流的响应时间小于5 s。因此,该修饰电极可作为无酶传感器用于对H2O2的快速检测。传感器的催化还原电流与H2O2浓度在10 μM-16 mM范围内呈现良好的线性关系,检出限为2.36 μM（S/N=3）。     

基于碳纳米管修饰丝网印刷碳糊电极的葡萄糖和尿酸生物传感器

在丝网印刷碳糊电极上利用吸附法固定葡萄糖氧化酶或尿酸酶,并用碳纳米管进行修饰,铁氰化钾作为电子传递剂,制作用于测量人体血浆中葡萄糖和尿酸浓度的生物传感器.葡萄糖传感器的响应时间仅为5 s,响应电流范围为1.2～30μA,线性测量范围为1～33.3 mM,尿酸传感器响应时间为和电流范围分别为50 s,0.7～14μA,线形测量范围是2～20 mg/dL.用碳纳米管修饰酶电极,改善了电极表面条件,加快了电极反应速度,并提高了传感器的灵敏度.通过碳纳米管修饰电极,葡萄糖传感器的灵敏度从0.333 8μA/mM提高到0.843 2μA/mM,尿酸传感器的灵敏度从0.402 8μA/(mg/dL)提高到0.713 8μA/(mg/dL).     

一次性免疫传感器快速检测阪崎肠杆菌的研究

为改善基于多壁碳纳米管/ Nafion生物传感器电化学信号及储存稳定性,采用[BMIM] PF6/Nafion复合物将辣根过氧化物酶标抗体包埋固定于MWCNT/Nafion修饰的丝网印刷碳电极上,构建了一种新的免疫传感器.用原子力显微镜表征电极各层修饰后的表面形态,用循环伏安法(CV)和交流阻抗法(EIS)考察修饰电极...     

Acetylthiocholine/acetylcholine and thiocholine/choline electrochemical biosensors/sensors based on an organically modified sol–gel glass enzyme reactor and graphite paste electrode

Electrochemical sensors for acetylthiocholine and acetylcholine are described. The non-mediated electrochemistry of acetylthiocholine and thiocholine is studied on the surface of graphite paste electrode and results show that acetylthiocholine is directly oxidized/reduced at >0.32 V vs. Ag/AgCl in both acidic and basic medium. In basic medium, both cathodic and anodic peak currents are less as compared to that of the same amount in acidic medium, which shows that the kinetics of non-enzymatic hydrolysis of acetylcholine into electroactive thiocholine is faster in acidic medium and slower in basic medium. Thiocholine is directly oxidized/reduced at >0.35 V vs. Ag/AgCl with relatively larger anodic current compared to cathodic peak current similar to that of acetylcholine results recorded in acidic medium (pH 6.0). The electrochemical sensor/biosensors for acetylthiocholine/acetylcholine and thiocholine/choline are developed using two enzyme reactors: (1) acetylcholinesterase (AChE) encapsulated organically modified sol–gel glass, and (2) choline oxidase (ChO) immobilized within mediators (tetracyanoquinodimethane (TCNQ), tetrathiafulvalene (TTF), and dimethyl ferrocene (dmFc))-modified graphite paste electrodes. The AChE-immobilized into organically modified sol–gel glass behaves as the reactor for enzymatic hydrolysis of acetylthiocholine/acetylcholine into thiocholine/choline, whereas mediator- and ChO-modified paste electrodes are used for the detection of thiocholine/choline through mediated mechanism. The electrochemistry of AChE-generated thiocholine is studied at the mediator-modified electrodes in the presence and absence of ChO. It is observed that thiocholine undergoes both mediated and non-mediated oxidation in the absence of ChO as well as oxidation through enzyme-catalyzed mediated reactions. The results based on cyclic voltammetry on the oxidation of thiocholine at the surface of mediator-modified electrodes in the presence and absence of ChO are reported. In the presence of the ChO large anodic current is observed near the mediator's redox potentials as compared to the anodic current in the absence of enzyme, which shows mediated bioelectrochemistry of thiocholine. The typical response curves for the detection of thiocholine/choline using mediators and ChO-modified electrodes below 0.24 V vs. Ag/AgCl in 0.1 M Tris–HCl buffer pH 8.0 are reported. Comparative analytical performance on the mediated electrochemical responses of the biosensors is discussed.     

微阵列电极电化学生物传感器

以微阵列电极为基础的电化学生物传感器近几年来发展迅速,是实现生物传感器微型化和集成化的一个重要途径。介绍了微阵列电极以及作为信号转换器在电化学生物传感器中应用的有关进展情况,特别是在基因研究中的应用。     

酶传感器的应用

酶传感器是电化学生物传感器中研究最早、应用最广的一类传感器,也是近年来生物传感器研究的热点。简要介绍了酶传感器的发展历程,着重介绍酶传感器在食品工业、环境监测、生物医学、军事领域等方面的应用,并对酶传感器的发展进行了展望。     

