氯霉素在过氧化聚多巴胺修饰电极上的电化学行为及测定

利用多巴胺(DA)的自聚反应在玻碳电极(GCE)表面形成聚多巴胺(PDA)膜,将聚多巴胺修饰电极浸入碱溶液中进行电化学处理,制得过氧化聚多巴胺修饰电极(OPDA/GCE)。通过方波伏安法直接测定氯霉素在OPDA/GCE上的电化学响应信号,得到待测溶液中氯霉素的浓度。对多巴胺的自聚时间、氯霉素在修饰电极上的电化学性质、测试条件、溶解氧的影响及去除方法等进行考察。结果表明,氯霉素在OPDA/GCE上的还原峰电流与其浓度在3.0×10-6~1.1×10-3mol/L范围内呈良好的线性关系,检出限(S/N=3)为7.8×10-7mol/L,牛奶和蜂蜜样品的加标回收率分别为83.4%~94.1%和91.5%~108.6%。该修饰电极制备方法简便易行、成本低、便于批量制备,用其检测氯霉素操作简单、选择性好。     

聚多巴胺修饰电极对痕量铅的测定研究

通过多巴胺(DA)的自聚反应在玻碳电极(GCE)表面修饰一层聚多巴胺(PDA)膜,对DA的自聚条件和方波溶出伏安法测试条件进行优化。优化的实验条件为:以2 mg/m L DA的Tris-HCl(0.01 mol/L,p H8.5)溶液为自聚溶液,自聚反应时间为2.5 h,铅的测试底液为0.1 mol/L HCl溶液,修饰电极在铅测试溶液中于-1.0 V富集300 s时,溶出峰的峰形好,且峰电流大。峰电流与铅浓度分别在0.1~1.0μg/L和1.0~10.0μg/L范围内呈良好的线性关系,检出限为0.016 5μg/L。实验结果表明,该聚多巴胺修饰电极制备简单、灵敏度高、成本低,可用于加碘盐、纯净水和自来水中痕量铅的测定。     

对巯基苯硼酸／纳米金修饰玻碳电极用于葡萄糖的识别

采用自组装技术,将对巯基苯硼酸(MPBA)自组装于带正电荷纳米金(nano-gold,NG)修饰的玻碳电极(GCE)表面,从而制得用于识别葡萄糖的无酶传感器(MPBA/NG/GCE).通过交流阻抗技术和循环伏安法考察了MPBA/NG/GCE修饰电极的表面电化学特性,同时研究了葡萄糖在该修饰电极上的电化学行为,讨论了利用该修饰电极测定葡萄糖的最佳条件.结果表明:在优化的条件下,氧化峰电流与葡萄糖浓度在1.0～150.0 mmol/L范围内呈良好的线性关系,其回归方程为ΔIp (μA)=3.37+0.342c(mmol/L),相关系数为r=0.999,检出限为3.8×10-5 mol/L (S/N=3),可用于葡萄糖分子的电化学识别.     

用分子筛修饰制备的NO传感器的电化学性能研究

采用层层组装方法(LBL),将纳米方钠石分子筛进一步修饰到经镍(Ⅱ)四磺酸基酞菁(NiTSPc)和全氟磺酸离子交联聚合物(NafionR)修饰的玻碳电极(GCE/NiTSPc/NafionR)表面上,制得一新型NO传感器GCE/NiTSPc/NafionR/(PDDA/Zeolite)5 (PDDA即聚二甲基二烯丙基氯化铵),并对其电化学性能进行了研究.结果表明,纳米方钠石分子筛修饰膜不仅可提高电极检测NO的灵敏度(由26 Ma/(mol·L-1)升至29 Ma/(mol·L-1)),还可提高电极抵抗共存物干扰的能力.Nafion修饰层可使电极对抗坏血酸、多巴胺、肾上腺素及亚硝酸钾的响应分别降低19%、0%、11%、33%,而进一步修饰纳米方钠石分子筛后,电极对上述干扰物质的响应分别降低了68%、51%、52%和39%.     

