基于普鲁士蓝(PB)膜修饰铂电极的葡萄糖传感器的研究

在制备PB膜修饰铂盘电极的基础上,利用修饰电极对过氧化氢的电催化还原特性,得到了性能优良的葡萄糖传感器。作者系统地考察了有关修饰膜制备和测试实验条件对传感器性能的影响,结果表明传感器的最佳工作电位是0．05V,测试溶液的最适PH值为6．5,在选定的工作条件下,传感器的检测灵敏度为80nA/mmol.L^-1,线性范围为0．1－5mmol.L^-1,响应时间为1．5min,寿命在1个月以上,表观米氏常数为21mmol.L^-1。本方法制得的传感器能有效消除抗坏血酸,尿酸的干扰,有望用于血液中葡萄糖的直接测定。     

四硫富瓦烯为电子媒介体的葡萄糖生物传感器的研究

本采用四硫富瓦烯（ＴＴＦ）作为葡萄糖氧化酶与玻碳电极之间的电子媒介体，把葡萄糖氧化酶因定在Ｎａｆｉｏｎ－ＴＴＦ修饰电极上，制成葡萄糖生物传感器。用这种传感器测定人体血清中葡萄糖的含量，其线性范围在４．０×１０＾－５～１０＾－３ｍｏｌ／Ｌ之间，响应时间为２０ｓ。该传感器具有选择性、重现性好，灵敏度高等优点。     

基于表面重建螺旋型铂铱电极的葡萄糖生物传感器

通过对螺旋型铂铱电极表面进行化学腐蚀和电化学沉积铂纳米粒子实现电极表面的重建和优化,研究了螺旋型铂铱电极在不同腐蚀时间和电沉积时间下的形貌及对过氧化氢(H2O2)的催化活性.对表面重建的工作电极涂覆氧化酶和半透膜,制备出了铂纳米粒子/葡萄糖氧化酶/环氧聚氨酯酶电极,并将其用作葡萄糖传感器的工作电极.传感器计时电流检测结果表明,表面重建后的酶电极传感器对葡萄糖的检测范围扩大为2~45 mmol/L,优于裸铂铱酶电极传感器,电流响应值和灵敏度得到明显提升,同时传感器还具有良好的稳定性和选择性.     

基于聚吡咯的平面型葡萄糖传感器的研究

在含有葡萄糖氧化酶的聚吡咯饰的电极表面涂覆一层明胶，再用戊二醛交联剂备了葡萄糖传感器，该传感器的基础电极采用薄膜沉积和剥离技术制作，包括一个工作电极和一个对电极（兼作参比电极），该传感器线性范围为０．１～４ｍｍｏｌ／Ｌ，响应时间和灵敏度分别为１５～２５ｓ和１８．１ｍＡ／ｍｏｌ．ｃｍ＾２，传感器在４℃冰箱中存放６个月其活性仍有９０％以上。     

基于石墨烯/DNA/纳米金的无酶葡萄糖传感器研究

本文利用电解剥离法制得石墨烯/DNA复合材料,通过化学还原法将纳米金颗粒固定在石墨烯/DNA复合材料表面制得石墨烯/DNA/纳米金(Gr/DNA/GNPs)复合材料,最终构建了一种基于Gr/DNA/GNPs修饰电极的无酶葡萄糖生物传感器。通过循环伏安法考察了不同修饰电极在碱性葡萄糖溶液中的电化学行为,并探讨了溶液中OH-离子强度、扫描电位范围及Gr/DNA/GNPs修饰量对传感器响应特性的影响。在优化实验条件下,采用循环伏安法检测葡萄糖的线性范围为8.0×10-5~5.0×10-2mol·L-1,检出限为1.2×10-5mol·L-1(S/N=3)。对2.0×10-3mol·L-1的葡萄糖平行测定5次,其相对标准偏差为3.2%。实验结果表明该传感器具有较高的灵敏度、较好的重现性、稳定性及抗干扰能力。本方法可成功用于人血清样品中葡萄糖含量的测定,回收率为97.4%~102.8%。     

聚中性红修饰玻碳电极葡萄糖生物传感器

以中性红为电子媒介体,电聚合于Nafion修饰的玻碳电极表面,以戊二醛作交联剂固定葡萄糖氧化酶,最后覆盖一层Nafion膜防止酶流失,构建一种新型葡萄糖生物传感器.详细探讨了传感器的电化学性能及对葡萄糖的最佳响应条件.结果表明,30℃时,传感器在pH 7.0的PBS中对葡萄糖的线性响应范围为1.0×10-5~5.0×10-3mol.L-1.该传感器制作简单、性能优良,有潜在应用前景.     

