硫化物在乙酰二茂铁修饰碳糊电极上的电化学行为及电分析

研究了S2-在乙酰二茂铁(AFc)修饰碳糊电极(AFc/CPE)上的电催化氧化行为及其电化学分析方法。实验结果表明,AFc/CPE对S2-的电化学氧化具有良好的催化作用。用计时电流法(CA)测定了S2-在AFc/CPE上的电催化氧化反应速率常数k为(2.60±0.05)×105 L.mol-1.s-1。用方波伏安法(SWV)测得催化氧化峰电流与S2-的浓度在5.0×10-5～1.0×10-3 mol.L-1范围内呈良好线性关系,检出限(S/N=3)为1.3×10-7 mol.L-1,同时运用SWV法对造纸废水水样中S2-的含量进行了电化学定量测定。     

Precursor Modified Electrodes: Electrochemical Detection of Captopril

A fast and facile method for captopril determination is reported using an electrode modified to contain the precursor of a species which can selectively and suitably detect the target. Cyclotriveratrylene (CTV) is first incorporated into a carbon paste electrode then the precursor is converted into cyclotricatechylene (CTC) using voltammetric methods at the point in time when the captopril detection is sought. The resulting cyclotricatechylene (CTC) was used to mediate the electrochemical detection of the thiol containing drug, captopril, via electrocatalytic oxidation. Optimization towards the detection method was investigated by changing experimental conditions including pH and mediator loading. Optimal analytical parameters were determined in acidic conditions which gave a real measurable limit of detection of 1 µM for captopril detection.     

Electrochemical Detection of Alloxan on Reduced Graphene Oxide Modified Glassy Carbon Electrode

Alloxan is a toxic reagent that strongly induces the diabetes by destroying insulin‐producing β‐cells in the pancreas of living organisms. The reduction product of alloxan is dialuric acid, which is responsible for the intracellular generation of ROS to enhance the stress in living cells to cause kidney disease or diabetic nephropathy. Herein, we studied for the first time the electrochemical properties of alloxan on reduced graphene oxide modified glassy carbon electrode (rGO/GCE) in 0.1 M phosphate buffer solution (PBS) at pH 7. The obtained results were compared with graphene oxide modified GCE (GO/GCE) and bare GCE surfaces. The modified rGO/GCE showed well defined redox couple with 10 fold increase in both reduction as well as oxidation peak current for alloxan than that of GO/GCE and bare GCE. Differential pulse voltammetry (DPV) technique shows the linear increase in both oxidation and reduction peak current of alloxan in the range of 30 μM to 3 mM with LOD of 1.2 μM. An amperometric signal of alloxan is also increases with respect to each addition of 50 μM of alloxan on rGO/GCE at constant potential of ?0.05 V. The linear range of alloxan is observed between 50 μM to 750 μM (S/N=3). This kind of rGO/GCE surface is more suitable platform or sensor matrix for estimating unknown concentration of alloxan molecule in the real biological systems.     

Graphene Nanocomposites Based Electrochemical Sensing Platform for Simultaneous Detection of Multi-drugs

Three reduced graphene oxide nanocomposites were employed to achieve the simultaneous electrochemical determination of multi-drugs including acetaminophen (ACTM), carbendazim (CB) and ciprofloxacin (CFX). All nanocomposite modified electrodes showed improved current responses for three drugs. Notably cauliflower-like platinum nanoparticles decorated reduced graphene oxide modified electrode (or Pt−RGO/GCE) exhibited the best performance in terms of electrochemical stability. Using Pt−RGO/GCE, the linear detect ranges of 30–120 μM, 25–115 μM and 10–25 μM, and detection limit values of 3.49, 2.96, and 1.53 μM were achieved for ACTM, CB and CFX respectively. The electrode was further used for the successful determination of above drugs in tap and river water using differential pulse voltammetry. From the obtained results, we believe that Pt-RGO/GCE is highly promising for the fabrication of robust electrochemical sensors for simultaneously determining ACTM, CB and CFX or similar types of drugs in the future.     

