Amperometric sensor for nitrite using a glassy carbon electrode modified with alternating layers of iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin and cobalt(II) tetrasulfonated phthalocyanine

The development of a highly sensitive amperometric sensor for nitrite using a glassy carbon electrode modified with alternated layers of iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and cobalt(II) tetrasulfonated phthalocyanine (CoTSPc) is described. The modified electrode showed an excellent catalytic activity and stability for the nitrite oxidation decreasing the peak potentials about 200 mV toward less positive values and presenting much higher peak currents than those obtained on the bare GC electrode. A linear response range of 0.2-8.6 μmol l⁻¹, with a sensitivity of 0.37 μA l μmol⁻¹ and detection limit of 0.04 μmol l⁻¹ were obtained with this sensor. The repeatability of the proposed sensor, evaluated in term of relative standard deviation, was verified to be 1.4% for 10 measurements of 0.2 μmol l⁻¹ nitrite solution. Interference caused by common ions has been investigated in simulated mixtures containing high concentration level of interfering ions and the sensor was found to be tolerant against these ions. The developed sensor was applied for the nitrite determination in water samples and the results were in agreement with those obtained by a comparative method described in the literature. The average recovery for these samples was 100.1 (±0.7)%.     

Alternating Layers of Iron(III) Tetra(N‐methyl‐4‐pyridyl)‐porphyrin and Copper Tetrasulfonated Phthalocyanine for Amperometric Detection of 4‐Nitrophenol in Nanomolar Levels

The present work describes the development of a highly sensitive amperometric sensor for 4‐NP in nanomolar levels using a glassy carbon electrode modified with alternating layers of CuTSPc and FeT4MPyP. After optimizing the operational conditions, the sensor provided a linear response range for 4‐NP from 5 up to 100 nmol L^?1 with sensitivity, detection, and quantification limits of 14 nA L nmol^?1, 1.9 nmol L^?1, and 5.4 nmol L^?1, respectively. The proposed sensor showed a stable response for at least 200 successive determinations. This modified electrode can be used to the determination of 4‐NP in water samples.     

Sensitive voltammetric determination of paracetamol by poly (4-vinylpyridine)/multiwalled carbon nanotubes modified glassy carbon electrode

A novel glassy carbon electrode (GCE) modified with a composite film of poly (4-vinylpyridine) (P4VP) and multiwalled carbon nanotubes (P4VP/MWCNT GCE) was used for the voltammetric determination of paracetamol (PCT). This novel electrode displayed a combined effect of P4VP and MWCNT on the electro-oxidation of PCT in a solution of phosphate buffer at pH 7. Hence, conducting properties of P4VP along with the remarkable physical properties of MWCNTs might have combined effects in enhancing the kinetics of PCT oxidation. The P4VP/MWCNT GCE has also demonstrated excellent electrochemical activity toward PCT oxidation compared to that with bare GCE and MWCNT GCE. The anodic peak currents of PCT on the P4VP/MWCNT GCE were about 300 fold higher than that of the non-modified electrodes. By applying differential pulse voltammetry technique under optimized experimental conditions, a good linear ratio of oxidation peak currents and concentrations of PCT over the range of 0.02–450 μM with a limit of detection of 1.69 nM were achieved. This novel electrode was stable for more than 60 days and reproducible responses were obtained at 99% of the initial current of PCT without any influence of physiologically common interferences such as ascorbic acid and uric acid. The application of this electrode to determine PCT in tablets and urine samples was proposed.     

阿奇霉素在多壁碳纳米管修饰电极上的电化学行为及其测定

运用循环伏安法与线性扫描伏安法研究了阿奇霉素在多壁碳纳米管修饰玻碳电极上的电化学行为,建立了一种直接测定阿奇霉素的电化学分析方法。结果表明,与裸玻碳电极相比,多壁碳纳米管修饰电极能显著提高阿奇霉素的氧化峰电流,阿奇霉素的电极过程完全不可逆,存在典型的吸附特性。在优化的实验条件下,氧化峰电流与阿奇霉素浓度在3.0×10-7～2.5×10-5 mol/L和2.5×10-5～5.0×10-4 mol/L范围内呈现良好的线性关系,检出限为1.0×10-7 mol/L。     

