基于电沉积石墨烯阪崎肠杆菌免疫传感器研究

为研制一种新型免疫传感器并用于快速检测阪崎肠杆菌(E.sakazakii),采用自组装方法将辣根过氧化物酶标记的阪崎肠杆菌抗体(HRP-anti-E.sakazakii)固定于修饰有电沉积石墨烯(ERGO)的丝网印刷碳电极上,制得一次性酶免疫传感器。采用循环伏安法(CV)考察不同修饰电极的电化学特性,根据CV还原峰电流值的变化对E.sakazakii进行快速检测。在优化的检测条件下,该方法检测E.sakazakii的线性范围为102～109cfu/mL,检测限为9.1×101cfu/mL(S/N=3)。该酶免疫传感器灵敏度高,并具有良好的特异性、重现性(RSD=6.4%)、稳定性(4℃无菌容器中放置15d后电流响应为初始值的90.05%),具有一定潜在应用价值。     

纳米金掺杂石墨烯修饰玻碳电极选择性测定多巴胺

构建纳米金(Au)掺杂石墨烯(GS-Nafion)修饰玻碳电极(GCE)的电化学传感器(GCE/GS/Nafion/Au),研究多巴胺(DA)和抗坏血酸(AA)在上述电极的电化学行为,并用于DA的选择性测定。将GS-Nafion溶液涂覆于GCE表面制得GCE/GS/Nafion电极,采用化学镀方法于GCE/GS/Nafion电极表面生成Au制得GCE/GS/Nafion/Au电极,采用扫描电镜(SEM)表征GS、化学镀Au和电极的制备过程,循环伏安(CV)法和示差脉冲伏安(DPV)法研究DA的电化学性质。在优化的实验条件下,DA浓度与DPV法氧化峰电流大小在1.0×10-7～1.0×10-4mol/L之间呈线性关系,线性相关系数为0.9988,检出限为4.2×10-8mol/L。该电极制备过程简单、灵敏度高、抗干扰性强,可以用于DA的测定,结果令人满意。     

Electrochemical detection of ascorbic acid (vitamin C) using a glassy carbon electrode

A method for the detection of ascorbic acid (AA) was developed using square wave anodic stripping voltammetric (SWASV) analysis with a glassy carbon electrode (GCE). The results indicated a sensitive oxidation peak current of AA on the GCE. A linear curve was obtained within a concentration range of 1-130.0 microg/L with a preconcentration time of 270 s. The relative standard deviation of 30.0 microg/L observed was 0.1016% (n = 12) under optimum conditions. The low detection limit (S/N) was pegged at 0.30 microg/L. Results showed that the method developed can be used to assay biological and pharmaceutical samples, and food samples, as well as other materials requiring AA analyses.     

氧化石墨烯修饰玻碳电极快速检测香菇中多菌灵

制备了氧化石墨烯修饰玻碳电极,并用电化学阻抗谱对修饰电极进行表征。利用循环伏安法研究了多菌灵的电化学行为,用差分脉冲伏安法对香菇中多菌灵的含量进行了测定。实验结果表明,多菌灵在修饰电极上出现了一个不可逆氧化峰,多菌灵浓度在1～100μmol/L范围内,差分脉冲伏安法的氧化峰电流与多菌灵浓度呈现良好的线性关系,检出限为0.5μmol/L。该方法简便、快捷、灵敏度高,可用于检测香菇中多菌灵含量。     

纳米金/石墨烯修饰电极测定食品中的诱惑红

利用滴涂法制备石墨烯修饰电极,采用电化学还原法将纳米金粒子修饰到石墨烯修饰电极的表面,制备了纳米金/石墨烯修饰电极。研究诱惑红在纳米金/石墨烯修饰玻碳电极上的电化学行为,建立一种测定食品中诱惑红含量的新方法。结果表明,在pH=5.0的磷酸盐缓冲溶液中,-0.8⁰.8 V电位范围内,诱惑红在纳米金/石墨烯修饰玻碳电极上出现一对可逆的氧化还原峰,纳米金/石墨烯修饰玻碳电极对诱惑红的电化学反应具有很好的电催化作用;在8.00×10^-81.00×10^-5mol/L的范围内,氧化峰电流与诱惑红浓度成线性关系,检出限为8.00×10^-9mol/L。该修饰电极具有良好的灵敏度、选择性和稳定性,可用于食品中诱惑红含量的测定,回收率在96.9%¹01.6%之间,因此该方法可以用于测定食品中诱惑红的含量。      

