普鲁士蓝/多壁碳纳米管修饰电极测定维生素C

利用电化学方法在多壁碳纳米管修饰的玻碳电极表面聚合一层普鲁士蓝,制备普鲁士蓝/多壁碳纳米管修饰玻碳电极,运用循环伏安法研究了维生素C(vc)在该修饰电极上的电化学行为.该修饰电极对Vc显示出快速的电化学响应和较好的电催化活性,在pH为4.0的磷酸盐溶液中,Ve浓度与其氧化峰电流在8.0×10-4～1.0×10-2 mol/L范围内呈现良好的线性关系,相关系数为0.9993,检测限为6.4×10-5mol/L.该电极具有较好的稳定性和重现性.     

对硝基苯酚在铕离子掺杂类普鲁士蓝化学修饰玻碳电极上的电化学行为及分析测定

利用电化学沉积法制备了稀土Eu(Ⅲ)离子掺杂的类普鲁士蓝化学修饰玻碳电极,与裸玻碳电极相比,该修饰电极使对硝基苯酚的还原电位大大降低,峰电流显著增大,线性范围明显变宽。讨论了酸度、沉积量、扫速、底液等条件对对硝基苯酚在修饰电极上催化还原的影响。分别用循环伏安法和示差脉冲伏安法进行定量分析,对硝基苯酚的还原电流与浓度在2.0×10-5~2.0×10-3mol/L和2.0×10-7~8.0×10-6mol/L范围内呈良好的线性关系,检出限(3σ)为6.0×10-8mol/L。该电极可用于环境水样检测。     

普鲁士蓝纳米碳管修饰玻碳电极测定吡虫啉的研究

用纳米碳管修饰的玻碳电极以0.1 mol/L NH3-NH4Cl缓冲溶液为底液,用线性扫描伏安法对吡虫啉农药进行了测定。吡虫啉在-1.04 V出现的还原峰电流的大小与吡虫啉的浓度在1.34×10-7~2.94×10-5mol/L范围内呈良好的线性关系。本方法的检出限为5.0×10-8mol/L。本文对不同的修饰电极性能进行了研究,结果发现在玻碳电极上先修饰普鲁士蓝再修饰纳米碳管的电极对吡虫啉的响应最好,峰型最好,峰电流最大,测定最灵敏。     

聚L-半胱氨酸/还原氧化石墨烯/Nafion修饰玻碳电极对芦丁的电化学传感行为研究

本文采用滴涂法制备了还原氧化石墨烯/Nafion溶液修饰玻碳电极(rGO/Nafion/GCE),用电化学聚合法将L-半胱氨酸(L-Cys)聚合在rGO/Nafion/GCE表面,得到Poly-L-Cys/rGO/Nafion/GCE。采用伏安法研究了芦丁在该修饰电极上的电化学行为及其影响因素。结果表明,L-Cys的电聚合圈数对修饰电极的电化学性能具有一定的影响。在最优条件下,芦丁的峰电流与其浓度在2.0×10~(-8)~1.0×10~(-5) mol/L内呈现好的线性关系,检出限(S/N=3)为1.0×10~(-8) mol/L。     

普鲁士蓝/氧化锆复合材料的电化学行为及对H2O2的电催化

通过一步电沉积技术制备了普鲁士蓝/氧化锆修饰玻碳电极。采用电化学阻抗技术表征修饰电极。采用循环伏安法研究了pH值和扫描速率对该修饰电极的电化学行为的影响。结果表明:普鲁士蓝的峰电流与其扫描速率的一次方在一定范围内呈良好的线性关系。此外,该修饰电极在含有KCl(1.0mol/L)的磷酸盐缓冲溶液(0.1mol/L,pH=7.0)中,对H2O2具有明显的电催化作用,在无酶检测H2O2领域具有潜在的应用价值。     

纳米金/Nafion/石墨烯修饰玻碳电极检测对苯二酚的研究

采用一步电化学共还原的方法将纳米金(AuNPs)、Nafion、电化学还原石墨烯(ERGO)修饰到玻碳电极(GCE)表面,制成修饰电极AuNPs/Nafion/ERGO/GCE。以扫描电镜对其进行表征,用循环伏安法和微分脉冲伏安法研究对苯二酚在该修饰电极上的电催化行为。优化了实验参数,对苯二酚在2.0～100μmol/L及100～800μmol/L浓度范围内与其氧化峰电流呈良好的线性关系,检出限为0.3μmol/L。用该修饰电极成功地进行了实际水样中对苯二酚含量的测定。     

