Electrochemical Determination of Dopamine Using a Poly(3,4-Ethylenedioxythiophene)-Reduced Graphene Oxide-Modified Glassy Carbon Electrode

Poly(3,4-ethylenedioxythiophene) was deposited on a reduced graphene oxide-decorated glassy carbon electrode through an electrochemical polymerization. The resulting glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode was applied as an electrochemical biosensor for the determination of dopamine in the presence of ascorbic acid and uric acid. The material deposited on glassy carbon electrode was investigated in terms of morphology and structural analysis. The comparison of electrochemical behavior of the glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode with the glassy carbon electrode-graphene oxide, glassy carbon electrode-reduced graphene oxide, and glassy carbon electrode-poly(3,4-ethylenedioxythiophene) electrodes exhibited high electrocatalytic activity for dopamine detection. Electrochemical kinetic parameters of glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene), including the charge transfer coefficient α (0.49) and electron transfer rate constant k_s (1.04), were determined and discussed. The glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode was studied for the determination of dopamine by differential pulse voltammetry and exhibited a linear range from 19.6 to 122.8?µM with a sensitivity of 3.27?µA?µM^?1?cm^?2 and a detection limit of 1.92?µM. The developed biosensor exhibited good selectivity toward dopamine with high reproducibility and stability.     

Electrochemical Determination of Capsaicin and Silymarin Using a Glassy Carbon Electrode Modified by Gold Nanoparticle Decorated Multiwalled Carbon Nanotubes

The goal of this study was to develop a suitable electroanalytical method for the determination of primary compounds in the extracts of capsaicin and silymarin. For this purpose, a glassy carbon electrode immobilized with multiwalled carbon nanotubes decorated with gold nanoparticles was characterized by high resolution transmission electron microscopy and attenuated total reflectance infrared spectroscopy. The developed electrochemical sensor had a linear dynamic range from 0.15 to 35.0 µM. In addition, the limits of quantification for silymarin and capsaicin with the gold nanoparticle decorated multiwalled carbon nanotubes were 0.1564 and 0.2761 µg L^?1 with relative standard deviations (n = 3) of 1.65% and 2.09% and equivalent mass percentages of 93.33% and 62.02%, respectively. The methodology may be employed for the determination of capsaicin and silymarin in pharmaceutical and food products.     

Polyfurfural-Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode for the Direct Determination of Nitrofurazone

An electrochemical sensor based on a polyfurfural-electrochemically reduced graphene oxide modified glassy carbon electrode has been developed for the sensitive and rapid determination of nitrofurazone. The morphologies and properties of the sensor were characterized by electrochemical impedance spectroscopy, scanning electron microscopy, cyclic voltammetry, and differential pulse voltammetry (DPV). In pH 7.0 Britton–Robinson buffer solution, the as-prepared polyfurfural-electrochemically reduced graphene oxide modified glassy carbon electrode shows excellent electrocatalytic performance for the electrochemical reduction of nitrofurazone, and the reduction peak current is about 9.45, 1.31, and 1.25 times higher than that of the bare glassy carbon electrode, polyfurfural modified glassy carbon electrode, and electrochemically reduced graphene oxide modified glassy carbon electrode, respectively. The DPV determination of nitrofurazone indicates that the linear range and detection limit of nitrofurazone are 1–50 and 0.25?µmol/dm³, respectively. In addition, this sensor exhibits high selectivity, reproducibility, stability, and also was successfully used to directly determine nitrofurazone in the commercial antibacterial lotion with comparative sensitivity to high-performance liquid chromatography, showing its promising application prospects.     

Electrochemical Determination of Carbofuran in Tomatoes by a Concanavalin A (Con A) Polydopamine (PDA)-Reduced Graphene Oxide (RGO)-Gold Nanoparticle (GNP) Glassy Carbon Electrode (GCE) with Immobilized Acetylcholinesterase (AChE)

A new biosensor method was developed to determine residual carbofuran in tomatoes in a rapid and convenient fashion based on immobilizing acetylcholinesterase (AChE) on an electrode modified by concanavalin A (Con A)/polydopamine (PDA)-reduced graphene oxide (RGO)-gold nanoparticle (GNP) nanocomposites. The specific binding between Con A and AChE was investigated by the Ellman method and cyclic voltammetry (CV). The synthesis of nanocomposites was monitored by ultraviolet-visible absorption spectroscopy, scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The results showed that, due to the specific binding and good electrical conductivity, the biosensor had 2.2 times higher bioactivity, leading to high sensitivity with a low Michaelis constant of 0.10?mM. Parameters that affect the response of the biosensor, such as the pH, enzyme loading, ionic concentration, and inhibition time, were optimized. When used for the detection of carbofuran, this biosensor showed a wide range of applicability from 5?µg/kg to 40?µg/kg with a detection limit of 0.012?µg/kg. In addition, the biosensor demonstrated good recovery values of 101% and 90% for 10?µg/kg and 100?µg/kg of the analyte, good stability, high repeatability, and a rapid detection time of 20?min for carbofuran in tomatoes, which provides significant advantages for future analysis.     