Isophtalic acid terminated graphene oxide modified glassy carbon nanosensor electrode: Cd2+ and Bi3+ analysis in tap water and milk samples

In this study, graphene oxide was derivative with 5-aminoisophtalic acid by amidization reaction. The nanomaterial in suspension was denoted as graphene oxide-isophtalic acid. The graphene oxide-isophtalic acid suspension was covered on the glassy carbon electrode surface under the infrared lamb. The graphene oxide was characterized with transmission electron microscopy and x-ray diffraction. Surface characterization of the glassy carbon/graphene oxide-isophtalic acid was performed with x-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The ultrasensitive nanoplatform for the simultaneous electrochemical square-wave anodic stripping voltammetry assay of Bi³⁺ and Cd²⁺ in aqueous solution has been developed on the glassy carbon/graphene oxide-isophtalic acid. The linearity range of Bi³⁺ and Cd²⁺ were 1.0×10^?8 – 1.0×10^?12 M (S/N = 3). The responses of species were practically unaltered with the increase of various species concentration. The detection limits of Cd²⁺ and Bi³⁺ were determined as 8.1×10^?13 M and 1.06×10^?13 M, respectively. The electrode performance was checked with tap water and commercially milk samples.     

Electrochemical determination of theophylline in foodstuff,tea and soft drinks based on urchin-like CdSe microparticles modified glassy carbon electrode

A simply electrochemical method based on CdSe microparticles modified glassy carbon electrode (GCE) was developed to determine theophylline using cyclic voltammetry and differential pulse voltammetry. Theophylline showed a well-defined oxidation peak at the fabricated electrode in phosphate buffer solution and the oxidation peak current is much higher than that at the bare GCE, indicating that CdSe can effectively improve the oxidation of theophylline. Several effect factors on theophylline determination were optimised, such as CdSe amount, solution pH, scan rate and accumulation time. Under the optimal conditions, the oxidation peak current of theophylline was proportional to its concentration in the range of 1.0–40 and 40–700 μM with a correlation coefficient of 0.9974 and 0.9956, respectively. The limit of detection was estimated to be 0.4 μM (S/N = 3). The developed method showed good reproducibility and excellent selectivity. The fabricated electrode was successfully used to determine theophylline in tea, carbonated cola drink, fruit juice drink, fermented milk drink and preserved fruit with acceptable recovery.     

Application of reduced graphene oxide and carbon nanotube modified electrodes for measuring the enzymatic activity of alcohol dehydrogenase

An electrochemical method was developed to measure the enzymatic activity of alcohol dehydrogenase (ADH) by monitoring the amount of reduced nicotinamide adenine dinucleotide (NADH) generated in the catalysed oxidation of ethanol by ADH. The concentration of NADH was determined by amperometric measurements, which recorded the oxidation current of NADH versus time on reduced graphene oxide and functionalised multi-walled carbon nanotube modified electrodes. The initial reaction rates and the apparent Michaelis constants of the enzymatic reaction were obtained in the absence and presence of Al³⁺ and nanometre-sized tridecameric aluminium polycationic (nano-Al₁₃) species. The results showed that Al³⁺ and nano-Al₁₃ exhibited inhibitory effect on the enzymatic activity of ADH. Fluorescence and circular dichroism spectra indicated the inhibitory effect was likely caused by the conformational changes of ADH and/or NADH induced by Al³⁺ and nano-Al₁₃.     