钴卟啉修饰碳纤维束葡萄糖酶微电极的研究

生物电化学传感器的微型化研究是目前生物传感器研究中的一个很活跃的方向。我们曾用钴卟啉修饰碳纤维柱电极,并以它为基底制成了葡萄糖微传感器。为加强电极的抗折断能力,本文把约1千支碳纤维(φ9μm)做成碳纤维束盘微电极,在其表面修饰四苯基钴卟啉后,以其为基底制成了葡萄糖酶电极。将其用于流动注射分析,可以大大提高线性响应上限。     

非图案化法制备柔性连续葡萄糖监测传感器

以聚多巴胺作为前驱体,在聚酰亚胺薄膜表面化学沉积一层牢固致密的金层,以该镀金薄膜两面的金层作为基体电极,在其中一面镀铂黑作为参比-对电极,在另一面依次电沉积铂黑层、电泳形成Nafion/碳纳米管网络层、电吸引形成葡萄糖氧化酶层构成工作电极,并整体涂覆聚氨酯外膜,制备了一种柔性葡萄糖传感器.考察了此传感器对葡萄糖的检测性能,以及各层表面形态结构对传感器性能的影响.传感器在0.3V的工作电位下对葡萄糖的线性响应范围是2.0 ～ 32.0 mmol/L,响应灵敏度为25 μA· (mmol/L)-1·cm-2,检出限为0.05 mmol/L (S/N=3),且传感器有良好的长期稳定性和抗干扰性,可用于皮下连续血糖监测.     

碳纳米管负载铂-二氧化钌纳米颗粒用于葡萄糖传感器的研究

建立了多壁碳纳米管(MWNTs)负载铂二二氧化钌纳米颗粒的液相化学还原法.以Nafion为固定剂,将Pt-RuO2/MWNTs复合材料修饰于玻碳电极的表面,制备了一种无酶型葡萄糖传感器.实验表明:复合材料修饰的电极对葡萄糖响应电流明显,并且受抗坏血酸(AA)、多巴胺(DA)和尿酸(UA)的干扰小.本实验采用安培法测定葡萄糖,线性范围为2 0×10 3～1.0×10-2 mol/L(R～0.9965);灵敏度为119.26 μA cm-2(mmol/L)-1;检出限为1.25×10 -5 mol/L(信噪比为3);响应时间为4.8 s.PtRuO2/MWNTs修饰电极可作为性能良好的无酶型葡萄糖传感器.     

“葡萄糖的两种电分析化学测定法之比较”仪器分析综合实验设计

综合设计性实验是培养大学生独立解决问题能力和创新能力的重要途径。开设“葡萄糖的两种电分析化学测定法之比较”综合设计性实验,大学生通过自主设计化学修饰电极和生物传感器的两种电分析化学传感器来测定葡萄糖,对比两种方法的线性范围、灵敏度和选择性等指标,自主选择合适的方法实现对果汁中葡萄糖含量的测定。本项目能使学生较深入了解仪器分析方法的前沿工作,提升学生学习的兴趣和实验教学的效果,培养学生创新性学习的科研素质。     

Improved Blood Compatibility at a Glucose Enzyme Electrode Used for Ejctraoorpokeal Monitoring

Abstract

A glucose enzyme electrode based on glucose oxidase has been used in an extracorporeal flow system which allows standardization during monitoring. The detection limit for glucose was 0.02 mmol/l, and the linear range, which extended to 5 mmol/l glucose, allowed measurement of whole blood after dilution. Restandardization following whole blood exposure led to a loss of sensitivity which was attributed to coating of electrode membranes by blood constituents. The problem was largely overcome through use of silane-treated membranes and the operation of electrodes in a narrow channel flow cell.     

