Anodic stripping voltammetric determination of mercury using multi-walled carbon nanotubes film coated glassy carbon electrode

An electrochemical method for the determination of trace levels of mercury based on a multi-walled carbon nanotubes (MWNT) film coated glassy carbon electrode (GCE) is described. In 0.1 mol L^–1 HCl solution containing 0.02 mol L^–1 KI, Hg²⁺ was firstly preconcentrated at the MWNT film and then reduced at –0.60 V. During the anodic potential sweep, reduced mercury was oxidized, and then a sensitive and well-defined stripping peak at about –0.20 V appeared. Under identical conditions, a MWNT film coated GCE greatly enhances the stripping peak current of mercury in contrast to a bare GCE. Low concentrations of I^– remarkably improve the determining sensitivity, since this increases the accumulation efficiency of Hg²⁺ at the MWNT film coated GCE. The stripping peak current is proportional to the concentration of Hg²⁺ over the range 8×10^–10–5×10^–7 mol L^–1. The lowest detectable concentration of Hg²⁺ is 2×10^–10 mol L^–1 at 5 min accumulation. The relative standard deviation (RSD) at 1×10^–8 mol L^–1 Hg²⁺ was about 6% (n=10). By using this proposed method, Hg²⁺ in some water samples was determined, and the results were compared with those obtained by atomic absorption spectrometry (AAS). The two results are similar, suggesting that the MWNT-film coated GCE has great potential in practical analysis.     

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.     

Study on electrochemical behavior of tryptophan at a glassy carbon electrode modified with multi-walled carbon nanotubes embedded cerium hexacyanoferrate

Electrochemical behavior of cerium hexacyanoferrate (CeHCF) incorporated on multi-walled carbon nanotubes (MWNTs) modified GC electrode is investigated by scanning electron microscopy (SEM) and electrochemical techniques. The CeHCF/MWNT/GC electrode showed potent electrocatalytic activity toward the electrochemical oxidation of tryptophan in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of 240 mV. The anodic peak currents increased linearly with the concentration of tryptophan in the range of 2.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M with a detection limit of 2.0 × 10⁻⁸ M (at a S/N = 3). And the determination of tryptophan in pharmaceutical samples was satisfactory.     

对硝基苯酚在多壁碳纳米管修饰玻碳电极上的电化学行为及分析测定

水中对硝基苯酚主要来源于化工、制药行业,它有致癌作用。人们已对它的测定方法进行了大量的研究,最早采用的测定方法是分光光度法,其检测限偏高;色谱法测定对硝基苯酚,操作繁琐,仪器昂贵,分析成本高。后来又发展了一种操作更方便的直接用于测定的电化学方法。本文旨在利用碳纳米管对对硝基苯酚的吸附性能,研究对硝基苯酚在多壁碳纳米管修饰电极上的电化学行为。     

Sensitive voltammetric determination of tyrosine using multi-walled carbon nanotubes/4-aminobenzeresulfonic acid film-coated glassy carbon electrode

A chemically modified electrode is constructed based on the multi-walled carbon nanotubes (MWNTs)/4-aminobenzeresulfonic acid (4-ABSA) film-coated glassy carbon electrode. The electrocatalytic oxidation of tyrosine (Tyr) is investigated on the surface of the MWNTs/4-ABSA-modified electrode using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The prepared modified electrode shows voltammetric responses with high sensitivity and selectivity for Tyr in optimal conditions, which makes it very suitable for sub-micromolar detection of Tyr. A sensitive oxidation peak at +0.64 V is employed to determine Tyr. Good linear relationship between the oxidation peak current and the Tyr concentration in the range of 1 × 10⁻⁷ to 5 × 10⁻⁵ mol/L is obtained in phosphate buffer solution with pH 7.0. By use of modified electrode, the voltammetric detection limit for Tyr in DPV measurements is 8 × 10⁻⁸ mol/L (S/N = 3). Good sensitivity, selectivity and stability of the low-cost modified electrode make it very suitable for the determination of trace amounts of Tyr in pharmaceutical and clinical preparations.     