基于多壁碳纳米管/二茂铁接枝壳聚糖的核/壳结构组合物多层膜电极的组装及其电催化

以聚二烯丙基二甲基氯化铵(PDDA)修饰的玻碳电极(GCE)为基础电极, 利用静电层-层自组装的方法将多壁碳纳米管/二茂铁接枝壳聚糖的核/壳结构组合物(MWCNTs@CHIT-Fc)和聚苯乙烯磺酸钠(PSS)在该电极表面进行交替多层组装. 用循环伏安(CV)、紫外-可见光谱(UV-Vis)和扫描电子显微镜(SEM)等方法对组装过程进行了跟踪表征. 用CV方法研究了抗坏血酸(AA)在该多层膜电极上的电催化氧化. 研究结果表明, 当MWCNTs@CHIT-Fc为6个双层时, AA在该修饰电极上的氧化峰电位与裸GCE相比降低了约0.4 V. 用控制电位电流法研究了不同MWCNTs@CHIT-Fc双层时AA的电流响应. 用该电极测定了AA的灵敏度, 检测限及线性范围等性能参数可通过控制组装的MWCNTs@CHIT-Fc双层数进行调节.     

基于层-层自反应的葡萄糖氧化酶有序多层膜电极

以胱胺修饰的金电极为基础电极, 利用席夫碱反应使经高碘酸根氧化的葡萄糖氧化酶在该电极表面进行自身的层-层有序组装. 用电化学交流阻抗法对多层酶膜形成过程的跟踪结果表明, 该多层酶膜的生长是一个逐步形成的均匀过程. 用循环伏安法和I-t曲线法研究了该酶电极对葡萄糖的电催化氧化. 实验结果表明, 当采用羟基二茂铁作为人工电子转移媒介体时, 该酶电极对葡萄糖具有很好的电催化氧化功能. 该传感器制作简便, 响应迅速, 性能稳定, 催化电流与葡萄糖浓度在一定范围内成正比, 并且可以通过控制葡萄糖氧化酶的组装层数来调节该生物传感器的灵敏度与检测限.     

基于层层静电吸附天青Ⅰ和纳米金固定过氧化物酶生物传感器的研究

在玻碳电极(GCE)上,构造了一种以对氨基苯磺酸电聚合膜(PABSA)为基底,利用层层静电自组装技术固定多层天青Ⅰ(AI)和纳米金(nano-Au)制备的复合薄膜(nano-Au/AI)n,然后通过静电吸附辣根过氧化物酶(HRP)制得过氧化氢生物传感器[HRP/(nano-Au/AI)n/PABSA/GCE].采用循环伏安法和计时电流法考察了该传感器的电化学性质,并且研究了该修饰电极对H2O2的催化还原作用.在优化的实验条件下,该传感器的响应电流与其浓度在3.5×10-6～3.6×10-3 mol/L范围内呈现良好的线性关系,检出限为1.2×10-6 mol/L.该传感器的米氏常数为1.5 mmol/L,表明所固定的酶具有较高的生物活性.     

基于层层组装镍铝水滑石/聚电解质的无酶葡萄糖传感器

采用共沉淀法合成了镍铝水滑石(NiAl-LDH),将NiAl-LDH与聚苯乙烯磺酸钠(PSS)通过层层自组装法构筑了PSS/NiAl-LDH多层膜电极,并将其用于葡萄糖分析。X射线衍射光谱、红外光谱和SEM结果表明：共沉淀法合成的NiAl-LDH具有典型的水滑石特征峰及形貌。紫外-可见光谱表明：NiAl-LDH可与PSS均匀有效地组装构筑多层膜。电化学研究表明：NiAl-LDH修饰电极能有效地催化氧化葡萄糖。该传感器对葡萄糖在5.0×10-7~6.6×10-4 mol/L范围内呈良好的线性响应,灵敏度为8.9×10-4 A?L?mol-1,检出限(S/N=3)为2.8×10-7 mol/L。     

