A sensitive hydrazine electrochemical sensor based on electrodeposition of gold nanoparticles on choline film modified glassy carbon electrode

A highly sensitive hydrazine sensor was developed based on the electrodeposition of gold nanoparticles onto the choline film modified glassy carbon electrode (GNPs/Ch/GCE). The electrochemical experiments showed that the GNPs/Ch film exhibited a distinctly higher activity for the electro-oxidation of hydrazine than GNPs with 3.4-fold enhancement of peak current. The kinetic parameters such as the electron transfer coefficient (α) and the rate of electron exchange (k) for the oxidation of hydrazine were determined. The diffusion coefficient (D) of hydrazine in solution was also calculated by chronoamperometry. The sensor exhibited two wide linear ranges of 5.0 × 10⁻⁷-5.0 × 10⁻⁴ and 5.0 × 10⁻⁴-9.3 × 10⁻³ M with the detection limit of 1.0 × 10⁻⁷ M (s/n = 3). The proposed electrode presented excellent operational and storage stability for the determination of hydrazine. Moreover, the sensor showed outstanding sensitivity, selectivity and reproducibility properties. All the results indicated a good potential application of this sensor in the detection of hydrazine.     

Modified glassy carbon electrode with multiwall carbon nanotubes as a voltammetric sensor for determination of noscapine in biological and pharmaceutical samples

A simple and highly sensitive method is described for direct voltammetric determination of noscapine in blood and pharmaceutical sample. Glassy carbon electrode with effective method is modified with multiwall carbon nanotubes (MWNTs) to cause activation of multiwall carbon nanotubes structures for electrocatalyzes of noscapine oxidation. The cyclic voltammetric (CV) results indicated that MWNTs remarkably enhances electrocatalytic activity toward the oxidation of noscapine, which is leading to considerable improvement of anodic peak current for noscapine, and allows the development of a highly sensitive voltammetric sensor for detection of noscapine in pharmaceutical and clinical samples. Under the optimum condition, the calibration curve was linear in the concentration range 4.0 × 10⁻⁷–1.0 × 10⁻⁴ mol L⁻¹ with the detection limit of 8.0 × 10⁻⁸ mol L⁻¹ and relative standard deviation (R.S.D.%) lower than 1.0% (n = 5). Finally, some kinetic parameters were determined and multistep mechanism for oxidation of noscapine for first time was proposed.     

Sensitive electrochemical determination of acetaminophen in pharmaceutical formulations at multiwalled carbon nanotube-alumina-coated silica nanocomposite modified electrode

A highly sensitive electrochemical sensor for the determination of acetaminophen at the multiwalled carbon nanotube-alumina-coated silica (MWCNT-ACS) nanocomposite modified glassy carbon electrode is reported. The morphology of the MWCNT-ACS nanocomposite was characterized by field emission scanning electron microscopy. The electrocatalytic properties of the MWCNT-ACS nanocomposite modified glassy carbon electrode were characterized by cyclic voltammetry and square-wave voltammetry in the presence of acetaminophen. The MWCNT-ACS nanocomposite modified glassy carbon electrode exhibited the abilities to raise the current response and to decrease the electrooxidation potential. In cyclic voltammetric responses, the oxidation peak current of acetaminophen obtained at the MWCNT-ACS modified glassy carbon electrode was 100 times greater than that of bare glassy carbon electrode. The MWCNT-ACS nanocomposite modified glassy carbon electrode for the determination of acetaminophen displayed a sensitivity of 376.5 A M⁻¹ cm⁻² and a detection limit of 0.05 μM using square-wave voltammetry. The analytical applicability of the developed method was achieved by analyzing the content of acetaminophen in five commercial drugs without pretreatment.     