基于碳纳米管微传感器阵列和随机共振的气体检测方法研究

提出了一种基于多壁碳纳米管微传感器阵列和非线性随机共振算法的新型气体检测方法。微传感器阵列包括碳纳米管阳极传感器和碳纳米管阴极传感器以减小检测系统的交叉灵敏度。实验检测了乙醇、丙酮和氨气三种气体,传感器阵列响应输入随机共振系统进行处理,结果表明,信噪比曲线参数能够标定气体浓度和种类,且随机共振处理方法可以有效的降低系统的交叉灵敏度,检测系统具有较好的灵敏度和重复性,具有较好的实用价值。     

AChE/PAMAM-Au/CNTs/GC传感器用于有机磷农药检测的研究

该文制备了一种多层AChE/PAMAM-Au/CNTs/GC乙酰胆碱酯酶的酶抑制电流型传感器应用于有机磷农药的检测,主要利用碳纳米管良好的导电性和吸附性,以及PAMAM(G4)-Au树枝状复合物特殊的结构及导电性能,利用有机磷农药对乙酰且日碱酯酶的抑制作用,以硫代乙酰胆碱(ATCh)为底物,实现了对有机磷农约的检测.实验表明,该方法快速简单,线性范围宽,灵敏度高.固定在传感器上的乙酰胆碱酯酶具有良好的酶动力学响应,其米氏常数(KMapp)为1.66 mmol/L.对有机磷农药呋喃丹的最低检测限达到4.0 nmol/L.     

Batch welding of aligned carbon nanotube onto metal electrodes

A novel batch welding of aligned carbon nanotubes (CNTs) onto metallic electrodes is developed by radio frequency induction heating. The experiments had achieved optimum contact between CNTs and metal electrodes, two hundred samples had the same trend of reduction of contact resistance after heating process, and this reduction was irreversible, which demonstrated good reproducibility of induction heating for CNT welding. Because of its non-contact and selective heating, induction heating provide a potential approach to reproducible large-scale fabrication and wide applications of CNTs devices.     

pH型有机磷水解酶生物传感器的稳态模型

从分析pH型有机磷水解酶(OPH)生物传感器(简称OPH-pH型传感器)的工作原理出发,建立了描述稳态检测过程的扩散传质方程组,并根据方程组的特点将二阶微分方程组简化为二阶微分方程和非线性方程的求解,从而建立了OPH-pH型传感器的稳态模型。模型的计算结果给出了传感器性能的影响因素,可对传感器的设计提供一定的理论指导,自行制备的传感器实验结果与模型的计算结果基本吻合,验证了模型的正确性。     

Enzyme monolayer-functionalized field-effect transistors for biosensor applications

A gate surface of an ion-selective field-effect transistor was modified with a monolayer enzyme array that stimulates biocatalytic reactions that control the gate potential. Stepwise assemblage of the biocatalytic layer included primary silanization of the Al₂O₃-gate with 3-aminopropyltriethoxysilane, subsequent activation of the amino groups with glutaric dialdehyde and the covalent attachment of the enzyme to the functionalized gate surface. Urease, glucose oxidase, acetylcholine esterase and α-chymotrypsin were used to organize the biocatalytic matrices onto the chip gate. The resulting enzyme-based field-effect transistors, ENFETs, demonstrated capability to sense urea, glucose, acetylcholine and N-acetyl- -tyrosine ethyl ester, respectively. The mechanism of the biosensing involves the alteration of the pH in the sensing layer by the biocatalytic reactions and the detection of the pH change by the ENFET. The major advantage of the enzyme-thin-layered FET devices as biosensors is the fast response-time (several tens of seconds) of these bioelectronic devices. This advantage over traditional thick-polymer-based ENFETs results from the low diffusion barrier for the substrate penetration to the biocatalytic active sites and minute isolation of the pH-sensitive gate surface from the bulk solution.     

Gas sensing properties of platinum derivatives of single-walled carbon nanotubes: A DFT analysis

The limitations of intrinsic carbon nanotube (CNT) based devices to examine toxic gases motivate us to investigate novel sensors which can possibly overcome sensitivity problems. Pt–CNT assemblies (with Pt deposited externally as well as internally Pt-doped ones) interacting with NO₂ and NH₃ are studied and compared with unmodified CNTs. DFT calculations show that Pt can enhance adsorption and charge transfer processes to a very large degree. Incoming gas molecules cause changes in the electronic structure and charge distribution of the Pt-substituted CNTs that are both larger and more far-reaching than in their unmodified counterparts. Their relatively high stability is unaffected by the complexation with NO₂ and NH₃. CNTs with defective surface were also investigated. The sensing performance of Pt-doped CNT is found to be superior to defected CNTs.     

Alkaline phosphatase biosensors based on layered double hydroxides matrices: Role of LDH composition

Alkaline phosphatase (AlP) biosensors were developed based on the immobilization of this enzyme by adsorption or coprecipitation methods in different layered double hydroxides (LDH) matrices: Zn₂Al–Cl and Mg₂Al–CO₃. Several characteristics of the AlP/LDH membranes, such as the enzyme immobilization procedure, permeability, buffering effect were investigated. It appeared that the basic nature of the MgAl–LDH nanomaterial improved the stability of the immobilized AlP regarding pH. The synergy between the LDH immobilization matrix and the use of hydroquinone diphosphate (HQDP) as substrate provided a very fast and stable response for the AlP/MgAl–LDH biosensors at 0.4 V.