Polyaniline Langmuir-Blodgett film modified glassy carbon electrode as a voltammetric sensor for determination of Ag ions

A highly sensitive electrochemical sensor made of a glassy carbon electrode (GCE) coated with a Langmuir-Blodgett film (LB) containing polyaniline (PAn) doped with p-toluenesulfonic acid (PTSA) (LB/PAn-PTSA/GCE) has been used for the detection of trace concentrations of Ag⁺. UV-vis absorption spectra indicated that the PAn was doped by PTSA. The surface morphology of the PAn LB film was characterized by atomic force microscopy (AFM). The electrochemical properties of this LB/PAn-PTSA/GCE were studied using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The LB/PAn-PTSA/GCE was used as a voltammetric sensor for determination of trace Ag⁺ at pH 5.0 using linear scanning stripping voltammetry. Under the optimal experimental conditions, the stripping current was proportional to the Ag⁺ concentration over the range from 6.0 × 10⁻¹⁰ mol L⁻¹ to 1.0 × 10⁻⁶ mol L⁻¹, with a detection limit of 4.0 × 10⁻¹⁰ mol L⁻¹. The high sensitivity, selectivity, and stability of this LB/PAn-PTSA/GCE also demonstrated its practical utility for simple, rapid and economical determination of Ag⁺ in water samples.     

DNA Langmuir-Blodgett modified glassy carbon electrode as voltammetric sensor for determinate of methotrexate

A highly sensitive electrochemical biosensor for the detection of trace amounts of methotrexate has been designed. Double stranded (ds)DNA molecules are immobilized onto a pretreated glassy carbon electrode (GCE(ox)) surface with Langmuir-Blodgett (LB) technique. The adsorptive voltammetric behaviors of methotrexate on DNA-modified electrode were explored by means of cyclic voltammetry (CV) and square wave voltammetry (SWV). The oxidation mechanism was proposed and discussed in this work. In addition, the optimum experimental conditions for the detection of methotrexate were explored, and the currents measured by SWV presented a good linear property as a function of the concentrations of methotrexate in the range of 2.0 × 10⁻⁸ to 4.0 × 10⁻⁶ mol L⁻¹, with an LOD of 5.0 × 10⁻⁹ mol L⁻¹. The method proposed was applied for the determination of methotrexate in pharmaceutical dosage and diluted human urine with wonderful satisfactory successfully.     

Nafion/MWCNT修饰玻碳电极伏安法测定痕量镉

用阳极溶出伏安法考察了Nation/多壁碳纳米管(MWCNT)复合修饰玻碳电极测量痕量镉的优化条件.在pH 5.8的磷酸盐缓冲液中,当Cd2 在Nation/MWCNT修饰电极表面富集时间为3 min,电位扫速为150 mV/s时,该修饰电极在伏安图上能出现一灵敏的氧化峰,峰电位约为-0.78 V.利用该峰可以进行痕量镉的检测,峰电流与Cd2 浓度在8.0×10-10-1.0×10-8mol/L.的范围内呈良好线性关系,相关系数为0.999,检出限可达100×10-11mol/L(S/N=3).该法用于人发样品中镉含量的测定,平均回收率为98.7%.     

Simultaneous voltammetric determination of dopamine and adenosine using a single walled carbon nanotube – Modified glassy carbon electrode

The simultaneous voltammetric determination of adenosine (ADS) and dopamine (DA) using a single wall carbon nanotube (SWCNT) modified glassy carbon electrode (GCE) is reported. This has physiological importance in controlling Parkinson’s disease. In phosphate buffer medium of pH 7.2, the concentration vs. peak current plots were linear in the range 1–100 μM for ADS and DA. A comparison of the voltammetric response of DA at acid-treated (purified and super-purified) and untreated SWCNT modified GCE indicates that the oxidation peak current of DA decreases considerably at the treated SWCNT modified GCE. This indicates that metallic impurities in nanotubes play a large role in enhancing the electrochemical current. The detection limit (3σ) and sensitivity observed for ADS and DA were 34.7 μM, 7 μM and 9.5 nA μM⁻¹, 77.9 nA μM⁻¹, respectively.     