Sensitive Electrochemical Determination of Hydrogen Peroxide Using Copper Nanoparticles in a Polyaniline Film on a Glassy Carbon Electrode

Rapid and accurate determination of hydrogen peroxide is necessary in biochemistry and environmental science. In this paper, a sensitive hydrogen peroxide electrochemical sensor was developed by cyclic voltammetry deposition of polyaniline–copper nanocomposite film on a glassy carbon electrode. The synthesized polyaniline/Cu composites were characterized by scanning electron microscopy and X-ray diffraction. With a typical working potential of 0.4?V (versus Ag/AgCl) and a pH value of 6.0, the prepared electrochemical sensor achieved linear range of 1.0–500?µM for hydrogen peroxide detection. A relative standard deviation of 4.9% for n?=?7 and 10.0?µM of H₂O₂ and a limit of detection of 0.33?µM at a signal-to-noise ratio?=?3 were observed. The sensor was successfully used for the analysis of tap water, and a spiked recovery of 93.0?±?2.1% was obtained, further confirming the sensor’s accuracy and feasibility.     

聚乙撑二氧噻吩阳极降解的研究

研究了聚乙撑二氧噻吩(PEDOT)膜在水溶液中的阳极降解过程. 研究发现PEDOT的阳极过程可以分为p掺杂区[电位范围－0.3～0.5 V (相对于饱和甘汞电极; vs. SCE)]、过渡区[电位范围0.6～1 V (vs. SCE)]、过氧化区[电位范围1.2～1.6 V (vs. SCE)]三个电位区域. 用电化学阻抗谱法、循环伏安法、红外光谱技术、膜电阻测量以及电子自旋共振技术分别研究了PEDOT膜在这三个电位区域的行为. 结果表明: PEDOT膜在这三个电位区域的性质有明显不同. 在p掺杂区PEDOT膜的官能团、共轭结构、导电性均保持, 即在这个电位区发生可逆的掺杂/脱掺杂反应, 膜几乎不降解. 在过渡区和过氧化区, PEDOT膜均发生了降解. 与传统的导电聚合物在高电位的阳极降解的过氧化过程不同, 我们认为膜在较高电位(过渡区)发生一个驰豫过程, 该过程使得膜的官能团改变, 但是膜的共轭结构和导电性均保持; 而在更高的电位区(过氧化区)膜的降解和一般意义的过氧化降解相同, 此时膜的官能团、共轭结构、导电性均发生不可逆的破坏.     

聚(三聚氰胺)与金纳米粒共修饰玻碳电极用于芦丁的电化学测定

通过电聚合和电沉积方法首次制得聚(三聚氰胺)和金纳米粒共修饰的电极(PMel/Au/GCE),并对修饰电极进行交流阻抗电化学分析。采用循环伏安法研究了芦丁在修饰电极上的电化学行为,发现其氧化峰电流和还原峰电流较裸玻碳电极(GCE)以及聚(三聚氰胺)修饰的电极(PMel/GCE)明显增强,提高了检测的灵敏度。对溶液的pH值、金纳米粒子电沉积时间、三聚氰胺电聚合时间和扫描速率等实验条件进行了优化。采用示差脉冲伏安法对芦丁进行定量分析,芦丁浓度分别在7.8×10-9~1.2×10-6mol/L和1.2×10-6~1.5×10-5mol/L范围内与峰电流呈线性,其相关系数(r2)分别为0.997和0.993,检出限(S/N=3)为5.5×10-9mol/L。将该电极用于市售芦丁片检测,回收率为96.4%~101.8%。     