Pt石墨烯-碳纳米管修饰玻碳电极对甲醛的电催化氧化

该文首先制备了石墨烯-碳纳米管复合材料,然后通过水热法将Pt纳米粒子修饰于该复合材料表面,制成了Pt／石墨烯（Graphene,Gr）-碳纳米管（Carbonnanotubes,CNTs）／玻碳电极（Glassycarbonelectrode,GCE）传感器。在磷酸盐缓冲溶液（pH=2．3）中利用循环伏安法研究了甲醛在Pt／Gr—CNTs／GCE上的电化学行为。实验结果表明,Pt／Gr-CNTs对甲醛具有良好的电催化氧化作用。     

基于纳米银/石墨烯/酪氨酸酶/聚酰胺-胺的双酚A传感器

采用石墨烯纳米材料,并结合酪氨酸酶、聚酰胺-胺(PAMAM)和纳米银修饰玻碳电极研制了新型BPA生物传感器。运用循环伏安法和电化学交流阻抗考察了修饰电极的电化学行为。由于石墨烯独特的物理化学性质,结合聚酰胺-胺和纳米银的协同作用,该修饰电极对于BPA有较好的电流响应。在最佳条件下,该传感器对双酚A的线性检测范围为1.0×10-7～3.3×10-5mol/L,检测限为3.0×10-8 mol/L(信噪比为3),相关系数为0.998。     

肉桂酸修饰电极对尿酸的研究测定

用恒电位沉积方法制备了肉桂酸修饰电极,研究了尿酸(UA)在该修饰电极上的电化学行为.研究表明,在优化的实验条件下,尿酸在修饰电极上有良好的电催化响应,其氧化峰电流与浓度在2.0×10-6～4.0×10-4 mol/L范围内成很好的线性关系,检出限为1.0×10-6 mol/L.该修饰电极制备简单、稳定性好、检测方便.     

苯磺酸氨氯地平在石墨烯修饰玻碳电极上的电分析方法

研究了苯磺酸氨氯地平(ADB)在石墨烯(GR)修饰玻碳电极(GR/GCE)上的电化学行为及电化学动力学性质,据此建立了ADB电分析方法。采用电化学阻抗(EIS)法,循环伏安(CV)法,计时电流(CA)法,计时电量法(CC)等测定电极动力学参数。结果表明,ADB在GCE上的直接电化学较迟缓,GR对ADB的电化学氧化具有明显的电催化作用,其氧化峰电流增大了近4倍。用微分脉冲伏安法(DPV)在优化条件下测得氧化峰电流与ADB在6×10-7~1×10-4mol/L浓度范围内呈良好线性关系,检出限(S/N=3)为8.0×10-8 mol/L。该方法可用于市售ADB药品含量的电化学定量测定。     

Electrochemical determination of imidacloprid using nanosilver Nafion/nanoTiO2 Nafion composite modified glassy carbon electrode

A novel biocompatible environment friendly nanosilver Nafion^®/nanoTiO₂ Nafion^® modified glassy carbon electrode was prepared by a simple procedure and characterized. This modified electrode was used as a sensing electrode for the detection of imidacloprid. Cyclic voltammetry, differential pulse voltammetry and amperometry were used in this work. The reduction potential of imidacloprid on this electrode is lower compared to other electrodes reported in the literature. The LOD and LOQ values obtained for the sensing of imidacloprid on this modified electrode are comparable to the values reported in the literature.     

Anodic stripping voltammetric determination of copper(II) using a functionalized carbon nanotubes paste electrode modified with crosslinked chitosan

The development and application of a functionalized carbon nanotubes paste electrode (CNPE) modified with crosslinked chitosan for determination of Cu(II) in industrial wastewater, natural water and human urine samples by linear scan anodic stripping voltammetry (LSASV) are described. Different electrodes were constructed using chitosan and chitosan crosslinked with glutaraldehyde (CTS-GA) and epichlorohydrin (CTS-ECH). The best voltammetric response for Cu(II) was obtained with a paste composition of 65% (m/m) of functionalized carbon nanotubes, 15% (m/m) of CTS-ECH, and 20% (m/m) of mineral oil using a solution of 0.05 mol L⁻¹ KNO₃ with pH adjusted to 2.25 with HNO₃, an accumulation potential of −0.3 V vs. Ag/AgCl (3.0 mol L⁻¹ KCl) for 300 s and a scan rate of 100 mV s⁻¹. Under these optimal experimental conditions, the voltammetric response was linearly dependent on the Cu(II) concentration in the range from 7.90 × 10⁻⁸ to 1.60 × 10⁻⁵ mol L⁻¹ with a detection limit of 1.00 × 10⁻⁸ mol L⁻¹. The samples analyses were evaluated using the proposed sensor and a good recovery of Cu(II) was obtained with results in the range from 98.0% to 104%. The analysis of industrial wastewater, natural water and human urine samples obtained using the proposed CNPE modified with CTS-ECH electrode and those obtained using a comparative method are in agreement at the 95% confidence level.     