Simultaneous voltammetric determination of tramadol and acetaminophen using carbon nanoparticles modified glassy carbon electrode

A sensitive and selective electrochemical sensor was fabricated via the drop-casting of carbon nanoparticles (CNPs) suspension onto a glassy carbon electrode (GCE). The application of this sensor was investigated in simultaneous determination of acetaminophen (ACE) and tramadol (TRA) drugs in pharmaceutical dosage form and ACE determination in human plasma. In order to study the electrochemical behaviors of the drugs, cyclic and differential pulse voltammetric studies of ACE and TRA were carried out at the surfaces of the modified GCE (MGCE) and the bare GCE. The dependence of peak currents and potentials on pH, concentration and the potential scan rate were investigated for these compounds at the surface of MGCE. Atomic force microscopy (AFM) was used for the characterization of the film modifier and its morphology on the surface of GCE. The results of the electrochemical investigations showed that CNPs, via a thin layer model based on the diffusion within a porous layer, enhanced the electroactive surface area and caused a remarkable increase in the peak currents. The thin layer of the modifier showed a catalytic effect and accelerated the rate of the electron transfer process. Application of the MGCE resulted in a sensitivity enhancement and a considerable decrease in the anodic overpotential, leading to negative shifts in peak potentials. An optimum electrochemical response was obtained for the sensor in the buffered solution of pH 7.0 and using 2 μL CNPs suspension cast on the surface of GCE. Using differential pulse voltammetry, the prepared sensor showed good sensitivity and selectivity for the determination of ACE and TRA in wide linear ranges of 0.1-100 and 10-1000 μM, respectively. The resulted detection limits for ACE and TRA was 0.05 and 1 μM, respectively. The CNPs modified GCE was successfully applied for ACE and TRA determinations in pharmaceutical dosage forms and also for the determination of ACE in human plasma.     

Nafion修饰玻碳电极伏安法测定痕量锡

报道了一种用Nafion修饰玻碳电极测定痕量锡的新方法。研究了Nafion膜的有关特性和测定的优化条件,当富集时间为3min时,峰电流与Sn(Ⅳ)浓度在1×10-9~1×10-7mol/L的范围呈良好的线性关系,检测限为2.46×10-10mol/L。该法用于实际水样中痕量锡的测定,平均回收率为97.24%。     

Electrocatalytic reduction of nitrite on tetraruthenated metalloporphyrins/Nafion glassy carbon modified electrode

This paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35 nm thick and tetraruthenated metalloporphyrins layers 190 nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues.These modified electrodes are able to reduce nitrite at −660 mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.     

Determination of analgesics in pharmaceutical formulations and urine samples using nano polypyrrole modified glassy carbon electrode

Three analgesics (acetaminophen, acetylsalicylic acid, and dipyrone) were determined electrochemically using nano polypyrrole modified glassy carbon electrode. The cyclic voltammetric behavior of the three analgesics was studied in aqueous acid, neutral, and alkaline conditions. One well-defined oxidation peak each for acetaminophen and acetylsalicylic acid and three oxidation peaks for dipyrone were observed in the cyclic voltammograms. The influence of pH, scan rate, and concentration reveal the irreversible diffusion controlled loss of 4e⁻ in acid and neutral media and 2e⁻/1H⁺ in basic medium for acetaminophen. In the case of acetylsalicylic acid, 2e⁻ and 1H⁺ loss in acidic and neutral pH and 2e⁻ and 2H⁺ loss in basic pH were observed and the oxidation was irreversible and controlled by adsorption. Irreversible removal of 2e⁻ and 1H⁺ in all pH media was observed for dipyrone and the oxidation was controlled by diffusion. A systematic study of the experimental parameters that affect the differential pulse stripping voltammetric response was carried out and optimized conditions which yield maximum peak current were arrived at. Scanning electron microscopy (SEM) analysis confirms good accumulation of the drugs on the electrode surface. The calibration was made under optimum conditions. The range of study for acetaminophen, acetylsalicylic acid, and dipyrone was 50–250, 40–300, and 100–400 ng/mL and the lower limit of determination was 45, 25, and 70 ng/mL respectively. The suitability of the method for the determination of the three analgesics in pharmaceutical preparations and urine samples was also ascertained.     