DNA/聚(3,4-乙烯基二氧噻吩)修饰电极的制备及其用于亚硝酸根的电化学行为及测定研究

采用恒电流和电沉积两步法制备了脱氧核糖核酸-聚(3,4-乙烯基二氧噻吩)(DNA-PEDOT)复合膜修饰玻碳电极。用电化学阻抗法(EIS)和循环伏安法(CV)表征了不同修饰电极的修饰可行性和表面的电子传递能力。结果表明,DNA可以牢固地结合在PEDOT膜上,并能改善PEDOT膜的性质。研究了NO2-在DNA-PEDOT修饰电极上的电化学行为,提出了一种新的检测NO2-的电化学方法。在0.1 mol/L pH7.0的磷酸盐缓冲溶液(PBS)中,NO2-在DNA-PEDOT修饰电极上于0.88 V左右出现1个较好的氧化峰,考察了该氧化峰的性质及其影响因素。示差脉冲伏安法(DPV)的结果表明,NO2-的DPV氧化峰电流与其浓度在0.3~1.0、1.0~20、20~100μmol/L 3个范围内呈良好的线性关系,检出限(S/N=3)为60 nmol/L,并考察了可能存在的干扰物质对测定的影响。结果显示,该复合膜修饰电极对NO2-的检测具有良好的稳定性和选择性。将其用于实际样品的检测,结果满意。     

聚对硝基苯偶氮间苯二酚修饰电极伏安法测定多巴胺

采用循环伏安法研究了多巴胺(DA)在聚对硝基苯偶氮间苯二酚(p-nitrobenzenazo resorcinol,简称NBAR)膜修饰电极上的电化学行为,用差示脉冲伏安法对多巴胺的含量进行测定.结果表明,聚NBAR膜修饰电极对DA有明显的电催化作用.在pH4.0的磷酸盐缓冲液中,氧化峰电流与DA浓度在5.0×10-6~8.0×10-4mol/L范围内呈良好的线性关系,检测限为6.0×10-7mol/L.修饰电极可有效消除针剂中其它组分对DA测定的干扰,已用于实际样品DA含量的测定,结果令人满意.     

Electrochemical Determination of Reduced Glutathione at Multiwalled Carbon Nanotubes/Poly(bromocresol green)Modified Glassy Carbon Electrode

A multiwalled carbon nanotubes/poly(bromocresol green) modfied glassy carbon electrode (MWNTs-PBG/GCE) was used to investigate the electrochemical behavior of reduced glutathione(GSH). GSH showed an irreversible oxidation process on MWNTs-PBG/GCE with an oxidation peak at 0.77 V(vs. SCE) in a phosphate buffer solution(pH=4.0). The kinetic parameters of the electrochemical behavior of GSH on MWNTs-PBG/GCE were calculated. Under the optimal conditions and with the help of amperometric method, a linear relationship was obtained between the oxidation peak current and GSH concentration in the range from 2×10–7 mol/L to 5×10–6 mol/L with the detection limit as 1×10–8 mol/L(signal-to-noise ratio of 3). The current reached the steady-state current within about 5 s. The modified electrode surface had very good reproducibility and stability.     

聚对氨基苯磺酸/石墨烯修饰玻碳电极伏安法测定痕量汞

制备了对氨基苯磺酸/石墨烯复合膜修饰电极,研究了汞在修饰电极上的电化学行为。 在0.1 mol/L、pH=4.0的磷酸盐缓冲液中,以此修饰电极为工作电极,在-1.2 V搅拌富集5 min,用差分脉冲伏安法测定0.31 V处的溶出峰电流。 结果表明,该电极显著提高了汞离子的电化学响应信号。 在优化条件下,峰电流与Hg2+的浓度在1.0×10-6~5.0×10-4 mol/L范围内呈良好的线性关系,相关系数为0.995。 方法的检出限为5.0×10-7 mol/L。 将该法用于水样中痕量汞的测定,回收率为92.2%~105.2%。     

Electrochemical Determination of Lead(II) in Environmental Waters Using a Sulfydryl Modified Covalent Organic Framework by Square Wave Anodic Stripping Voltammetry (SWASV)

A novel sulfhydryl-modified covalent organic framework was designed for the selective determination of lead(II) using square wave anodic stripping voltammetry. The introduction of sulfhydryl groups enhanced the selectivity and sensitivity of the covalent organic framework for analytes. The sulfhydryl-modified covalent organic framework was characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. Under the optimized conditions, a sulfhydryl-modified covalent organic framework/gold electrode was successfully used for the determination of lead(II) in water samples. The newly developed square wave anodic stripping voltammetry method exhibited wide linearity (0.05 to 20?ng mL^?1, r?=?0.991), a low limit of detection (0.015?ng mL^?1) and good precision, with a relative standard deviation values <5.1%. The limit of detection was lower than 10?ng mL^?1, the level of lead(II) in drinking water permitted by the World Health Organization. The recoveries of three spiked samples ranged from 90.0% to 104.0%, with relative standard deviations <4.9%. Satisfactory reproducibility and good repeatability demonstrated that the newly developed method is very suitable for the detection of lead(II) in real water samples, with significant advantages over existing methods.     