Electrochemical Investigation of Metal Oxide Conducting Electrodes for Direct Detection of Sulfide

This study examined the performance of four conducting metal oxide electrodes for the direct electrochemical analysis of sulfide; the electrode materials studied were indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO) and gallium doped zinc oxide (GZO). Cyclic voltammetry (CV) results obtained using the ITO, AZO, GZO and FTO electrodes showed direct electrooxidation peak potential of sulfide at 381, 507, 400, and 850 mV vs. Ag/AgCl, respectively; however, the less positive oxidation potential and high catalytic current response of the ITO electrode made it the electrode of choice for the direct oxidation of sulfide. The effects of different electrolytes and buffer solutions on the CV responses were also evaluated. A linear concentration range up to 350 µM and a detection limit of 8.0 µM were achieved. CV response was highly reproducible, remaining unaffected even after 50 measurements. The sensor was found to have good selectivity, with no interference from sulfite, sulfate or chloride ions. The present findings demonstrate that the bare ITO electrode can be used as the basis of an inexpensive, sensitive, selective and robust sulfide sensor.     

Reduced Graphene Oxide Nanocomposite Modified Electrodes for Sensitive Detection of Ciprofloxacin

The synthesis of novel nanocomposites with great sensing enhancement has played an important role in analytical chemistry, especially in the electrochemical detection of drug molecules. In this work, we report a wet chemical method for the preparation of a gold nanoparticle coated β‐cyclodextrin functionalized reduced graphene oxide nanocomposite. A number of different analytical techniques including ultraviolet‐visible spectroscopy, fourier transform infrared spectroscopy, scanning electron microscope and energy dispersive X‐ray spectroscopy were employed to characterize the as‐synthesized nanocomposite. With excellent electrocatalytic properties and high supramolecular recognition ability, the as‐synthesized nanocomposite was used to modify a glassy carbon electrode surface for the sensitive determination of ciprofloxacin using voltammetric technique. The current response of ciprofloxacin on the nanocomposite modified electrode was greatly enhanced compared to that on the bare and other modified electrodes. Using differential pulse voltammetry, the oxidation peak currents increased linearly with the ciprofloxacin concentrations in the range between 0.01 to 120 μM with a detection limit of 2.7 nM. The electrochemical testing results showed good stability and reproducibility. Therefore, the nanocomposite could be a potential candidate for the development of electrochemical sensors for sensitive and selective determination of ciprofloxacin or similar drugs in the future.     

Electrochemical Sensor for Sensitive Determination of Capsaicin Using Pd Decorated Reduced Graphene Oxide

In this work, the reduced graphene oxide functionalized with poly dimethyl diallyl ammonium chloride (PDDA) modified palladium nanoparticles (PDDA‐rGO/Pd) had been facile synthesized and used as the sensing layer for sensitive determination of capsaicin. The prepared composite was characterized by transmission electron microscopy, UV‐visible absorption spectroscopy. The image demonstrated that Pd nanoparticles were uniformly distributed on the graphene surface. The electrochemical properties of the prepared sensor were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the nanocomposite exhibits attractive electrocatalytic activity towards the oxidation of capsaicin. This attributed to the synergistic action of the excellent properties of Pd nanoparticles and graphene nanosheets. Under optimized conditions, the electrochemical sensor possessed a dynamic linear range from 0.32 μM to 64 μM with a detection limit of 0.10 μM (S/N=3) for capsaicin detection. Moreover, the cost‐effective and simple fabrication procedure, good reproducibility and stability as well as acceptable accuracy for capsaicin determination in actual samples are also the main advantages of this method, which might have broad application in other amide alkaloid detection.     

二氧化锆/石墨烯复合材料对亚硝酸盐的电化学传感研究

制备了一种二氧化锆/还原氧化石墨烯(ZrO2NPs/rGO)复合材料修饰电极的亚硝酸盐电化学传感器,并成功用于亚硝酸盐的检测.采用循环伏安法和电流-时间曲线考察了修饰电极的电化学行为.实验结果表明,ZrO2NPs/rGO复合材料修饰电极对亚硝酸盐具有良好的电流响应.在最优实验条件下,电流-时间曲线中的电流响应信号与亚硝酸盐浓度在3.0×10Symbolm@@_7～1.0×10Symbolm@@_6 mol/L和1.0×10Symbolm@@_6～6.0×10Symbolm@@_6 mol/L的范围内呈良好的线性关系,检测限为1.0×10Symbolm@@_7 mol/L(S/N 3).该传感器灵敏性高、稳定性和重现性好.使用此传感器检测实际样品香肠中的亚硝酸盐的回收率为93.7％～110.4％,相对标准偏差为1.6％～2.1％.     