Preparation and application of a new glucose sensor based on iodide ion selective electrode

An electrode for glucose has been prepared by using an iodide selective electrode with the glucose oxidase enzyme. The iodide selective electrode used was prepared from 10% TDMAI and PVC according our previous study. The enzyme was immobilized on the iodide electrode by holding it at pH 7 phosphate buffer for 10 min at room temperature. The H₂O₂ formed from the reaction of glucose was determined from the decrease of iodide concentration that was present in the reaction cell. The iodide concentration was followed from the change of potential of iodide selective electrode. The potential change was linear in the 4×10⁻⁴ to 4×10⁻³ M glucose concentration (75-650 mg glucose/100ml blood) range. The slope of the linear portion was about 79 mV per decade change in glucose concentration. Glucose contents of some blood samples were determined with the new electrode and consistency was obtained with a colorimetric method. The effects of pH, iodide concentration, the amount of enzyme immobilized and the operating temperature were studied. No interference of ascorbic acid, uric acid, iron(III) and Cu(II) was observed. Since the iodide electrode used was not an AgI-Ag₂S electrode, there was no interference of common ions such as chloride present in biological fluids. The slope of the electrode did not change for about 65 days when used 3 times a day.     

Study on the United Glucose Oxidase Electrode Constructed by Composite Electrode

A novel type of united glucose oxidase (GOD) electrode was designed. Glucose oxidase and ferrocene (Fc), which was a mediator, were added into the composite electrode that was constructed by graphite powder, acetylene black, and epoxy resin. These three materials in composite electrode kept constant proportion in weight. And the optimum amounts of GOD and Fc among united enzyme electrode were 5% and 2%, respectively. The glucose was detected linearly in the concentration range 0.01–9.0 mM with a 20-s steady-state response time and 36 nA/mM of the sensitivity at 0.15 V applied potential. And electrode fouling problem and the response current from the interferents were avoided. The response current of the united GOD electrode had no obvious deterioration within 80 days when stored at 4°C in a refrigerator. The detecting results of human serum by the united GOD electrode had good consistency with that by standard enzyme method. The maximum deviation between these two detecting values was 5%. It might be used for detecting the blood sugar in clinical assay.     

A glucose biosensor using methyl viologen redox mediator on carbon film electrodes

A new methyl viologen-mediated amperometric enzyme electrode sensitive to glucose has been developed using carbon film electrode substrates. Carbon film electrodes from resistors fabricated by pyrolytic deposition of carbon were modified by immobilization of glucose oxidase through cross-linking with glutaraldehyde in the presence of bovine serum albumin. The mediator, methyl viologen, was directly immobilised with the enzyme together with Nafion cation-exchange polymer. The electrochemistry of the glucose oxidase/methyl viologen modified electrode was investigated by cyclic voltammetry and by electrochemical impedance spectroscopy. The biosensor response to glucose was evaluated amperometrically; the detection limit was 20 μM, the linear range extended to 1.2 mM and the reproducibility of around 3%. When stored in phosphate buffer at 4 °C and used every day, the sensor showed good stability over more several weeks.     

An electrochemiluminescent sensor for glucose employing a modified carbon nanotube paste electrode

A carbon nanotube paste (CNTP) electrode and a carbon nanotube paste/glucose oxidase (CNTP/GOx) electrode were prepared, and the electrochemiluminescent (ECL) behavior of luminol in the presence of glucose was investigated in detail at each of these electrodes. Compared to the classical carbon paste (CP) electrode, the CNTP electrode incorporating glucose oxidase greatly enhanced the response of the ECL sensor to glucose due to the electrocatalytic activity of the carbon nanotubes, the specificity of the enzymatic reaction, and the sensitivity of the luminol ECL reaction. Under optimal conditions, the electrode was found to respond linearly to glucose in the concentration range 1.0x10(-6) approximately 2.0x10(-3) mol/L, and the detection limit (defined as the concentration that can be detected at a signal-to-noise ratio of 3) was found to be a glucose concentration of 5.0x10(-7) mol/L. The method used to prepare the CNTP/GOx electrode was very convenient, and the electrode surface could be renewed in the case of fouling by simply polishing or cutting it to expose a new and fully active surface. The relative standard deviations (RSD) were found to be 6.8% and 8.9% for the CNTP electrode and the CNTP/GOx electrode (n=6). The electrode retained 95% of its initial response after two weeks.     