基于修饰石墨烯/纳米金复合膜固定乙酰胆碱酯酶的敌百虫传感器

结合氨基功能化离子液体修饰石墨烯(IL-GR)、纳米金(Au)等纳米材料的独特性质,以壳聚糖(CHIT)为交联剂,首先在玻碳电极表面固定IL-GR,然后吸附胶体金制得Au/IL-GR-CHIT复合膜,最后固定乙酰胆碱酯酶(AChE)制得新型有机磷检测酶传感器(AChE/Au/IL-GR-CHIT/GCE),并用于白菜样品中敌百虫农药的测定。采用透射电镜(TEM)对纳米材料进行了表征,循环伏安法(CV)和差示脉冲伏安法(DPV)研究了传感器的电化学性质。纳米复合物不仅为保持AChE的生物活性提供了适宜的微环境,并且对传感器性能的改善显示出强大的协同效应。在优化实验条件下,抑制率(A)与敌百虫浓度的负对数在2.0×10-10~1.0×10-6mol/L范围内呈良好的线性关系,检出限(S/N=3)为2.1×10-12mol/L。用于蔬菜中敌百虫含量的测定,回收率为97.5%~107.2%。     

基于乙酰胆碱酯酶生物传感平台的西维因检测

为给农药西维因检测提供一种新方法,根据西维因抑制乙酰胆碱酯酶活性的原理,以黑珍珠2000（BP2000）为乙酰胆碱酯酶的固定化材料,采用滴凃电极法构建了基于乙酰胆碱酯酶的西维因生物传感平台. 结果表明,固定在BP2000 上的乙酰胆碱酯酶保持了对氯化乙酰胆碱的催化活性,并且由于BP2000 材料的引入,提升了电极有效的电化学活性表面积,而且电极上物质的电化学氧化拥有较低氧化电位（0.630 V）并伴随质子传输. 由BP2000 搭建成功的乙酰胆碱酯酶生物传感平台对西维因检测的线性响应范围为2.0 ng·mL^-1 ~ 12.5 ng·mL^-1,检测限为3.15 ng·mL^-1. 本研究对酶生物传感平台和酶生物燃料电池体系中酶电极的构建提供了一种简单方法及高效载体.     

尿酸在普鲁士蓝修饰电极上的电化学行为及其分析应用

用恒电位电解法制备了普鲁士蓝修饰玻碳电极,研究了尿酸(UA)在该电极上的电化学行为,并提出了一种新的用于检测UA的方法。在 0. 1mol/L(pH5. 0 )的醋酸缓冲溶液中, 0. 100mol/LKCl作为支持电解质,UA在普鲁士蓝修饰电极上于 0. 470V处产生一灵敏的氧化峰,方波伏安法测定其氧化峰电流与UA浓度在 2. 5×10-6 ~2. 0×10-4 mol/L范围内呈良好的线性关系,相关系数为 0. 9986,检出限为 1. 1×10-6 mol/L。该电极制作简单,重现性良好,可用于UA的测定。     

基于Nafion/碳纳米粒子修饰的葡萄糖传感器

采用滴涂法制备了Nafion/碳纳米粒子复合物修饰玻碳电极,该电极对H2O2具有良好的电催化氧化性能。还利用滴涂法制备了Nafion/碳纳米粒子复合物包裹的葡萄糖酶电化学生物传感器,该生物传感器对葡萄糖有着良好的电催化作用。应用该传感器对葡萄糖进行了检测,检测线性范围为2.0×10-6～6.0×10-3mol/L,检出限为1.6×10-6mol/L(S/N=3),实验结果表明该传感器具有良好的稳定性、重现性和抗干扰能力。对小鼠血清样品中的葡萄糖进行检测,结果令人满意。     

Cuprous Oxide/Nitrogen-doped Graphene Nanocomposites as Electrochemical Sensors for Ofloxacin Determination

Cu₂O/nitrogen-doped grapheme(NG) nanocomposite material was prepared via a facile one step chemical reduction and characterized by means of X-ray diffraction(XRD) and scanning electron microscopy(SEM). A new electrochemical sensor was then fabricated by coating Cu₂O/nitrogen-doped graphene nanocomposite with Nafion on glassy carbon electrode(Cu₂O/NG/Nafion/GCE). The electrochemical response of this modified electrode toward ofloxacin was examined by cyclic voltammetry. The results indicate that Cu₂O/NG/Nafion composite-modified electrode exhibits higher catalytic activity in the electrochemical oxidation of ofloxacin compared with glassy carbon electrode(GCE), Cu₂O/Nafion modified electrode(Cu₂O/Nafion/GCE), and N-doped graphene/Nafion modified electrode(NG/Nafion/GCE). Under optimal conditions, the peak current was found to be linearly proportional to the concentration of ofloxacin in the 0.5-27.5 μmol/L and 27.5-280 μmol/L ranges with a lower detection limit of 0.34 μmol/L, higher sensitivity of 39.32 μA·L·mmol^-1 and a shorter reaction time of less than 2 s. In addition, Nafion can enhance the stability of the modified electrode and prevent some negative species. Thus the modified electrode exhibits good selectivity and a long working life. The Cu₂O/NG/Nafion composite modified electrode shows promising application in electrochemical sensors, biosensors, and other related fields because of its excellent properties.     