Electrochemical Determination of Pyrogallol at Conducting Poly(3,4‐ethylenedioxythiophene) Film‐Modified Screen‐Printed Carbon Electrodes

The electrochemical oxidation of pyrogallol at electrogenerated poly(3,4‐ethylenedioxythiophene) (PEDOT) film‐modified screen‐printed carbon electrodes (SPCE) was investigated. The voltammetric peak for the oxidation of pyrogallol in a pH 7 buffer solution at the modified electrode occurred at 0.13 V, much lower than the bare SPCE and preanodized SPCE. The experimental parameters, including electropolymerization conditions, solution pH values and applied potentials were optimized to improve the voltammetric responses. A linear calibration plot, based on flow‐injection amperometry, was obtained for 1–1000 µM pyrogallol, and a slope of 0.030 µA/µM was obtained. The detection limit (S/N=3) was 0.63 µM.     

Enhanced Electrochemical Determination of Catechol and Hydroquinone Based on Pd Nanoparticles/Poly(Taurine) Modified Glassy Carbon Electrode

Here, Pd nanoparticles and poly(taurine) film was prepared on the glassy carbon electrode surface (Pd/Poly(TAU)/GCE) by the rapid electrochemical technique. The proposed composite surface was characterized by scanning electron microscopy(SEM), X‐ray photoelectron spectroscopy(XPS) and electrochemical impedance spectroscopy(EIS). Enhanced electron transfer ability and higher electroactive surface area were achieved at Pd/Poly(TAU)/GCE as compared to the bare GCE and polymer film electrode. The new and highly stable Pd/Poly(TAU)/GCE was employed for the individual and simultaneous determination of hydroquinone and catechol which were environmentally toxic. Under the optimized conditions, HQ and CC were individually determined by using the differantial pulse voltammetry in the linear ranges of 0.008–100 μM and 0.001–100 μM with the detection limits of (LOD) 2.1 nM and 0.68 nM, respectively. In case of simultaneous determination, LODs were found as 10 nM and 0.88 nM for HQ and CC, respectively. The content of both analytes in the real sample analysis was evaluated in the river water and tap water successfully.     

Application of a Glassy Carbon Electrode Modified with Poly(Glutamic Acid) in Caffeic Acid Determination

Glassy carbon electrodes were coated with films of poly(glutamic acid) (PG), and the modified electrode proved to be very effective in the oxidation of caffeic acid. The performance of the film was also tested with ascorbic acid, coumaric acid, ferulic acid, sinapic acid and chlorogenic acid. At pH 5.6, all the hydroxycinnamic acids yield a higher peak current intensity when oxidized after incorporation in the PG-modified electrode, and only the oxidation of ascorbic acid exhibits overpotential reduction. At pH 3.5 only caffeic and chlorogenic acid are incorporated in the modified electrode and exhibit a well-defined oxidation wave at +0.51 V and +0.48 V, which is the base for their determination. Linear calibration graphs were obtained from 9 × 10⁻⁶ mol L⁻¹ to 4 × 10⁻⁵ mol L⁻¹ caffeic acid by linear voltammetric scan and from 4 × 10⁻⁶ mol L⁻¹ to 3 × 10⁻⁵ mol L⁻¹ by square wave voltammetric scan. The method was successfully applied to the determination of caffeic acid in red wine samples without interference from other hydroxycinnamic acids or ascorbic acid.     

Platinum Nanoparticles/Poly(isoleucine) Modified Glassy Carbon Electrode for the Simultaneous Determination of Hydroquinone and Catechol

A new electrochemical sensor based on Poly(Isoleucine) modified glassy carbon electrode decorated with platinum nanoparticles (Pt/Poly(Isoleucine)/GCE) was developed for sensitive individual and simultaneous determination of hydroquinone (HQ) and catechol (CC). Scanning electron microscopy (SEM), Electrochemical impedance spectroscopy (EIS), Cyclic voltammetry (CV) and Differential pulse voltammetry (DPV) were performed in order to characterize the Pt/Poly(Isoleucine)/GCE nanocomposite. For simultaneous determination of HQ and CC, Pt/Poly(Isoleucine)/GCE showed wide linear range between the 0.01–100.0 μM. The detection limits were 0.006 μM for HQ and 0.005 μM for CC. The Pt/Poly(Isoleucine)/GC electrode exhibited good sensitivity and reliability in the simultaneous electroanalysis of two isomers in PBS of pH 7.5. The modified electrode was used to detect the isomers in naturel samples.     