盐酸左氧氟沙星在聚L-精氨酸/多壁碳纳米管修饰电极上的电化学行为

运用循环伏安法、线性扫描伏安法、计时电量法等研究了盐酸左氧氟沙星在聚L-精氨酸/多壁碳纳米管修饰电极上的电化学行为。实验表明:盐酸左氧氟沙星在聚L-精氨酸/多壁碳纳米管修饰电极上的电极反应过程为等电子等质子吸附控制的不可逆过程,在pH=6.0的Na2HPO4-NaH2PO4支持电解质中,其氧化峰电流与浓度在7.0×10-6~1.0×10-4mol·L-1范围内呈良好的线性关系,相关系数R为-0.9992,检出限为5.0×10-6mol·L-1,样品测定回收率为98.26%~101.70%。     

Electro-oxidation and determination of trazodone at multi-walled carbon nanotube-modified glassy carbon electrode

A simple and rapid electrochemical method was developed for the determination of trace-level trazodone, based on the excellent properties of multi-walled carbon nanotubes (MWCNTs). The MWCNT-modified glassy carbon electrode was constructed and the electrochemical behavior of trazodone was investigated in detail. The cyclic voltammetric results indicate that MWCNT-modified glassy carbon electrode can remarkably enhance electrocatalytic activity towards the oxidation of trazodone in neutral solutions. It leads to a considerable improvement of the anodic peak current for trazodone, and allows the development of a highly sensitive voltammetric sensor for the determination of trazodone. Trazodone could effectively accumulate at this electrode and produce two anodic peaks at about 0.73 V and 1.00 V. The electrocatalytic behavior was further exploited as a sensitive detection scheme for the trazodone determination by differential-pulse voltammetry. Under optimized conditions, the concentration range and detection limit are 0.2-10 μM and 24 nM, respectively for trazodone. The proposed method was successfully applied to trazodone determination in pharmaceutical samples. The analytical performance of this sensor has been evaluated for detection of analyte in urine as a real sample.     

Nd_2O_3/多壁碳纳米管修饰电极检测亚硝酸根

制备了纳米Nd2O3/多壁碳纳米管修饰电极并用于亚硝酸盐的检测。采用原子力显微镜、X-粉末衍射仪表征制备的纳米材料。实验表明:修饰电极对亚硝酸根的氧化具有明显地电催化作用。利用示差脉冲伏安法测定亚硝酸盐,其氧化峰电流和其浓度在20μmol·L-1-20 mmol·L-1范围内呈现良好的线性关系,检测线为0.83μmol·L-1(S/N=3)。更重要的是,实验结果表明:与Nd2O3修饰电极相比,多壁碳纳米管能显著地提高电极的稳定性。此外,修饰电极具有良好的选择性,能用于样品的检测,结果令人满意。     

Electrochemical behavior and voltammetric determination of norfloxacin at glassy carbon electrode modified with multi walled carbon nanotubes/Nafion

A simple and rapid electrochemical method is developed for the determination of trace-level norfloxacin, based on the excellent properties of multi-walled carbon nanotubes (MWCNTs). The MWCNTs/Nafion film-coated glassy carbon electrode (GCE) is constructed and the electrochemical behavior of norfloxacin at the electrode is investigated in detail. The results indicate that MWCNTs modified glassy carbon electrode exhibited efficiently electrocatalytic oxidation for norfloxacin (NFX) with relatively high sensitivity, stability and life time. Under conditions of cyclic voltammetry, the current for oxidation of selected analyte is enhanced significantly in comparison to the bare GCE. The electrocatalytic behavior is further exploited as a sensitive detection scheme for the analyte determinations by linear sweep voltammetry (LSV). Under optimized condition in voltammetric method the concentration calibration range and detection limit (S/N=3) are 0.1-100 micromol/L and 5 x 10(-8)mol/L for NFX. The proposed method was successfully applied to NFX determination in tablets. The analytical performance of this sensor has been evaluated for detection of the analyte in urine as a real sample.     

Voltammetric studies of sumatriptan on the surface of pyrolytic graphite electrode modified with multi-walled carbon nanotubes decorated with silver nanoparticles

Multi-walled carbon nanotube decorated with silver nanoparticles (AgNPs-MWCNT) is used as an effective strategy for modification of the surface of pyrolytic graphite electrode (PGE). This modification procedure improved colloidal dispersion of the decorated MWCNTs in water, affording uniform and stable thin films for altering the surface properties of the working electrode. Robust electrode for sensing applications is obtained in a simple solvent evaporation process. The electrochemical behavior of sumatriptan (Sum) at the bare PGE and AgNPs-MWCNT modified PGE is investigated. The results indicate that the AgNPs-MWCNT modified PGE significantly enhanced the oxidation peak current of Sum. A remarkable enhancement in microscopic area of the electrode together with strong adsorption of Sum on the surface of the modified electrode resulted in a considerable increase in the peak current of Sum. Experimental parameters, such as scan rate, pH, accumulation conditions and amount of the modifier used on the PGE surface are optimized by monitoring the CV responses toward Sum. It is found that a maximum current response can be obtained at pH 7.4 after accumulation at open circuit for 150 s. Further experiments demonstrated that the oxidative peak currents increased linearly with Sum concentration in the range of 8.0 × 10⁻⁸-1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 4.0 × 10⁻⁸ mol L⁻¹. The modified electrode showed high sensitivity, selectivity, long-term stability and remarkable voltammetric reproducibility in response to Sum. These excellent properties make the prepared sensor suitable for the analysis in pharmaceutical and clinical preparations. The modified electrode was successfully applied for the accurate determination of trace amounts of Sum in pharmaceutical preparations.     