Synthesis,characterization and the electrocatalytic application of prussian blue/titanate nanotubes nanocomposite

A novel kind of nanocomposite, titanate nanotubes (TNTs) decorated by electroactive Prussian blue (PB), was fabricated by a simple chemical method. The as-prepared nanocomposite was characterized by XRD, XPS, TEM, FT-IR and Cyclic voltammetry (CV). Experimental results revealed that PB was adsorbed on the surface of TNTs, and the adsorption capacity of TNTs was stronger than that of anatase-type TiO₂ powder (TNP). The PB-TNTs nanocomposite was modified onto a glassy carbon electrode and the electrode showed excellent electroactivity. The modified electrode also exhibited outstanding electrocatalytic activity towards the reduction of hydrogen peroxide and can serve as an amperometric sensor for H₂O₂ detection. The sensor fabricated by casting Nafion (NF) above the PB-TNTs composite film (NF/PB-TNTs/GCE) showed two linear ranges of 2 × 10^?5–5 × 10^?4 M and 2 × 10^?3–7 × 10^?3 M, with a detection limit of 1 × 10^?6 M. Furthermore, PB-TNTs modified electrode with Nafion (NF/PB-TNTs/GCE) showed wider linear range and better stability compared with PB-TNTs modified electrode without Nafion (PB-TNTs/GCE) and PB modified electrode with Nafion (NF/PB/GCE).     

Rapid amperometric detection of coliforms based on MWNTs/Nafion composite film modified glass carbon electrode

A multi-wall carbon nanotubes (MWNTs)/Nafion modified glassy carbon electrode (GCE) was fabricated for the rapid amperometric detection of coliforms, represented by Escherichia coli (E. coli). In the bacterial solution, beta-galactosidase which was used as an indicator of coliforms reacted with substrate, p-aminophenol-beta-galactopyranoside (PAPG), and produced p-aminophenol (PAP). PAP was detected by MWNTs/Nafion modified GCE. Due to the cation-exchange capacity of Nafion and the electrocatalytic ability of MWNTs, the detection sensitivity of PAP was improved and the detection time of coliforms was shortened. The bacterial can be detected within 5h ranging from 10 to 10(4)cfu/mL. The MWNTs/Nafion modified GCE was easy to be constructed and regenerated. To our best knowledge, it was the first time to use MWNTs/Nafion modified GCE to detect the concentration of coliforms.     

A novel amperometric sensor and chromatographic detector for determination of parathion

A novel amperometric sensor and chromatographic detector for determination of parathion has been fabricated from a multi-wall carbon nano-tube (MWCNT)/Nafion film-modified glassy-carbon electrode (GCE). The electrochemical response to parathion at the MWCNT/Nafion film electrode was investigated by cyclic voltammetry and linear sweep voltammetry. The redox current of parathion at the MWCNT/Nafion film electrode was significantly higher than that at the bare GCE, the MWCNT-modified GCE, and the Nafion-modified GCE. The results indicated that the MWCNT/Nafion film had an efficient electrocatalytic effect on the electrochemical response to parathion. The peak current was proportional to the concentration of parathion in the range 5.0×10^–9–2.0×10^–5 mol L^–1. The detection limit was 1.0×10^–9 mol L^–1 (after 120 s accumulation). In high-performance liquid chromatography with electrochemical detection (HPLC–ED) a stable and sensitive current response was obtained for parathion at the MWCNT/Nafion film electrode. The linear range for parathion was over four orders of magnitude and the detection limit was 6.0×10^–9 mol L^–1. Application of the method for determination of parathion in rice was satisfactory.     

Highly sensitive and selective dopamine biosensor based on a phenylethynyl ferrocene/graphene nanocomposite modified electrode

A new ferrocene derivative (1-[(4-amino) phenylethynyl]ferrocene, Fc-NH(2)) was synthesized for the first time. The ferrocene derivative molecule contained the phenylethynyl skeleton, ferrocene and amino groups with excellent electrochemical properties. The graphene/Fc-NH(2) nanocomposite was prepared by mixing graphene solution and Fc-NH(2) solution in one pot and the nanocomposite was utilized to construct a Nafion/graphene/Fc-NH(2) modified glassy carbon electrode (GCE). The ferrocene derivative immobilized on the graphene can enhance the charge-transport ability of the nanocomposite, stabilize the graphene and prevent the leakage of ferrocene. The detection signal of dopamine (DA) was significantly amplified on the Nafion/graphene/Fc-NH(2)/GCE. It was experimentally demonstrated that the signal enhancement results from the synergy amplification effect of graphene and the Fc-NH(2). The oxidation peak currents of DA were linearly related to the concentrations in the range of 5 × 10(-8) to 2 × 10(-4) M with the detection limit of 20 nM in the absence of uric acid (UA) and ascorbic acid (AA). In the presence of 10(-3) M AA and 10(-4) M UA, the linear response range was 1 × 10(-7) to 4 × 10(-4) M, and the detection limit was 50 nM at S/N = 3. Using the proposed Nafion/Fc-NH(2)/graphene/GCE, DA was successfully determined in real samples with the standard addition method.     