Cauliflower‐like Platinum Particles Decorated Reduced Graphene Oxide for Sensitive Determination of Acetaminophen

Over the past years, the development of electrochemical sensing platforms for the sensitive detection of drug molecules have received great interests. In this research study, we introduced cauliflower‐like platinum particles decorated reduced graphene oxide modified glassy carbon electrode (Pt?RGO/GCE) as an electrochemical sensing platform for highly sensitive determination of acetaminophen (ACTM). The sensor was prepared via a simple and environmentally friendly two‐step electrodeposition method at room temperature. The combination of conductive RGO nanosheets and unique structured Pt particles (average 232 nm in diameter) provided an efficient interface with large effective surface area which greatly facilitated the electron transfer of ACTM. The experimental conditions that might affect the drug detection were studied in detail and optimized for best performance. The Pt?RGO/GCE was able to detect ACTM up to the limit of 2.2 nM with a linear concentration range from 0.01 to 350 μM. With its high reproducibility, excellent stability and selectivity, the as‐fabricated sensor was successfully applied to the ACTM content measurement in commercial tablets.     

基于还原石墨烯/纳米银复合材料的电化学传感器测定双酚A

石墨烯特有的褶皱层状结构以及银纳米粒子良好的催化性能,使其在电化学方面具有良好的应用潜能.本研究以柠檬酸钠为还原剂,通过水热反应原位制备出还原石墨烯/纳米银复合材料(rGO/AgNPs),用于修饰玻碳电极,研究了双酚A的电化学行为.循环伏安法(CV)和方波伏安法(SWV)的实验结果表明,双酚A可以在rGO/AgNPs修饰电极表面发生快速的氧化还原反应,基于此实现了对双酚A的高灵敏检测.在最优条件下,双酚A的氧化峰电流与其浓度在0.1~40.0μmol/L范围内呈良好的线性关系(r2=0.996),检出限为50.7 nmol/L(S/N=3).将其用于实际环境和塑料样品中双酚A的检测,回收率为91.7%~102.9%.     

Measurement of the Antipsychotic Clozapine Using Reduced Graphene Oxide Nanocomposites-Au/Pd/Pt Electrodes

Enhanced methods of drug monitoring are required to support the individualization of therapeutic drug dosing. Clozapine is one of the most important medications for managing schizophrenia, and timely measurement of serum clozapine levels has been identified as a barrier to the broader use of clozapine. For the first time, reduced graphene oxide nanocomposites were used to construct an electrochemical clozapine (Clz) sensor. The Reduced graphene oxide (Rego) nanocomposites were synthesized and characterized by using X-Ray Diffraction (XRD), Fourier-Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM) techniques. The Clz sensing electrode was fabricated by drop coating of Rego nanocomposites suspension and Nafion solution on the pencil graphite electrode, respectively. The electrochemical behavior and influence of various physicochemical parameters of sensing electrodes were investigated by using cyclic voltammetry (CV) and differential voltammetry (DPV) techniques. The designed sensor displayed decent linear range, detection limit, reproducibility, and reusability results. Under optimum experimental parameters a linear dynamic range of 0.05–10 μM clozapine was observed with actual detection limit of 50 nM. Furthermore, the designed sensing electrode was used to measure the amount of Clz in real samples.     

磁性石墨烯修饰辛基酚印迹传感器制备及应用研究

以辛基酚(4-OP)为模板分子,多巴胺为功能单体,采用电聚合技术在磁性石墨烯修饰碳电极表面制备对辛基酚具有高选择性与灵敏性的印迹电化学传感器。采用循环伏安法(CV)和差分脉冲伏安法(DPV)对此印迹传感器的电化学性能进行详细表征;采用扫描电子显微技术对修饰电极的形貌进行表征。结果表明,此印迹电化学传感器对辛基酚具有良好的特异识别性能。采用 DPV 法考察了孵化时间和洗脱溶剂对印迹传感器性能影响,结果表明,最佳孵化时间为14 min。此印迹电化学传感器的响应电流(△IR )与辛基酚在5.0×10-6~5.0×10-9 mol/ L 范围内浓度的负对数(-lgC)呈良好的线性关系,线性方程为△IR ( mA)=-0.25lgC(mol/ L)+2.35,检出限为3.64×10-10 mol/ L (S/ N=3)。此印迹电化学传感器对辛基酚具有良好的选择性和灵敏性,成功用于实际水样中辛基酚的检测,回收率为96.0%~104.0%。     