A new sensor for the simultaneous determination of paracetamol and mefenamic acid in a pharmaceutical preparation and biological samples using copper(II) doped zeolite modified carbon paste electrode

A new chemically modified electrode is constructed based on a copper(II) doped zeolite modified carbon paste electrode (Cu²⁺Y/ZMCPE). It is demonstrated that this novel sensor could be used for the simultaneous determination of the pharmaceutically important compounds paracetamol (PAR) and mefenamic acid (MEF). The measurements were carried out using the differential pulse voltammetry (DPV) method. The prepared modified electrode shows voltammetric responses of high sensitivity, selectivity and stability for PAR and MEF under optimal conditions, which makes it a suitable sensor for simultaneous submicromolar detection of PAR and MEF in solution. The oxidation peak current for PAR in Briton Robinson buffer (pH = 10) was measured at various concentrations between 0.25 and 900 μM. (The detection limit was 0.1 μM and S/N was 3.) It proved linear (the correlation coefficient was 0.9987). For the MEF a linear correlation between oxidation peak current and concentration of MEF over the range 0.3–100 μM, with a correlation coefficient of 0.9991 and a detection limit of 0.04 μM, was obtained. The analytical performance of this sensor has been evaluated for the detection of PAR and MEF in human serum, human urine and a pharmaceutical preparation.     

Utilization of a montmorillonite-Ca-modified carbon paste electrode for the stripping voltammetric determination of diflunisal in its pharmaceutical formulations and human blood

A highly sensitive square-wave adsorptive anodic stripping voltammetric method was described for the determination of diflunisal in its formulations and human blood, utilizing a developed montmorillonite-Ca-modified carbon paste electrode (CPE). The peak current was significantly enhanced due to the strong adsorptive properties of montmorillonite-Ca clay. The optimal procedural parameters were frequency f = 80 Hz, scan increment ΔE _a = 10 mV, pulse-amplitude ΔE _i = 25 mV, and an accumulation potential E _acc of 0.0 V versus Ag/AgCl/3M KCl in acetate buffer of pH 5.0 using 10% (w/w) MMT-Ca-modified CPE. The described method was successfully applied for assay of diflunisal in different pharmaceutical formulations (Doloban^®, Dolozal^®, and Maxipan^® tablets) with mean percentage recoveries of 98.72 ± 0.35, 99.24 ± 0.89, and 98.20 ± 1.38, respectively. Furthermore, the method was successfully applied for assay of diflunisal in spiked human serum without the necessity of sample pretreatment or time-consuming extraction prior to the analysis. Mean percentage recovery of diflunisal in human serum was 99.16 ± 1.03 with a limit of detection of 3.0 × 10^?9 M (0.75 ng mL^?1). Due to this extremely low limit of detection, the proposed method was used to follow up the concentration of drug in blood samples of two male volunteers after oral administration of a single dose of Dolozal^®, 500 mg tablet.     

Carbon nanotube-modified glassy carbon electrode for anodic stripping voltammetric detection of Uranyle

A multi-wall carbon nanotube (MWNT) modified glassy carbon electrode (GCE) is described for the measurement of trace levels of uranium by anodic stripping voltammetry. In a pH 4.4 NaAc-Hac buffer containing 0.010 mol L⁻¹ Mg(NO₃)₂, UO₂ ²⁺ was adsorbed onto the surface of a MWNT film coated glassy carbon electrode and then reduced at −0.40 V vs. Ag/AgCl. During the positive potential sweep the reduced uranium was oxidized and a well-defined stripping peak appeared at +0.20 V vs. Ag/AgCl. Low concentrations of Mg²⁺ significantly enhanced the stripping peak currents since they induced UO₂ ²⁺ to adsorb at the electrode surface. The response was linear up to 1.2 × 10⁻⁷ mol L⁻¹ and the relative standard deviation at 2.0 × 10⁻⁸ mol L⁻¹ uranium was 5.2%. Potential interferences were examined. The attractive behavior of the new “mercury-free” uranium sensor holds promise for on-site environmental and industrial monitoring of uranium.     

Differential pulse voltammetric determination of chlorphenoxamine hydrochloride and its pharmaceutical preparations using platinum and glassy carbon electrodes

Voltammetric methods have been used for the determination of chlorphenoxamine hydrochloride (Ch-HCl) in raw material and in its pharmaceutical preparations (Allergex and Allergex caffeine tablet). It was found that Ch-HCl gives a characteristic cyclic voltammetric (CV) and differential pulse voltammetric (DPV) peak in acetonitrile using platinum and glassy carbon working electrodes. The I _p of the DPV peak increases linearly within the concentration range from 4.5 × 10⁻⁴ to 1.0 × 10⁻² mol L⁻¹ of the investigated drug. The concentration of Ch-HCl in raw drug material and in its pharmaceutical preparations was determined using the standard addition method, Randles–Sevcik equation and indirectly via its complexation with sodium tetraphenylborate (NaTPB). The obtained over all average recoveries were 101.44 and 100.49% with SD 0.45 and 0.38 (n = 4) for platinum and glassy carbon electrodes, respectively. The effect of scan rate, sample concentration, and supporting electrolyte on the I _p and E _p was also investigated.     