Electrochemical Determination of Phenylethanolamine A Based on Nafion/MWCNTs/AuNPs Modified Carbon Electrode

Phenylethanolamine A (PEA), a β‐agonist, was found to be illegally used as a growth promoter in pigs last year, causing Chinese government's great attention. Here, a sensitive electrochemical method was developed for detecting PEA by immobilization of gold nanoparticles (AuNPs), multiwalled carbon nanotubes (MWCNTs) and Nafion on the surface of a glassy carbon electrode (GCE). The Nafion/MWCNTs/AuNPs film was characterized by scanning electronic micrographs (SEM) and electrochemical impedance spectroscopy (EIS). The electrochemical behaviors of PEA at the modified GCE were investigated in detail. The synergetic effects of AuNPs, MWCNTs and Nafion amplify the electrochemical reduction signal of PEA, and result in high sensitivity for PEA determination. Under the optimal conditions, the electrochemical sensor shows a wide linear range of 0.01 to 10 (mol/L with a detection limit of 0.005 µmol/L. Moreover, the fabricated sensor presents high selectivity and long‐term stability, which paves a new way for simple, rapid, sensitive detection of PEA.     

An enhanced electrocatalytic oxidation and determination of 2,4-dichlorophenol on multilayer deposited functionalized multi-walled carbon nanotube/Nafion composite film electrode

The voltammetric (CV and DPV) behavior of multi-walled carbon nanotube/Nafion composite coupled with a glassy carbon electrode was investigated for the determination of 2,4-dichlorophenol. The structural and morphological evaluation by XRD and FESEM revealed that the acid treated MWCNT retained their morphology without any structural change. The existence of the possible functional groups was investigated by FTIR and Raman spectroscopy. Compared to bare GCE, a significantly reduced interfacial charge transfer resistance was noticed for MWCNT/Nafion/GCE by electrochemical impedance spectroscopy (EIS). The use of Nafion not only contributed to the non-covalent functionalization of MWCNT, but also protected the electrode surface against the polymerization of phenoxy radicals forming a passivating film. For MWCNT/Nafion/GCE, the combination of anti-passivating ability and excellent catalytic properties resulted in the rapid and direct electrochemical determination of 2,4-DCP. Under optimal experimental conditions, the DPV responses for MWCNT/Nafion/GCE is linear over the 1–150 μmol/L range with a detection limit (S/N = 3) of 0.01 μmol/L. The presence of many interfering species had no influence on the signals of 2,4-DCP. The proposed sensor was successfully tested for the determination of 2,4-DCP in tap water samples and the recovery was in the range of 99.0–102.5%.     

A Novel Electrochemical Method for the Analysis of Hydrogen Peroxide with the Use of a Glassy Carbon Electrode Modified by a Prussian Blue/Copper‐Gold Bimetallic Nanoparticles Hybrid Film

A novel Prussian blue/copper‐gold bimetallic nanoparticles hybrid film modified electrode was prepared by electrochemical deposition on a glassy carbon electrode (PB/Cu‐AuNPs/GCE). Morphology and electrochemistry of this electrode were studied by UV‐vis spectroscopy, scanning electron microscopy, X‐ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly better electrocatalytic activity for the reduction of hydrogen peroxide in comparison with the single PB/GCE and PB/AuNPs/GCE. This was attributed to the synergistic effect of PB and Cu‐Au bimetallic nanoparticles. Also, the sensor demonstrated an overall high level of performance for the analysis of H₂O₂ in the concentration range from 0.002 to 0.84 mM.     

Electrochemistry and voltammetric determination of L-tryptophan and L-tyrosine using a glassy carbon electrode modified with a Nafion/TiO2-graphene composite film

We describe a glassy carbon electrode (GCE) modified with a film composed of Nafion and TiO₂-graphene (TiO₂-GR) nanocomposite, and its voltammetric response to the amino acids L-tryptophane (Trp) and L-tyrosine (Tyr). The incorporation of TiO₂ nanoparticles with graphene significantly improves the electrocatalytic activity and voltammetric response compared to electrodes modified with Nafion/graphene only. The Nafion/TiO₂-GR modified electrode was used to determine Trp and Tyr with detection limits of 0.7 and 2.3 μM, and a sensitivity of 75.9 and 22.8 μA mM^?1 for Trp and Tyr, respectively.