Electrochemical Detection of Steroid Hormones Using a Nickel‐Modified Glassy Carbon Electrode

This paper demonstrates the development of an analytical method for detecting steroid hormones by coupling HPLC to electrochemical detection, using a nickel‐modified glassy carbon electrode. The method was evaluated in terms of sensitivity, linear dynamic range, limit of detection, and response stability. The developed method exhibited good figures of merit for the steroid hormones studied with no evidence of electrode fouling. As an example, the limit of detection (S/N=3) for E3 was 0.10 µM and the response precision (n=5) was 0.6 %. The application of the method for the analysis of a real river water sample is demonstrated.     

Determination of Sulfide by Hematoxylin Multiwalled Carbon Nanotubes Modified Carbon Paste Electrode

This study investigates a new approach for the amperometric determination of sulfide using a hematoxylin multiwalled carbon nanotubes modified carbon paste electrode (HM‐MWCNTs/CPE). The experimental results show that HM‐MWCNTs/CPE significantly enhances the electrocatalytic activity towards sulfide oxidation. Cyclic voltammetric studies show that the peak potential of sulfide shifted from +400 mV at unmodified CPE to +175 mV at HM‐MWCNTs/CPE. The currents obtained from amperometric measurements at optimum conditions were linearly correlated with the concentration of sulfide. The calibration curve was obtained for sulfide concentrations in the range of 0.5–150×10^?6 mol L^?1. The detection limit was found to be 0.2×10^?6 mol L^?1 for the amperometric method. The proposed method was successfully applied to a river water sample in Pardubice, Czech Republic.     

铁酞菁/氮掺杂石墨烯复合物的电化学传感研究

本文用快速简便的方法制备了铁酞菁/氮掺杂石墨烯（FePc/N-G）修饰电极,用于定量检测半胱氨酸. 采用电化学方法对修饰电极的性能进行了表征,结果表明氮掺杂石墨烯负载铁酞菁修饰电极对半胱氨酸具有更宽的线性响应范围和较高的灵敏度.     

Protein‐Directed In Situ Synthesis of Gold Nanoparticles on Reduced Graphene Oxide Modified Electrode for Nonenzymatic Glucose Sensing

A novel nonenzymatic glucose sensor was developed based on well‐dispersed gold nanoparticles, which were in situ grown under direction of protein on a reduced graphene oxide modified electrode. This electrode exhibited high electrocatalytic activity towards glucose oxidation without use of any enzyme or mediator. In application for the amperometric detection of glucose, a wide linear range of 0.02–16.6 mM, low detection limit of 5 µM and good selectivity were obtained. The attractive analytical performances of the proposed glucose sensor, coupled with the facile preparation method, provide a promising electrochemical platform for the development of effective nonenzymatic sensors.     

A Highly Sensitive Sensor Based on Reduced Graphene Oxide,Carbon Nanotube and a Co(II) Complex Modified Carbon Paste Electrode: Simultaneous Determination of Isoprenaline,Captopril and Tryptophan

This paper describes the development of a reduced graphene oxide (RGO), carbon nanotube (CNT) and Co(II) complex (cobalt(II) bis (benzoylacetone) ethylenediimino) (CBE) modified carbon paste electrode (CPE) for simultaneous determination of isoprenaline (IP), captopril (CAP) and tryptophan (Try). A pair of well‐defined redox peaks of Co(II) complex were obtained through a direct electron transfer between the Co(II) complex and the CPE. The proposed sensor showed very efficient electrocatalytic activity for anodic oxidation of IP in a 0.1 M phosphate buffer solution (pH 7.0). Square wave voltammetry (SWV) exhibited two linear dynamic ranges of 0.125–30.0 µM and 30.0–300.0 µM for IP. The detection limit for IP was found to be 50 nM. The proposed sensor was successfully applied for the determination of IP in real samples such as human blood serum, urine and IP ampoule.     