聚对氨基苯磺酸/石墨烯复合修饰电极对尿酸的选择性灵敏测定

采用电聚合方法在石墨烯纳米片(GN)的表面聚合一层聚对氨基苯磺酸(PABSA),制备了聚对氨基苯磺酸/石墨烯复合修饰玻碳电极(PABSA/GN/GCE)。研究了尿酸(UA)和抗坏血酸(AA)在该修饰电极上的电化学行为。与聚对氨基苯磺酸修饰电极(PABSA/GCE)及石墨烯单层膜修饰电极(GN/GCE)相比,复合修饰电极PABSA/GN/GCE显著提高了对UA和AA的检测灵敏度和分离度。在0.1 mol/L磷酸盐缓冲溶液(pH7.0)中,UA和AA的峰电位差达344 mV,表明PABSA/GN/GCE能实现对UA的选择性测定。UA的峰电流与其浓度呈良好的线性关系,线性范围为1.0×10-7～8.0×10-4mol/L,检出限为4.5×10-8mol/L。该复合修饰电极用于尿样中尿酸的测定,结果满意。     

维生素B_1自组装膜修饰金电极对多巴胺、尿酸的电催化作用

用维生素B1(VB1)在金电极上进行自组装,制备了VB1自组装膜修饰金电极(VB1-Au/SAMs/CME).利用循环伏安法初步研究了此自组装单分子膜修饰电极的电化学行为.结果表明: VB1在金电极表面具有特性吸附.以\3-/ 4-氧化还原电对为探针,考察了VB1自组装膜修饰金电极的电化学性质, VB1自组装膜的存在对\3-/4-的电子转移具有明显的阻碍作用.研究了多巴胺(DA)和尿酸(UA)在此电极上的电化学行为.实验结果表明, DA和UA在此电极上均可被电催化氧化.差分脉冲伏安(DPV)氧化峰电流与DA浓度在2.0×10-5～4.0×10-4 mol/L范围内呈线性关系;测定UA的线性范围为6.0×10-5～2.2×10-4 mol/L,而且可实现这两种物质的同时测定.     

Electrocatalysis and Amperometric Detection of the Reduced Form of Nicotinamide Adenine Dinucleotide at Toluidine Blue/Zinc Oxide Coated Electrodes

Thin toluidine blue (TBO) and zinc oxide (ZnO) hybrid films have been grown on glassy carbon electrode (GCE) and indium tin oxide coated (SnO₂) glass electrodes by using cyclic voltammetry (CV). Scanning electron microscopy (SEM) images revealed spherical and beads‐like shape of highly oriented TBO/ZnO hybrid films. Energy dispersive spectrometry (EDS) results declared that the films composed mainly of Zn and O. Moreover, TBO/ZnO hybrid films modified electrode is electrochemically active, dye molecules were not easily leached out from the ZnO matrix and the hybrid films can be considered for potential applications as sensor for amperometric determination of reduced nicotinamide adenine dinucleotide (NADH) at 0.0 V. A linear correlation between electrocatalytic current and NADH concentration was found to be in the range between 25 μM and 100 μM in phosphate buffer. In addition, we observed that dopamine, ascorbic acid and uric acid are not interference in amperometric detection of NADH in this proposed method. In addition, TBO/ZnO hybrid film modified electrode was highly stable and its response to the NADH also remained relentless.     

Study of the nonenzymatic glucose sensor based on highly dispersed Pt nanoparticles supported on carbon nanotubes

An amperometric biosensor for sensitive and selective detection of glucose has been constructed by using highly dispersed Pt nanoparticles supported on carbon nanotubes (Pt-MWCNTs) as sensing interface. The Pt-MWCNTs were synthesized by using the two-step pyrolysis method. This composite shows good electrocatalytic activity towards the oxidation of glucose in alkaline and thus can be used to selectively detect glucose. We found that detection potential and Nafion amount covered on the Pt-MWCNTs modified glassy carbon electrode had considerable influence on the selectivity for amperometric detection of glucose. Under optimal detection conditions (detection potential of 0.0 V versus SCE and 10 μL 1.5% Nafion), selective detection of glucose in the glucose concentration range of 1.0-26.5 mM (correlation coefficient, >0.999) can be performed. The results demonstrate that the Pt-MWCNTs composite is promising for the fabrication of nonenzymatic glucose sensors.     