1,10-Phenanthroline modified glassy carbon electrode for voltammetric determination of cadmium(II) ions

This study reports the electrochemical modification of glassy carbon (GC) electrode surface with the electro-polymerized form of 1,10-phenanthroline monohydrate (PMH), the characterization of this polyphenanthroline modified electrode (PPMH/GC) and the electroanalytical application suitable for the determination of Cd(II) ions. The PPMH/GC electrode was characterized by cyclic voltammetry, chronoamperometry and atomic force microscopy and formation of polyphenanthroline layer grafted to surface of GC electrode was evidenced. Selectivity of PPMH/GC electrode towards heavy metal ions was investigated by square wave voltammetry. The PPMH/GC electrode was found to be suitable for selective determination of Cd(II) in the solutions containing the mixture of heavy metal ions and showed high stability and reproducibility. The analytical methodology was successfully applied for monitoring the toxic metal ions in real samples.     

Voltammetric behavior of multi-walled carbon nanotubes modified electrode-hexacyanoferrate(II) electrocatalyst system as a sensor for determination of captopril

The study of electrochemical behavior and determination of captopril, as an angiontensin-converting enzyme inhibitor, is reported on multi-walled carbon nanotube (MCNT) modified glassy carbon electrode (GCE) and hexacyanoferrate(II) (HCF) electrocatalyst. The cyclic voltammetric results indicate that MCNTs and HCF system can remarkably enhance electrocatalytic activity toward the oxidation of captopril in acidic solutions. It is leading to a considerable improvement of the anodic peak current for captopril, and allows the development of a highly sensitive voltammetric sensor for detection of captopril in pharmaceutical and clinical samples. The investigation of captopril oxidation on the iron oxide nanoparticles modified carbon paste electrode does not show any electrocatalytic effect on the oxidation of captopril, suggesting that iron oxide impurities in the MCNTs are not the active sites in captopril sensing. Under optimized conditions on MCNTs-HCF system, the proposed method with respect to other reported electrochemical methods shows wider dynamic range (0.5–600 μM) with suitable selectivity, practical detection limit of 0.2 μM and good precision (R.S.D. <3%).     

基于石墨烯修饰玻碳电极伏安法测定6-苄氨基嘌呤

该文利用石墨烯修饰电极,构建了一种测定6-苄氨基嘌呤的新型的电化学方法。循环伏安实验表明,石墨烯修饰电极能显著降低6-苄氨基嘌呤的测定电位,提高其响应电流。6-苄氨基嘌呤在石墨烯修饰电极表面的电化学过程为扩散控制。在优化的实验条件下,6-苄氨基嘌呤与峰电流在浓度为1.0×10-8~1.0×10-6mol/L范围内呈现良好的线性关系,检测限为5.0×10-9 mol/L。考察了一些无机离子和有机化合物对6-苄氨基嘌呤测定的干扰,结果表明该传感器有较好的抗干扰能力。加标回收实验表明该修饰电极的回收率在91.0%~104.5%之间,表明该传感器能用于实际样品的检测。     

Cyclic voltammetry on electrode surfaces covered with porous layers: An analysis of electron transfer kinetics at single-walled carbon nanotube modified electrodes

Cyclic voltammetry is recorded of the oxidation of ferrocyanide on a glassy carbon electrode modified with multiple layers of single-walled carbon nanotubes. The current response is interpreted in terms of semi-infinite planar diffusion towards the macro-electrode surface and in terms of oxidation of the electroactive species trapped in pockets in between the nanotubes. A thin layer model is used to illustrate the effects of diffusion within a porous layer. It is found that a semi-infinite planar diffusion model alone is not appropriate for interpreting the kinetics of the electron transfer at this electrode surface. In particular, caution should be exercised in respect of comparing voltammetric peak-to-peak potential separations between naked electrodes and nanotube-modified electrodes for the inference of electrocatalysis via electron transfer via the nanotubes.     