Determination of trace metoclopramide by anodic stripping voltammetry with nafion modified glassy carbon electrode

A novel method is described for determination of metoclopramide (MCP) by second-derivative adsorptive anodic stripping voltammetry with a nafion-modified electrode. The stripping peak current is proportional to the concentration of MCP over the range 1.2×10⁻⁹–4.6×10⁻⁷ M. The detection limit is 8.0×10⁻¹¹ M with 4-min accumulation. The method has been successfully applied to the determination of MCP in human serum.     

Voltammetric determination of antibacterial drug gemifloxacin in solubilized systems at multi-walled carbon nanotubes modified glassy carbon electrode

A sensitive electroanalytical method for determination of gemifloxacin in pharmaceutical formulation has been investigated on the basis of the enhanced electrochemical response at multi-walled carbon nanotubes modified glassy carbon electrode in the presence of CTAB. Solubilized system of different surfactants including SDS, Tween-20 and CTAB were taken for the study of electrochemical behaviour of gemifloxacin at modified electrode. The reduction peak current increases in the presence of CTAB while other surfactants show opposite effect. The modified electrode exhibits catalytic activity, high sensitivity, stability and is applicable over wide range of concentration for the determination of gemifloxacin. The mechanism of electrochemical reduction of gemifloxacin has been proposed on the basis of CV, SWV, DPV and coulometeric techniques. The proposed squarewave voltammetric method shows linearity over the concentration range 2.47-15.5 μg/mL. The achieved limits of detection (LOD) and quantification (LOQ) are 0.90 ng/mL and 3.0 ng/mL respectively.     

Electrochemical parameters of ethamsylate at multi-walled carbon nanotube modified glassy carbon electrodes

In this paper, some electrochemical parameters of ethamsylate at a multi-walled carbon nanotube modified glassy carbon electrode, such as the charge number, exchange current density, standard heterogeneous rate constant and diffusion coefficient, were measured by cyclic voltammetry, chronoamperometry and chronocoulometry. The modified electrode exhibits good promotion of the electrochemical reaction of ethamsylate and increases the standard heterogeneous rate constant of ethamsylate greatly. The differential pulse voltammetry responses of ethamsylate were linearly dependent on its concentrations in a range from 2.0 x 10(-6) to 6.0 x 10(-5) mol L(-1), with a detection limit of 4.0 x 10(-7) mol L(-1).     

Adsorptive stripping voltammetric determination of 4-aminophenol at a single-wall carbon nanotubes film coated electrode

A single-wall carbon nanotubes (SWNT)-Nafion film coated glassy carbon electrode (GCE) was described for the determination of 4-aminophenol. In pH 3.0 sodium citrate-HCl buffer, the oxidation peak current of 4-aminophenol increases greatly at the SWNT-Nafion film coated GCE in contrast to that at both bare GCE and Nafion-film coated GCE. Moreover, the oxidation peak potential shifts to more negative potential. All the experimental parameters were optimized for the determination of 4-aminophenol. The oxidation peak current is proportional to the concentration of 4-aminophenol over the range from 5×10⁻⁹ to 2×10⁻⁶ mol l⁻¹. The detection limit is 8×10⁻¹⁰ mol l⁻¹ at 4 min of accumulation. Using the proposed method, 4-aminophenol in water samples was determined.     

An electrochemical sensing platform for trace analysis of Eriochrome Black T using multi-walled carbon nanotube modified glassy carbon electrode by adsorptive stripping linear sweep voltammetry

ABSTRACT

A highly sensitive electrochemical sensing platform was proposed for trace analysis of Eriochrome Black T in aqueous solutions by adsorptive stripping linear sweep voltammetry based on the open-circuit accumulation of Eriochrome Black T onto the fabricated multi-walled carbon nanotubes modified glassy carbon electrode surface. The proposed methodology was quite linear between 0.1 and 10 µM of Eriochrome Black T concentration with a correlation coefficient of 0.9981. The precision of the technique was acceptable with the relative standard deviations of lower than 13.4% for inter-day assays. In addition, the sensitivity properties of the proposed method were compared with those of the spectrophotometric method, which is frequently used in the literature for Eriochrome Black T analysis. The results showed that the proposed electrochemical sensing platform would be a more sensitive alternative to the existing spectrophotometric techniques. Finally, the methodology was successfully applied to the determination of Eriochrome Black T in a well water spiked at different concentration levels.     