An improved sensitivity non-enzymatic glucose sensor based on a CuO nanowire modified Cu electrode

CuO nanowires have been prepared and applied for the fabrication of glucose sensors with highly enhanced sensitivity. Cu(OH)(2) nanowires were initially synthesised by a simple and fast procedure, CuO nanowires were then formed simply by removing the water through heat treatment. The structures and morphologies of Cu(OH)(2) and CuO nanowires were characterised by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The direct electrocatalytic oxidation of glucose in alkaline medium at CuO nanowire modified electrodes has been investigated in detail. Compared to a bare Cu electrode, a substantial decrease in the overvoltage of the glucose oxidation was observed at the CuO nanowire electrodes with oxidation starting at ca. 0.10 V vs. Ag/AgCl (saturated KCl). At an applied potential of 0.33 V, CuO nanowire electrodes produce high and reproducible sensitivity to glucose with 0.49 microA/micromol dm(-3). Linear responses were obtained over a concentration range from 0.40 micromol dm(-3) to 2.0 mmol dm(-3) with a detection limit of 49 nmol dm(-3) (S/N = 3). The CuO nanowire modified electrode allows highly sensitive, low working potential, stable, and fast amperometric sensing of glucose, thus is promising for the future development of non-enzymatic glucose sensors.     

Pulsed Deposited Manganese and Vanadium Oxide Film Modified with Carbon Nanotube and Gold Nanoparticle: Chitosan and Ionic Liquid‐based Biosensor

Present study describes the synthesis of mixed oxide films of manganese and vanadium by electrochemical pulsed deposition technique on a glassy carbon electrode (GCE) modified with multiwall carbon nanotubes (MWCNT). The film was further decorated with gold nanoparticles to enhance the reduction signal of dissolved oxygen in pH 5.17 acetate buffer solution. All of the electrochemical synthesized modified electrodes have been characterized with Scanning electron microscopy(SEM), High‐resolution transmission electron microscopy (HRTEM), X‐Ray photoelectron spectroscopy (XPS), X‐Ray diffraction (XRD) techniques. The electrode obtained (AuNPs/MnOx?VOx/CNT/GCE) was utilized as a platform for glucose biosensor where the glucose oxidase enzyme was immobilized on the composite film with the aid of chitosan and an ionic liquid. The electrochemical performance of the biosensor was investigated by cyclic voltammetry and the relative parameters have been optimized by amperometric measurements in pH 5.17 acetate buffer solution. The developed biosensor exhibited a linear range for glucose between 0.1–1.0 mM and the limit of detection was calculated as 0.02 mM.     

维生素B_6在纳米Au-N,P/石墨烯修饰电极上的电化学行为

将金纳米粒子(AuNPs)电沉积在N,P/石墨烯(N,P/Graphene)修饰的玻碳电极表面,研究了维生素B_6(VB_6)在该修饰电极上的电化学行为。实验结果表明:VB_6在该修饰电极上出现一个良好的氧化峰,在最佳实验条件下,其氧化峰电流与VB_6的浓度在2.0×10~(-5)~4.0×10~(-4) mol/L范围内呈线性关系,相关系数R=0.998,检出限为9.2×10~(-6) mol/L。一些常见的物质如K~+、Na~+、Zn~(2+)、葡萄糖(Glu)不干扰VB_6的检测。此方法已用于片剂中VB_6含量的检测,获得较好结果。     

Amperometric Biosensors for Glucose Based on Layer‐by‐Layer Assembled Functionalized Carbon Nanotube and Poly (Neutral Red) Multilayer Film