银掺杂聚L-甲硫氨酸修饰电极测定6-巯基嘌呤

利用循环伏安法制备了银掺杂聚L-甲硫氨酸修饰玻碳电极(Ag-PLM/GCE),研究了6-巯基嘌呤在该修饰电极上的电化学行为,建立了循环伏安法测定6-巯基嘌呤的新方法.在pH6.5磷酸盐缓冲溶液中,扫描速率为140mV/s,6-巯基嘌呤在银掺杂聚L-甲硫氨酸修饰玻碳电极上出现一个氧化峰,峰电位为0.410V.用循环伏安法测定时,其峰电流与6-巯基嘌呤的浓度在3.00× 10-5～5.00×10-3mol/L范围内呈现良好的线性关系,检出限为5.0×10-6 mol/L.用于乐疾宁片剂中6-巯基嘌呤含量的测定,结果满意.     

Application of carbon ionic liquid electrode for the electrooxidative determination of catechol

A carbon ionic liquid electrode (CILE) was constructed using graphite powder mixed with N-butylpyridinium hexafluorophosphate (BPPF₆) in place of paraffin as the binder, which showed strong electrocatalytic activity to the direct oxidation of catechol. In pH 3.0 phosphate buffer solution (PBS) a pair of redox peaks appeared on the CILE with the anodic and the cathodic peak potential located at 387 and 330 mV (vs. SCE), respectively. The electrochemical behaviors of catechol on the CILE were carefully investigated, and the electrochemical parameters were calculated with the results of the electrode reaction standard rate constant k_s as 1.27 s⁻¹, the charge-transfer coefficient α as 0.58 and the electron transferred number n as 2. Under the selected conditions, the anodic peak current increased linearly with the catechol concentration over the range from 1.0 × 10⁻⁶ to 8.0 × 10⁻⁴ mol L⁻¹ by cyclic voltammetry at the scan rate of 100 mV s⁻¹. The detection limit was calculated as 6.0 × 10⁻⁷ mol L⁻¹ (3σ). The CILE showed good ability to separate the electrochemical responses of catechol and ascorbic acid (AA) with the anodic peak potential separation as 252 mV (vs. SCE). The proposed method was further applied to the synthetic samples determination with satisfactory results.     

Adsorptive voltammetry of Hg(II) ions at a glassy carbon electrode coated with electropolymerized methyl-red film

The glassy carbon electrode coated with electropolymerized methyl-red film, 1.2 × 10⁻⁶ m in thickness, (PMRE) showed high sensitivity towards Hg(II) ions. PMREs were adopted to accumulate and detect Hg(II) ions in a pH 2.56 Britton–Robinson buffer solution. Cyclic voltammogram of the accumulated Hg species on PMREs exhibited an anodic wave at 0.64 V and a cathodic wave at 0.13 V, due to the oxidation of accumulated Hg species on PMREs and the reduction of Hg(II) ions in the solution, respectively. For this heterogeneous adsorption of Hg(II) ions onto PMREs, the maximum surface concentration, adsorption equilibrium, and Gibbs energy change were evaluated to be 5.12 × 10⁻⁶ mol m⁻², 3.7 × 10⁵ l mol⁻¹, and −30.1 kJ mol⁻¹, respectively. The anodic peak current at 0.64 V was linear with the concentration of Hg(II) ions in the range of 1.1 × 10⁻¹⁰ to 1.1 × 10⁻⁷ M with a detection limit of 4.4 × 10⁻¹¹ M. The proposed method was utilized successfully for the detection of Hg(II) ions in the lake water.     