Determination of carbohydrates by capillary zone electrophoresis with amperometric detection at a nano-nickel oxide modified carbon paste electrode

In this paper, a nano-NiO modified carbon paste electrode in capillary zone electrophoresis with amperometric detection (CZE-AD) was firstly applied to the determination of carbohydrates. Effects of several important factors such as detection potential, the concentration of running buffer, separation voltage and injection time were investigated to acquire the optimum conditions. Under the selected optimum conditions, three carbohydrates: glucose, sucrose and fructose could be perfectly separated within 20 min. The relationships between peak current and concentration of three carbohydrates were linear over about 3 orders of magnitude with detection limits (S/N = 3) ranging from 3.0 × 10⁻⁷ to 6.0 × 10⁻⁷ mol L⁻¹. The electrode was stable, and can be used for at least one week. The proposed method has been successfully applied to monitor carbohydrates in the real samples with satisfactory assay results.     

Electrochemical determination of Sudan I using montmorillonite calcium modified carbon paste electrode

In the current work, a sensitive, rapid and convenient electrochemical method was developed for the determination of Sudan I utilizing the excellent properties of montmorillonite calcium (MMT-Ca). Compared with the unmodified carbon paste electrode (CPE), MMT-Ca modified CPE not only significantly enhances the oxidation peak current of Sudan I but also lowers the oxidation overpotential, suggesting that the MMT-Ca modified CPE can remarkably improve the determining sensitivity of Sudan I. The experimental conditions such as determining medium, the content of MMT-Ca and accumulation time were optimized for the determination of Sudan I. The oxidation peak current is proportional to the concentration of Sudan I over the range from 0.05 mg L⁻¹ (2.01 × 10⁻⁷ mol L⁻¹) to 1.0 mg L⁻¹ (4.03 × 10⁻⁶ mol L⁻¹), and the limit of detection is 0.02 mg L⁻¹ (8.06 × 10⁻⁸ mol L⁻¹) for 2-min accumulation. Finally this newly-proposed sensing method was successfully employed to detect Sudan I in practical samples and good recovery was achieved.     

Analysis of sudan I,sudan II,sudan III,and sudan IV in food by HPLC with electrochemical detection: Comparison of glassy carbon electrode with carbon nanotube-ionic liquid gel modified electrode

A method was developed for analyzing of sudan I, sudan II, sudan III, and sudan IV by high performance liquid chromatography coupled with an electrochemical detector. The electrochemical oxidation of each compound was investigated with a carbon nanotube-ionic liquid gel modified glassy carbon (MWNTs-IL-Gel/GC) electrode using cyclic voltammetry. The results were compared with those of glassy carbon electrodes. At the MWNTs-IL-Gel/GC electrode, highly reproducible, well-defined cyclic voltammograms for sudan oxidation were obtained. In the flow system, MWNTs-IL-Gel/GC exhibited highly reproducible and well-defined amperometric signals without peak tailing. In addition, the determination of sudan dyes by mean of isocratic reverse-phase HPLC, with amperometric detection at MWNTs-IL-Gel/GC and GC electrode, have been investigated. The chromatograms showed excellent separation. The detection limits ranged from 0.001 to 0.005 ppm. The method was sensitive, selective and could be applicable for the assay of sudan dyes in soft drink samples.     

聚三聚氰胺修饰玻碳电极测定食品中叔丁基对苯二酚

采用电化学聚合方法制备了聚三聚氰胺膜修饰玻碳电极(poly melamine film modified glassy carbon electrode,PMel/GCE),并采用循环伏安法研究了抗氧化剂叔丁基对苯二酚(tert-butylhydroquinone,TBHQ)在修饰电极上的电化学行为,发现其氧化还原峰电流较在玻碳电极(glassy carbon electrode,GCE)上明显增强,提高了检测的灵敏度。对三聚氰胺电化学聚合时间、扫描速率、电压、段数以及测定TBHQ溶液的pH值等实验条件进行了优化。在最佳的条件下,TBHQ在4.00×10-7~1.00×10-4mol/L内与其氧化峰电流呈线性关系,相关系数:R=0.997 5,检出限为2.00×10-9mol/L。将修饰电极用于食品中TBHQ的检测,回收率在96.9%~102.2%之间。     