纳米级金膜微电极的制作,表征及异相催化反应

报道了纳米级金膜微电极的制作方法，用ＸＰＳ及ＳＥＭ对电极表面进行了表征，考察了该电极的循环伏安及计时电流特性，在聚吡咯修饰微带金电极上成功地实现了葡萄糖氧化酶和电子传递媒体Ｆｅ（ＣＮ）６＾３－的同时固定，并研究了ＧＯＤ／Ｆｅ（ＣＮ）６＾３－／ＰＰｙ微酶电极对葡萄糖的响应，稳态响应电流与葡萄糖浓度之间存在Ｍｉｃｈｅａｌｉｓ－Ｍｅｎｔｅｎ动力学特征。     

Comparative study of first-, second- and third-generation amperometric glucose enzyme electrodes in continuous-flow analysis of undiluted whole blood

First-, second- and third-generation amperometric glucose enzyme electrodes were compared under flow-injection and steady-state conditions for the monitoring of undiluted whole blood. First-generation electrodes, based on the detection of hydrogen peroxide at a platinum electrode, are generally unsuitable because of the eventual poisoning of the electrode and because of their susceptibility to oxygen variation. Second-generation electrodes in which a mediator is used for the reoxidation of glucose oxidase are more suitable for the analysis of whole blood under both steady-state and flow-injection conditions. However, the choice of mediator is important. The best results with regard to linear range and stability were obtained with tetrathiafulvalene, whereas dimethylferrocene required considerable pretreatment before use. A third-generation electrode based on tetrathiafulvalene-tetracyanoquinodimethane where direct oxidation of glucose oxidase occurs also proved useful but showed lower stability and a smaller dynamic range compared with the second-generation devices. Flow-injection and steady-state studies were carried out using wall-jet cell geometry.     

葡萄糖在亚硝基五氰合铁酸铁修饰碳糊电极上的电化学行为研究

采用亚硝基五氰合铁酸铁(FePCNF)粉末与碳粉质量比为2∶3混合,制备了FePCNF修饰碳糊电极.研究了FePCNF修饰碳糊电极在KNO3溶液中的电化学行为和扫速、pH值及不同支持电解质的影响.该电极可用于催化氧化检测葡萄糖.实验表明:FePCNF修饰碳糊电极在0.5 mol/L KNO3溶液中有一对灵敏的氧化还原峰,峰电流与扫速呈线性关系.氧化峰电流与葡萄糖的浓度在2.0×10-6～2.4×10-5 mol/L之间有良好的线性关系(r=0.9934),检出限为6.3×10-7 mol/L.该电极具有良好的稳定性和重现性,适合于微量葡萄糖的检测.     

钴卟啉修饰电极为基底的葡萄糖酶电极

生物电化学传感器的开发和应用是目前电分析化学研究中的一个重要方向,其中最引人注目的是电流式生物电化学传感器的研究。传统的电流式生物电化学传感器的基础电极采用的是能检测氧气和过氧化氢的贵金属电极。本文采用四苯基钴卟啉化学修饰电极代替     

以聚邻苯二胺修饰的镀铂玻碳电极为基底的葡萄糖传感器

生物电化学传感器所面临的主要问题,就是干扰和污染。具有选择渗透性的聚合物膜可以防止电活性物质到达电极表面和大分子物质对基底电极的污染,提高电极的选择性,延长使用寿命。这方面的报道已很多。电聚合的邻苯二胺膜的选择渗透性已有报道。其优点是薄(<10nm),且具有自身的绝缘性,可以被均匀地聚合在电极表面。我们用这种聚合物膜修饰电极为基底电极,化学交联法将葡萄糖氧化酶(GOD)固定在基底电极表面,制备了葡萄糖