Electrochemical Detection of Three Monohydroxylated Polycyclic Aromatic Hydrocarbons Using Electroreduced Graphene Oxide Modified Screen‐printed Electrode

An electrochemical sensor for detection of three monohydroxylated polycyclic aromatic hydrocarbons (OH?PAHs) was fabricated by electrochemical reduction of graphene oxide (E‐rGO) on screen‐printed electrode (SPE). The E‐rGO film presents typical wrinkled structure with porous and cavity‐like nanostructure, providing large surface area, effective π‐electron system and high electrical conductivity. The developed E‐rGO/SPE sensor exhibits outstanding sensing performance for the target OH?PAHs, 2‐hydroxynaphthalene, 3‐hydroxyphenanthrene, and 1‐hydroxypyrene, within a linear range varying from 50–800 nM, 50–1150 nM, and 100–1000 nM, and with a limit of detection (LOD) of 10.1 nM, 15.3 nM, and 20.4 nM (S/N=3), respectively. The electrochemical sensor possesses excellent stability, acceptable reproducibility, and good anti‐interference ability. Additionally, the proposed sensor can be applied to the analysis of OH?PAHs in the urine samples with recoveries of 98.1–105.9 %.     

Magnetite Nanorods Stabilized by Polyaniline/Reduced Graphene Oxide as a Sensing Platform for Selective and Sensitive Non‐enzymatic Hydrogen Peroxide Detection

In this study, magnetite nanorods stabilized on polyaniline/reduced graphene oxide (Fe₃O₄@PANI/rGO) was synthesized via a wet‐reflux strategy. The possible formation of Fe₃O₄@PANI/rGO was morphologically and structurally verified by field emission scanning electron microscopy (FE‐SEM), Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Furthermore, the thermal stability of Fe₃O₄@PANI/rGO was measured by a thermogravimetric analyzer (TGA); the composite had good thermal stability owing to the ceramic nature of Fe₃O₄. The Fe₃O₄@PANI/rGO has been applied as a potential sensing platform for electrochemical detection of hydrogen peroxide (H₂O₂). By the combined efforts of extended active surface area, active carbon support, more catalytic active sites and high electrical conductivity, the Fe₃O₄@PANI/rGO exhibited an improved performance toward the non‐enzymatic detection of H₂O₂ in 0.5 M KOH with a fast response time (5 s), high sensitivity (223.7 μA mM^?1 cm^?2), low limit of detection (4.45 μM) and wide linear range (100 μM–1.5 mM). Furthermore, the fabricated sensor exhibited excellent recovery rates (94.2–104.0 %) during real sample analysis.     

Electrochemical Study and Application on Shikonin at Poly(diallyldimethylammonium chloride) Functionalized Graphene Sheets Modified Glass Carbon Electrode

The electrochemical behaviors of shikonin at a poly(diallyldimethylammonium chloride) functionalized graphene sheets modified glass carbon electrode(PDDA-GS/GCE) have been investigated. Shikonin could exhibit a pair of well-defined redox peaks at the PDDA-GS/GCE located at 0.681 V(E_pa) and 0.662 V(E_pc)[vs. saturated calomel electrode(SCE)] in 0.1 mol/L phosphate buffer solution(pH=2.0) with a peak-to-peak separation of about 20 mV, revealing a fast electron-transfer process. Moreover, the current response was remarkably increased at PDDA-GS/GCE compared with that at the bare GCE. The electrochemical behaviors of shikonin at the modified electrode were investigated. And the results indicate that the reaction involves the transfer of two electrons, accompanied by two protons and the electrochemical process is a diffusional-controlled electrode process. The electrochemical parameters of shikonin at the modified electrode, the electron-transfer coefficient(α), the electron-transfer number(n) and the electrode reaction rate constant(k_s) were calculated to be as 0.53, 2.18 and 3.6 s^-1, respectively. Under the optimal conditions, the peak current of differential pulse voltammetry(DPV) increased linearly with the shikonin concentration in a range from 9.472×10^-8 mol/L to 3.789×10^-6 mol/L with a detection limit of 3.157×10^-8 mol/L. The linear regression equation was I_p=0.7366c+0.7855(R=0.9978; I_p: 10^-7 A, c: 10^-8 mol/L). In addition, the modified glass carbon electrode also exhibited good stability, selectivity and acceptable reproducibility that could be used for the sensitive, simple and rapid determination of shikonin in real samples. Therefore, the present work offers a new way to broaden the analytical application of graphene in pharmaceutical analysis.