多壁碳纳米管修饰玻碳电极测定铜离子

以多壁碳纳米管(MWCNTs)修饰玻碳电极为工作电极,采用阳极溶出线性扫描法研究了铜离子的电化学测定方法。探讨了MWCNTs修饰层数、富集电位、富集时间、溶液pH、支持电解质对峰电流的影响。实验表明,铜离子浓度在1.0×10-8~1.0×10-5mol·L-1范围内与峰电流呈良好的线性关系,检测限为2.0×10-9mol·L-1,且该电极具有良好的稳定性和抗干扰能力。     

基于多壁碳纳米管/壳聚糖多层膜修饰玻碳电极邻苯二酚的测定

改进了碳纳米管在壳聚糖溶液中的分散方法,制备了多壁碳纳米管/壳聚糖多层膜修饰玻碳电极,对比了不同修饰层数膜电极的循环伏安和电化学阻抗行为,5层多壁碳纳米管/壳聚糖膜修饰玻碳电极的电化学性能优良.在最优实验条件下,该修饰玻碳电极对邻苯二酚(CAT)有灵敏的响应,CAT浓度在3.99×10-6～9.09×10-4mol/L范围内与氧化峰电流呈良好的线性关系,检出限为2.39×10-6mol/L(S/N=3).该修饰玻碳电极性能稳定,测定4×10-5mol/LCAT溶液,RSD(n=10)为2.1%;15周后,该电极的响应值仅降低1.9%.     

Catalytic oxidation of thiols at preheated glassy carbon electrode modified with abrasive immobilization of multiwall carbon nanotubes: applications to amperometric detection of thiocytosine, l-cysteine and glutathione

The performance of preheated glassy carbon electrode modified with carbon nanotubes is described. First glassy carbon electrode is heated for 5 min at 50 °C, then abrasive immobilization of multiwall carbon nanotubes on a preheated glassy carbon electrode was achieved by gentle rubbing of electrode surface on a filter paper supporting carbon nanotubes. Carbon nanotubes (CNTs)-modified glassy carbon electrodes exhibit strong and stable electrocatalytic response toward thiols oxidation in wide pH range. These properties permit an important decrease in over voltage for the oxidation of thiocytosine, glutathione and l-cysteine, as well as a dramatic increase in the peak currents in comparison with bare glassy carbon electrode. Furthermore, the thiols amperometric response of the coated electrodes is extremely stable, with more than 95% of the initial activity after 30 min stirring of 0.1 mM thiols. The electrocatalytic behavior is further exploited as a sensitive detection scheme for thiols detection by hydrodynamic amperometry. The substantial decrease in the overvoltage of the thiols oxidation associated with a stable amperometric response and antifouling properties of nanotubes films allow the development of highly sensitive thiols sensor without using any redox mediator. Such ability of carbon nanotubes to promote the thiols electron transfer reaction, short response time (5 s) and long-term stability, low detection limit, extended linear concentration range, high sensitivity suggest great promise for thiols amperometric sensors and detector for chromatographic analysis of thiol derivatives.     

Application of multi-walled carbon nanotubes modified carbon ionic liquid electrode for electrocatalytic oxidation of dopamine

A simple, sensitive, and reliable method based on a multi-walled carbon nanotubes (MWNTs) modified carbon ionic liquid electrode (CILE) has been successfully developed for determination of dopamine (DA) in the presence of ascorbic acid (AA). The acid-treated MWNTs with carboxylic acid functional groups could promote the electron-transfer reaction of DA and inhibit the voltammetric response of AA. Due to the good performance of the ionic liquid, the electrochemical response of DA on the MWNTs/CILE was better than that of other MWNTs modified electrodes. Under the optimum conditions a linear calibration plot was obtained in the range 5.0×10(-8) to 2.0×10(-4) mol L(-1) and the detection limit was 1.0×10(-8) mol L(-1).     

对氯酚在碳纳米管修饰玻碳电极上的电化学行为研究

研究了对氯酚在多壁碳纳米管修饰玻碳电极（MWNTs/GC）上的电化学行为。MWNTs/GC电极对对氯酚具有良好的电催化作用,相比玻碳电极对氯酚的氧化峰电位负移76 mV,峰电流达到玻碳电极上的8倍。通过线性扫描伏安法研究了富集时间、溶液pH和扫描速率对对氯酚氧化的影响。并采用计时电流法研究了氧化峰电流与对氯酚的浓度关系,结果显示峰电流与对氯酚的浓度在2.0×10^-7-2.0×10^-4mol/L范围内呈良好线性关系,检出限为8.8×10-8mol/L（S/N=3）。放置7 d后,对氯酚在碳纳米管上的峰电流仍能达到最初电流的96.2%,表明电极的稳定性较好。