Catalytic-voltammetric determination of the antioxidant tert-butylhydroxyanisole (BHA) at a nickel phthalocyanine modified carbon paste electrode

The voltammetric behaviour of the antioxidant tert-butylhydroxyanisole (BHA), at a carbon paste electrode modified with the electron mediator nickel phthalocyanine, is described, and a method for the determination of this antioxidant, based on its oxidation on the modified electrode, is proposed. Cyclic voltammograms showed a well-defined oxidation peak for BHA slightly shifted towards less positive potentials with respect to that obtained at the plain carbon paste electrode. The peak current measured at the modified electrode is considerably higher than that obtained at the unmodified electrode. A modifier percentage of 2%, a methanol percentage of 2% and a 0.1 mol/HClO(4) medium were chosen as working conditions. The i(p)vs v1 2 plot obtained by linear sweep voltammetry showed a linear relationship over the whole scan rate range studied (5-2000 mV/sec) which is typical of a diffusion-controlled current. Using differential pulse voltammetry at DeltaE = 50 mV, linear calibration graphs were obtained in the concentration ranges 1.0-30.0, 0.10-1.0 and 0.02-0.10 mg/l BHA. The detection limit was 0.0036 mg/l (2.0 x 10(-8) mol/l). Interferences from other substances commonly present in commercial antioxidant mixtures were tested. The developed method was applied to the determination of BHA in spiked potato flakes.     

The electrocatalytic activity of a supramolecular assembly of CoTsPc/FeT4MPyP on multi-walled carbon nanotubes towards L-glutathione, and its determination in human erythrocytes

The electrocatalytic activity of a supramolecular complex based on cobalt(II) phthalocyanine tetrasulfonate and iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin adsorbed on multi-walled carbon nanotubes for the oxidation of L-glutathione (GSH) was investigated at pH 7.4. Scanning electron microscopy and energy dispersive X-ray spectrometry were used to characterize the morphologies and composition of the materials. The modified electrode displayed efficient electrocatalytic activity in terms of oxidation of GSH at an oxidation potential of 0 V (versus Ag/AgCl). Cyclic voltammetry and amperometry indicated that the oxidation involves 2-electrons, with a heterogeneous rate constant of 4.9?×?10⁵ mol^?1 L s^?1. The response is linear from 2 to 210 μmol ?L^-1, the sensitivity is 1570 μA L mmol^?1, the detection limit is 0.03 μmol L^?1, and the relative standard deviation of 110 μmol L^?1 GSH was 2.6% (n?=?10). The modified electrode was applied to the determination of GSH in erythrocytes and the results were in agreement with those obtained by a method reported in the literature.     

Amperometric determination of glutathione and cysteine on a Pd-IrO(2) modified electrode with high performance liquid chromatography in rat brain microdialysate

A Pd/IrO(2) co-electrodeposited glassy carbon electrode was prepared and the electrochemical behavior of glutathione (GSH) at this chemically modified electrode (CME) has been studied by cyclic voltammetry (CV). The results indicated that the modified electrode efficiently exhibited electrocatalytic oxidation for GSH with relatively high sensitivity, stability, and long-life. Coupled with high-performance liquid chromatography (HPLC), the Pd/IrO(2) modified electrode was utilized for the electrochemical detection (ECD) of the thiocompounds, glutathione and cysteine (Cys). The peak currents were linear with the substance concentrations in the range of 1.0 x 10(-5) mol L(-1) to 8.0 x 10(-4) mol L(-1) for GSH and 4.0 x 10(-6) mol L(-1) to 2.0 x 10(-4) mol L(-1) for Cys. The detection limits were 2.0 x 10(-6) mol L(-1) for GSH and 5.0 x 10(-7) mol L(-1) for Cys with S/N of 3. The method has been successfully applied to assess the contents of GSH and Cys in rat brain microdialysates.     