Abstract

Multiwalled carbon nanotubes (MWNTs) were treated with a mixture of concentrated sulfuric and nitric acid to introduce carboxylic acid groups to the nanotubes. Conducting polymer film was prepared by electrochemical polymerization of neutral red (NR). By using a layer‐by‐layer method, homogeneous and stable MWNTs and poly (neutral red) (PNR) multilayer films were alternately assembled on glassy carbon (GC) electrodes. With the introduction of PNR, the MWNTs/PNR multilayer film system showed synergy between the MWNTs and PNR, with a significant improvement of redox activity due to the excellent electron‐transfer ability of carbon nanotubes (CNTs) and PNR. The electropolymerization is advantageous, providing both prolonged long‐term stability and improved catalytic activity of the resulting modified electrodes. The MWNTs/PNR multilayer film modified glassy carbon electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As compared to MWNTs and PNR‐modified GC electrodes, the magnitude of the amperometric response of the MWNTs/PNR composite‐modified GC electrode is more than three‐fold greater than that of the MWNTs modified GC electrode, and nine‐fold greater than that of the PNR‐modified GC electrode. With the immobilization of glucose oxidase onto the electrode surface using glutaric dialdehyde, a biosensor that responds sensitively to glucose has been constructed. In pH 6.98 phosphate buffer, nearly interference‐free determination of glucose has been realized at ?0.2 V vs. SCE with a linear range from 50 µM to 10 mM and response time <10s. The detection limit was 10 µM glucose (S/N=3).     

Amperometric determination of sulfide ion by glassy carbon electrode modified with multiwall carbon nanotubes and copper (II) phenanthroline complex

Electrocatalytic oxidation of sulfide ion on a glassy carbon electrode (GCE) modified with multiwall carbon nanotubes (MWCNTs) and a copper (II) complex was investigated. The Cu(II) complex was used due to the reversibility of the Cu(II)/Cu(III) redox couple. The MWCNTs are evaluated as a transducer, stabilizer and immobilization matrix for the construction of amperometric sensor based on Cu(II) complex adsorbed on MWCNTs immobilized on the surface of GCE. The modified GCE was applied to the selective amperometric detection of sulfide at a potential of 0.47 V (vs. Ag/AgCl) at pH 8.0. The calibration graph was linear in the concentration range of 5 µM–400 µM; while the limit of detection was 1.2 µM, the sensitivity was 34 nA µM^?1. The interference effects of SO₃ ^2?, SO₄ ^2?, S₂O₃ ^2?, S₄O₆ ^2?, Cysteine, and Cystein were negligible at the concentration ratios more than 40 times. The modified electrode is more stable with time and more easily restorable than unmodified electrode surface. Also, modified electrode permits detection of sulfide ion by its oxidation at lower anodic potentials.      

Phosphomolybdic acid functionalized graphene loading copper nanoparticles modified electrodes for non-enzymatic electrochemical sensing of glucose

A sensitive non-enzymatic glucose electrochemical biosensor (Cu/PMo₁₂-GR/GCE) was developed based on the combination of copper nanoparticles (CuNPs) and phosphomolybdic acid functionalized graphene (PMo₁₂-GR). PMo₁₂-GR films were modified on the surface of glassy carbon electrode (GCE) through electrostatic self-assembly with the aid of poly diallyl dimethyl ammonium chloride (PDDA). Then CuNPs were successfully decorated onto the PMo₁₂-GR modified GCE through electrodeposition. The morphology of Cu/PMo₁₂-GR/GCE was characterized by scanning electron microscope (SEM). Cyclic voltammetry (CV) and chronoamperometry were used to investigate the electrochemical performances of the biosensor. The results indicated that the modified electrode displayed a synergistic effect of PMo₁₂-GR sheets and CuNPs towards the electro-oxidation of glucose in the alkaline solution. At the optimal detection potential of 0.50 V, the response towards glucose presented a linear response ranging from 0.10 μM to 1.0 mM with a detection limit of 3.0 × 10⁻² μM (S/N = 3). In addition, Cu/PMo₁₂-GR/GCE possessed a high selectivity, good reproducibility, excellent stability and acceptable recovery, which indicating the potential application in clinical field.