聚对氨基苯磺酸修饰电极对桑枝中桑色素的灵敏测定

采用电聚合的方法制备了聚对氨基苯磺酸(PABSA)修饰电极,以循环伏安法和差分脉冲伏安法研究了桑色素在该修饰电极上的电化学行为。PABSA和黄酮类药物桑色素的π-π共轭作用使得桑色素在该修饰电极上产生的氧化峰更加灵敏。实验发现,在pH 7.0的磷酸盐缓冲介质中,桑色素在0.214 V处产生灵敏的氧化峰。在优化实验条件下,采用差分脉冲伏安法对桑色素进行定量测定,桑色素的氧化峰电流与其浓度呈良好的线性关系,线性范围为5.0×10-7~1.0×10-3 mol/L,检出限为1.0×10-7 mol/L。将该修饰电极用于桑枝生物样品中桑色素含量的测定,结果满意。该方法具有灵敏度高、重现性好的特点,且该修饰电极稳定性高,可重复使用。     

Met.(Cu,Ag)-TCNQ有机薄膜的EB CL像

自从1979年Potember等人首先发现了CuTCNQ有机薄膜具有受电流控制的电开关特性以来[1]，有关CuTCNQ及AgTCNQ这些阴离子基过渡金属盐（以下简称为Met．（CU、Ag）-TCNQ）有机薄膜的光存储特性、光电开关特性，以及某些气教特性的研究结果便不断报导出来[2-4]，引起人们极大的兴趣．作为很有前途的有机光电功能材料，至今对其电导及光电特性的机理研究仍显得十分薄弱，极大影响了它们进一步向实用器件方向的发展．由于CuTCNQ的晶体参数至今未见报导，我们依据CuTCNQ粉末X射线小角衍射谱对比AgTCNQ相应的粉末X射线衍射数据，…     

Highly Sensitive Electrochemical Sensor for Nitric Oxide Using the Self‐Assembled Monolayer of 1,8,15,22‐Tetraaminophthalocyanatocobalt(II) on Glassy Carbon Electrode

Glassy carbon (GC) electrode modified with a self‐assembled monolayer (SAM) of 1,8,15,22‐tetraaminophthalocyanatocobalt(II) (4α‐Co^IITAPc) was used for the selective and highly sensitive determination of nitric oxide (NO). The SAM of 4α‐Co^IITAPc was formed on GC electrode by spontaneous adsorption from DMF containing 1 mM 4α‐Co^IITAPc. The SAM showed two pairs of well‐defined redox peaks corresponding to Co^III/Co^II and Co^IIIPc^?1/Co^IIIPc^?2 in 0.2 M phosphate buffer (PB) solution (pH 2.5). The SAM modified electrode showed excellent electrocatalytic activity towards the oxidation of nitric oxide (NO) by enhancing its oxidation current with 310 mV less positive potential shift when compared to bare GC electrode. In amperometric measurements, the current response for NO oxidation was linearly increased in the concentration range of 3×10^?9 to 30×10^?9 M with a detection limit of 1.4×10^?10 M (S/N=3). The proposed method showed a better recovery for NO in human blood serum samples.     

High Sensitivity and Reproducibility of a Bismuth/Poly(bromocresol purple) Film Modified Glassy Carbon Electrode for Determination of Trace Amount of Cadmium by Differential Pulse Anodic Stripping Voltammetry

This work described a novel type of bismuth/poly(bromocresol purple) film modified glassy carbon electrode (denoted as Bi/Poly(BCP)/GCE) for anodic stripping analysis of trace Cd²⁺. The Bi/Poly(BCP)/GCE was fabricated in situ by depositing simultaneously bismuth and cadmium by reduction at ?1.20 V on the poly(BCP) film using a differential pulse voltammetry. Under the optimum conditions, the anodic stripping peak current response increased linearly with the Cd²⁺ concentrations in a range of 2.0×10^?8–1.0×10^?7 M and 1.0×10^?7–6.0×10^?6 M in 0.1 M NaAc‐HAc buffer solution (pH 5.0) with the detection limit of 6.5×10^?9 M (S/N=3). The Bi/poly(BCP)/GCE performed good reproducibility and high sensitivity. Finally, this proposed method was successfully applied to determine the concentration of Cd²⁺ in water samples.