Voltammetric determination of bisoprolol fumarate in pharmaceutical formulations and urine using single-wall carbon nanotubes modified glassy carbon electrode

The electrochemistry of bisoprolol fumarate (BF) has been investigated by differential pulse voltammetry at a single-wall carbon nanotubes (SWNTs) modified glassy carbon electrode (GCE). The prepared electrode showed an excellent electrocatalytic activity towards the oxidation of BF leading to a marked improvement in sensitivity as compared to bare glassy carbon electrode where electrochemical activity for the analyte cannot be observed. The SWNTs-modified GCE exhibited a sharp anodic peak at a potential of ∼950 mV for the oxidation of BF. Under optimum conditions linear calibration curve was obtained over the BF concentration range 0.01-0.1 mM in 0.5 M phosphate buffer solution (pH 7.2) with a correlation coefficient of 0.9789 and detection limit of 8.27 × 10⁻⁷ M. The modified electrode has been applied for the drug determination in human urine with no prior extraction and in commercial tablets. The proposed method has also been validated.     

Adsorptive stripping differential pulse voltammetric determination of venlafaxine and desvenlafaxine employing Nafion–carbon nanotube composite glassy carbon electrode

A Nafion-carbon nanotube-modified glassy carbon electrode (NAF-CNT-GCE) was developed for the determination of venlafaxine (VF) and desvenlafaxine (DVF). The electrochemical behavior of both these molecules was investigated employing cyclic voltammetry (CV), chronocoulometry (CC), electrochemical impedance spectroscopy (EIS) and adsorptive stripping differential pulse voltammetry (AdSDPV). The surface morphology of the electrodes has been studied by means of scanning electron microscopy (SEM). These studies revealed that the oxidation of VF and DVF is facilitated at NAF-CNT-GCE. After optimization of analytical conditions employing this electrode at pH 7.0 in Britton–Robinson buffer (0.05 M) for VF and pH 5.0 in acetate buffer (0.1 M) for DVF, the peak currents for both the molecules were found to vary linearly with their concentrations in the range of 3.81 × 10⁻⁸–6.22 × 10⁻⁵ M for VF and 5.33 × 10⁻⁸–3.58 × 10⁻⁵ M for DVF. The detection limits (S/N = 3) of 1.24 × 10⁻⁸ and 2.11 × 10⁻⁸ M were obtained for VF and DVF, respectively, using AdSDPV. The prepared modified electrode showed several advantages, such as simple preparation method, high sensitivity, very low detection limits and excellent reproducibility. The proposed method was employed for the determination of VF and DVF in pharmaceutical formulations, urine and blood serum samples.     

Electrochemical behavior and voltammetric determination of 4-aminophenol based on graphene-chitosan composite film modified glassy carbon electrode

The graphene-chitosan composite film modified glassy carbon electrode (GCE) was fabricated and used to determine 4-aminophenol (4-AP). In 0.1 M pH 6.3 phosphate buffer solution, the redox peak currents of 4-AP increased significantly and the peak-to-peak separation decreased greatly at graphene-chitosan composite film modified GCE compared with bare GCE and chitosan modified GCE, indicating that graphene possessed electrocatalytic activity towards 4-AP. The experimental conditions were optimized and the kinetic parameters were investigated. The oxidation mechanism was discussed. Under the optimal experimental conditions, the oxidation peak current was proportional to 4-AP concentration in the range from 0.2 to 550 μM with the correlation coefficient of 0.9930. The detection limit was 0.057 μM (S/N = 3). Using the proposed method, 4-AP was successfully determined in water samples and paracetamol tablets with standard addition method, suggesting that this method can be applied to determine 4-AP in environments and pharmaceuticals.     