日落黄在聚结晶紫膜修饰电极上的电化学行为及其测定

用电化学方法制备了聚结晶紫膜修饰玻碳电极,研究了日落黄在此修饰电极上的电化学行为,建立了测定日落黄的电化学分析新方法。结果表明:聚结晶紫膜修饰电极能催化日落黄的电化学反应。日落黄在聚结晶紫修饰电极上的氧化峰电流与其浓度在8.0×10-8².0×10-5mol/L范围内呈良好线性关系,检出限为2.0×10-8mol/L。该方法用于实际样品分析,结果满意。      

聚色氨酸修饰玻碳电极测定动物性食品中己烯雌酚

用循环伏安法制备了聚色氨酸修饰玻碳电极。研究了己烯雌酚在聚色氨酸修饰电极上的电化学行为,建立了一种直接测定动物性食品中己烯雌酚含量的新方法。实验结果表明:在p H=5.0的磷酸盐缓冲溶液体系中,己烯雌酚在聚色氨酸修饰玻碳电极上于-0.2⁰.8 V范围内出现一对可逆的氧化还原峰,与裸玻碳电极相比较,聚色氨酸修饰电极对己烯雌酚的电化学反应具有促进作用。己烯雌酚浓度在5.00×10^-81.00×10^-6mol/L范围内与其氧化峰电流成正比,检出限为2.00×10^-9mol/L,对己烯雌酚溶液平行测定6次的RSD为2.4%。该修饰电极具有良好的灵敏度、选择性和稳定性,可用于牛肉、鱼肉及奶粉中己烯雌酚含量的测定,回收率为96.0%¹02.3%,结果满意,方法具有实用价值。      

聚多巴胺修饰还原氧化石墨烯/聚吡咯导电织物的制备及其传感响应特性

为改善导电织物导电层与织物间的界面黏附性,构建有效接触的导电网络,提升传感响应特性,采用聚多巴胺(PDA)对涤纶/氨纶针织物表面进行修饰,制备以还原氧化石墨烯(RGO)和聚吡咯(PPy)为导电层的柔性传感器。借助傅里叶红外光谱仪、扫描电子显微镜、自制KTC传感测试盒、四探针方阻测试仪、万能拉伸试验机等对导电织物进行表征与分析。结果表明：经PDA修饰后的织物与RGO/PPy间的界面黏附性有明显改善,所构建导电网络更为连续,相较于未修饰的导电织物具有更好的耐久性和耐磨性;该织物柔性传感器的拉伸范围在0%～130%之间时,灵敏度增加至39.1,响应时间为0.06 s,可准确识别人体关节运动。     

Electrochemical reduction of carbon dioxide in an MFC-MEC system with a layer-by-layer self-assembly carbon nanotube/cobalt phthalocyanine modified electrode

Electrochemical reduction of carbon dioxide (CO(2)) to useful chemical materials is of great significance to the virtuous cycle of CO(2). However, some problems such as high overpotential, high applied voltage, and high energy consumption exist in the course of the conventional electrochemical reduction process. This study presents a new CO(2) reduction technique for targeted production of formic acid in a microbial electrolysis cell (MEC) driven by a microbial fuel cell (MFC). The multiwalled carbon nanotubes (MWCNT) and cobalt tetra-amino phthalocyanine (CoTAPc) composite modified electrode was fabricated by the layer-by-layer (LBL) self-assembly technique. The new electrodes significantly decreased the overpotential of CO(2) reduction, and as cathode successfully reduced CO(2) to formic acid (production rate of up to 21.0 ± 0.2 mg·L(-1)·h(-1)) in an MEC driven by a single MFC. Compared with the electrode modified by CoTAPc alone, the MWCNT/CoTAPc composite modified electrode could increase the current and formic acid production rate by approximately 20% and 100%, respectively. The Faraday efficiency for formic acid production depended on the cathode potential. The MWCNT/CoTAPc composite electrode reached the maximum Faraday efficiency at the cathode potential of ca. -0.5 V vs Ag/AgCl. Increasing the number of electrode modification layers favored the current and formic acid production rate. The production of formic acid was stable in the MFC-MEC system after multiple batches of CO(2) electrolysis, and no significant change was observed on the performances of the modified electrode. The coupling of the catalytic electrode and the bioelectrochemical system realized the targeted reduction of CO(2) in the absence of external energy input, providing a new way for CO(2) capture and conversion.     