Direct electron transfer of glucose oxidase at glassy carbon electrode modified with functionalized carbon nanotubes within a dihexadecylphosphate film

A glassy carbon electrode modified with functionalized multiwalled carbon nanotubes (CNTs) immobilized by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) in a dihexadecylphosphate film was prepared and characterized by cyclic voltammetry and scanning electron microscopy. It was used as a support for FAD or glucose oxidase (GOx) immobilization with EDC/NHS crosslinking agents. Cyclic voltammetry of GOx immobilized onto the surface of CNTs showed a pair of well-defined redox peaks, which correspond to the direct electron transfer of GOx, with a formal potential of −0.418 V vs. Ag/AgCl (3 M KCl) in 0.1 M phosphate buffer solution (pH 7.0). An apparent heterogeneous electron transfer rate constant of 1.69 s⁻¹ was obtained. The dependence of half wave potential on pH indicated that the direct electron transfer reaction of GOx involves a two-electron, two-proton transfer. The determination of glucose was carried out by square wave voltammetry and the developed biosensor showed good reproducibility and stability. The proposed method could be easily extended to immobilize and evaluate the direct electron transfer of other redox enzymes or proteins.     

Simultaneous determination of lead and cadmium at a glassy carbon electrode modified with Langmuir–Blodgett film of p-tert-butylthiacalix[4]arene

A glassy carbon electrode (GCE) modified with a Langmuir–Blodgett (LB) film of p-tert-butylthiacalix[4]arene (TCA) has been investigated as a disposable sensor for measuring the trace levels of lead and cadmium. The possibility of determining lead and cadmium at trace levels was examined with differential pulse stripping voltammetry in the measurement step. The electrochemical response was characterized with respect to supporting electrolyte, pH of solution, accumulation time, accumulation potential, layers of the LB films, and possible interferences. Calibration plots were found to be linear in the range 2 × 10⁻⁷ to 5 × 10⁻⁵ mol l⁻¹ (Cd²⁺) and 1 × 10⁻⁷ to 2.5 × 10⁻⁵ mol l⁻¹ (Pb²⁺); the detection limits were 2 × 10⁻⁸ mol l⁻¹ (Cd²⁺) and 8 × 10⁻⁹ mol l⁻¹ (Pb²⁺). Possible recognition mechanism was also discussed. From the analysis of real samples (river, lake and tap water) it can be concluded that the method is sensitive and reproducible in determining of these elements and can be used in the analysis of natural water samples.     

双层类脂膜修饰玻碳电极研究青蒿素与氯化血红素相互作用及其分析应用

青蒿素是一种很重要的抗疟药物.该文用电化学手段考察了在双层类脂膜体系中抗疟药物-青蒿素与氯化血红素的相互作用.氯化血红素在双层类脂膜修饰的玻碳电极上有很灵敏的还原峰电流.该还原峰电流随着底液中青蒿素的浓度增加而降低,这表明氯化血红素与青蒿素之间发生了相互作用,电流降低幅度与青蒿素浓度在9.1 ×10-9mol/L-1.7 ×10-6mol/L的范围内呈良好线性关系,相关系数为0.996,检测限为8.0×10-9mol/L.该文还探讨了在生物模拟膜体系中青蒿素的药物作用机制.     

Quartz crystal microbalance and electrochemical cytosensing on a chitosan/multiwalled carbon nanotubes/Au electrode

The piezoelectric quartz crystal microbalance (QCM) was used to monitor the adhesion of mammalian cells on a chitosan (CS)/multiwalled carbon nanotubes (MWCNTs) composite modified gold electrode. The morphology and chemical properties of the CS/MWCNTs film were characterized with scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. The human breast cancer cells (MCF-7) were adhered to and grown on the CS/MWCNTs film modified gold surface or a net CS film modified gold surface, and the process of which was continuously monitored and displayed by changes of the resonant frequency (Δf₀) and the motional resistance (ΔR₁) of the QCM. The attachment/spreading process of the MCF-7 cells on the QCM Au electrode decreased the Δf₀ and increased the ΔR₁ simultaneously, implying rather complicated effects (simultaneous mass, viscoelasticity and probable surface-stress load) on the sensor surface. The attachment rate and viability of the cells when proliferating on the two surfaces were detected by the MTT assay. The presence and state of cells on the electrode surface were confirmed by the fluorescent microscopy. Cyclic voltammetry and electrochemical impedance spectroscopy of the ferricyanide/ferrocyanide couple were examined before and after the cell adhesion. All data showed that the cell adhesion and proliferation processes were more efficient on the biocompatiable nanocomposite surfaces. The cell-based biosensor has potential for identification and screening of biologically active drugs and other biomolecules affecting cellular shape and attachment.