培氟沙星在碳糊电极上的阳极吸附伏安法研究

在0.40 mol/L的NaAc-HAc(pH 4.9)缓冲液中,使用JP-303极谱分析仪,培氟沙星在碳糊电极(CPE)上有一灵敏的吸附伏安氧化峰,峰电位为1.03 V(vs.SCE)。该氧化峰的二阶导数峰电流与培氟沙星的浓度在8.0×10-9~8.0×10-7mol/L(富集90 s)范围内成良好的线性关系,相关系数r为0.998,检出限为4.0×10-9mol/L(S/N=3,富集110 s)。探讨了培氟沙星在碳糊电极上的伏安性质和电极反应机理,并且成功应用于胶囊中培氟沙星含量的测定。     

碳糊电极阳极吸附伏安法测定阿司咪唑

在0.40mol/L的HAc-NaAc(pH 4.6)缓冲液中,阿司咪唑在碳糊电极(CPE)上有一灵敏的吸附氧化伏安峰,峰电位为0.84V(vs.SCE)。该氧化峰的二阶导数峰电流与阿司咪唑的浓度在2.0×10-9~1.0×10-7mol/L(富集90s)范围内呈良好的线性关系,相关系数r为0.9980,检出限为1.0×10-9mol/L,探讨了阿司咪唑在碳糊电极上的伏安性质和电极反应机理,并且成功地应用于息斯敏片含量的测定,加标回收率在99.7%~100.3%之间,结果与紫外分光光度法基本吻合。     

Electrochemistry and voltammetric determination of furazolidone with a multi-walled nanotube composite film-glassy carbon electrode

This study describes the electrochemical properties of furazolidone (Fu) at a glassy carbon electrode (GCE) modified with a multi-walled carbon nanotube (MWCNT) composite film. Cyclic voltammetry and chronoamperometry techniques were used for diagnostic purposes. The electrode (MWCNT-film-modified GCE) exhibited excellent electrocatalytic behavior for the reduction of Fu as evidenced by the enhancement of the 4e-reduction peak current and the shift in the reduction potential to more positive potential (by 50 mV) in comparison with a bare GCE. The formal potential, E ^0′, of Fu is pH dependent with a slope of 54.4 mV per unit of pH, close to the anticipated Nernestian value of −59 mV for a four-electron and four-proton processes. The transfer coefficient (α), standard rate constant of the surface reaction (k _s), diffusion coefficient (D), and surface concentration (Γ) for the MWCNT-film-modified GCE were calculated. On the other hand, Fu can be accumulated effectively on the MWCNT-film-modified GCE. Under the selected experimental conditions, i.e., solution pH 6, accumulation time 10 min, and accumulation potential −0.30 V, the peak current shows a dynamic linear range 3–800 μM with detection limit 2.30 μM. The method was successfully applied to analyze pharmaceutical formulations. The method used in this study was further applied for the determination of Fu.     

Electrochemical sensor based on a poly(para-aminobenzoic acid) film modified glassy carbon electrode for the determination of melamine in milk

A novel and simple sensor is developed in this paper for melamine detection, which is based on an electropolymerized molecularly imprinted polymer (MIP) of para-aminobenzoic acid (pABA). The poly(para-aminobenzoic acid) (P-pABA) film was deposited in a pABA solution by potentiodynamic cycling of potential with and without the template (melamine) on a glassy carbon electrode. The surface feature of the modified electrode was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The molecular imprinted sensor was tested by differential pulse voltammetry (DPV) to verify the changes in redox peak currents of hexacyanoferrate. Several important parameters controlling the performance of the P-pABA were investigated and optimized. In the optimal conditions, the relative redox peak currents of hexacyanoferrate were linear. The concentration of melamine ranged from 4.0 μM to 0.45 mM, with a linear correlation coefficient of 0.9992. The detection limit was 0.36 μM (S/N = 3). The MIP sensor was successfully applied to the determination of melamine in milk products and showed high selectivity, sensitivity, and reproducibility. The results of this research demonstrate that it is feasible to use the molecular imprinting methodology when preparing sensing devices for analytes that are electrochemically inactive.     

Fabrication of Fc-SWNTs modified glassy carbon electrode for selective and sensitive determination of dopamine in the presence of AA and UA

The electrochemistry of dopamine (DA) was investigated by cyclic voltammetry (CV) and differential pulse voltammograms (DPV) at a glassy carbon electrode modified by the hybridization adducts of Fc-SWNTs. The electro-oxidation of DA could be catalyzed by Fc/Fc⁺ couple as a mediator and had a higher electrochemical response due to the unique carbon surface of carbon nanotubes. The anodic peaks of DA, ascorbic acid (AA) and uric acid (UA) in their mixture can be well separated by the prepared electrode. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 5.0 × 10⁻⁶ to 3.0 × 10⁻⁵ M with a correlation coefficient of 0.9998 and a detection limit of 5.0 × 10⁻⁸ M based on the equation C_m = 3s_b1/m. The modified electrode has been successfully applied for the assay of DA in human blood serum. This work provides a simple and easy approach to selectively detect DA in the presence of AA and UA.