A novel electrochemical immunosensor based on Fe3O4@graphene nanocomposite modified glassy carbon electrode for rapid detection of Salmonella in milk

Foods contaminated by foodborne pathogens have always been a great threat to human life. Herein, we constructed an electrochemical immunosensor for Salmonella detection by using a Fe₃O₄@graphene modified electrode. Because of the excellent electrical conductivity and mechanical stability of graphene and the large specific surface area of Fe₃O₄, the Fe₃O₄@graphene nanocomposite exhibits an excellent electrical signal, which greatly increased the sensitivity of the immunosensor. Gold nanoparticles were deposited on Fe₃O₄@graphene nanocomposite by electrochemical technology for the immobilization of the antibody. Cyclic voltammetry was selected to electrochemically characterize the construction process of immunosensors. The microstructure and morphology of related nanocomposites were analyzed by scanning electron microscopy. Under optimized experimental conditions, a good linear relationship was achieved in the Salmonella concentration range of 2.4 × 10² to 2.4 × 10⁷ cfu/mL, and the limit of detection of the immunosensor was 2.4 × 10² cfu/mL. Additionally, the constructed immunosensor exhibited acceptable selectivity, reproducibility, and stability and provides a new reference for detecting pathogenic bacteria in milk.     

辣根过氧化物酶/聚乙烯醇缩丁醛/碳纳米管修饰玻碳电极检测过氧化氢

制备了辣根过氧化物酶/聚乙烯醇缩丁醛/碳纳米管修饰玻碳电极的过氧化氢生物传感器。以对苯二酚为电子媒介,采用循环伏安法和电流时间法考察了该传感器对H2O2的催化性能。讨论了媒介体浓度、工作电位、温度、pH对电极响应的影响。结果表明传感器对H2O2表现出良好的电催化性能。在pH=7.0,对苯二酚浓度4.2mmol/L,工作电位-250mV的实验条件下,H2O2浓度在1.67×10-7～1.29×10-5mol/L及1.58×10-5～1.17×10-3mol/L范围内与传感器的电流响应呈线性关系,检出限(S/N=3)为5.554×10-8mol/L。该传感器制备方法简单,成本低,稳定性好,对HO有快速灵敏的响应。     

Electrochemical behaviour of Sudan I at Fe3O4 nanoparticles modified glassy carbon electrode and its determination in food samples

In this work, a simple and sensitive electrochemical method was developed to determine Sudan I based on magnetic Fe₃O₄ nanoparticles modified glassy carbon electrode using cyclic voltammetry and differential pulse voltammetry. The sensor exhibited an obviously electrocatalytic activity towards the oxidation of Sudan I, which can be confirmed by the increased oxidation peak current and the decreased oxidation peak potential when compared with the bare GCE. The determination conditions, such as pH, modifier amount, accumulation time and accumulation potential, were optimised. And some kinetic parameters were calculated. Under the optimum experimental conditions, the oxidation current of Sudan I was proportional to its concentration from 0.01 to 1 μM and 1 to 20 μM. The detection limit was estimated to be 0.001 μM (S/N = 3). The developed method was successfully applied to determine Sudan I content in food samples with satisfactory results.     

还原氧化石墨烯分子印迹传感器的研制及其在磺胺间甲氧嘧啶检测中的应用

目的 建立一种印迹电化学传感器快速测定磺胺间甲氧嘧啶的方法。方法 以磺胺间甲氧嘧啶为目标分子, 在弱碱性条件下, 利用多巴胺在还原氧化石墨烯(reduced grapheme oxide, rGO)修饰后的玻碳电极上自聚制得分子印迹聚合膜。采取循环伏安法和差分脉冲伏安法分别对印迹膜的传感性能进行综合研究。结果 在最佳的优化条件下, 磺胺间甲氧嘧啶在20~1600 nmol/L的浓度范围内与峰电流具有良好线性关系, 相关系数r2=0.9964, 检出限为6.7 nmol/L (S/N=3)。实际样品测定的加标回收率为92.4%~108.3%。结论 该方法准确、灵敏, 适合于实际样品中磺胺间甲氧嘧啶残留的测定。