Voltammetric determination of cefpirome at multiwalled carbon nanotube modified glassy carbon sensor based electrode in bulk form and pharmaceutical formulation

A new, simple and low cost voltammetric method for the determination of cefpirome in pharmaceutical preparations has been developed using multiwalled carbon nanotube modified glassy carbon electrode (MWCNT), which showed stable response with enhanced selectivity and sensitivity over the bare glassy carbon electrode. A multiwalled carbon nanotube (MWCNT) modified glassy carbon electrode (GCE) is used for the simultaneous determination of cefpirome by differential pulse voltammetry and square wave voltammetry. Results indicated that cathodic peak of cefpirome is greatly improved at MWCNT modified GC electrode as compared with the bare GC electrode showing excellent electrocatalytic activity towards cefpirome reduction. Linear calibration curves are obtained over the concentration range 100-600 μg mL(-1) in Britton Robinson buffer at pH 4.51 with limit of detection (LOD) and limit of quantification (LOQ) are 0.647 μg mL(-1) and 2.159 μg mL(-1) using SWV and 5.540 μg mL(-1) and 18.489 μg mL(-1) using DPV, respectively. The described method is rapid and can be successfully applied for the determination of cefpirome in bulk form and pharmaceutical formulations.     

A highly sensitive amperometric sensor for oxygen based on iron(II) tetrasulfonated phthalocyanine and iron(III) tetra-(N-methyl-pyridyl)-porphyrin multilayers

The development of a highly sensitive sensor for oxygen is proposed using a glassy carbon (GC) electrode modified with alternated layers of iron(II) tetrasulfonated phthalocyanine (FeTsPc) and iron(III) tetra-(N-methyl-pyridyl)-porphyrin (FeT4MPyP). The modified electrode showed excellent catalytic activity for the oxygen reduction. The reduction potential of the oxygen was shifted about 330 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare GC electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves 4 electrons with a heterogenous rate constant (k_obs) of 3 × 10⁵ mol⁻¹ L s⁻¹. A linear response range from 0.2 up to 6.4 mg L⁻¹, with a sensitivity of 4.12 μA L mg⁻¹ (or 20.65 μA cm⁻² L mg⁻¹) and a detection limit of 0.06 mg L⁻¹ were obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation (R.S.D.) was 2.0% for 10 measurements of a solution of 6.4 mg L⁻¹ oxygen. The sensor was applied to determine oxygen in pond and tap water samples showing to be a promising tool for this purpose.     

Electrocatalytic characteristics of a 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone modified carbon-paste electrode in the oxidation of ascorbic acid.

A carbon-paste electrode spiked with 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone was constructed by the incorporation of 1-[4-(ferrocenyl ethynyl)phenyl]-1-ethanone in a graphite powder silicon oil matrix. It shown by cyclic voltammetry and double potential-step chronoamperometry, which this ferrocene derivative modified a carbon-paste electrode, can catalyze the ascorbic acid oxidation in an aqueous buffered solution. It has been found that under the optimum conditions (pH 7.00), the oxidation of ascorbic acid at the surface of this carbon paste modified electrode occurs at a potential of about 260 mV less positive than that of an unmodified carbon-paste electrode. The catalytic oxidation peak current was linearly dependent on the ascorbic acid concentration, and a linear calibration curve was obtained in the range of 6 x 10(-5) M-7 x 10(-3) M of ascorbic acid with a correlation coefficient of 0.9997. The detection limit (2sigma) was determined to be 6.3 x 10(-5) M. This method was also used for the determination of ascorbic acid in some pharmaceutical samples, such as effervescent tablets, ampoules and multivitamin syrup, by using a standard addition method. The reliability of the method was established by a parallel determination against the official method.     

Comparison of inorganic films and poly(4-vinylpyridine) coatings as electrode modifiers for flow-injection systems

A glassy-carbon electrode modified with a ruthenium-containing inorganic film was used for the flow-injection determination of As(III). The linear working range was 5-100 muM, and the detection limit was 300 pg. The response was reproducible for periods of several days. A glassy-carbon electrode modified by adsorption of a quaternized poly(4-vinylpyridine) film impregnated with hexachloroiridate(II and III) was used for the oxidation of nitrite. The calibration graphs were non-linear and varied from day to day, and the peak widths were broad. Nitrite determination at a platinum electrode modified by adsorption of iodine gave results analogous to the As(III) study; however, an overlayer of quaternized poly(4-vinylpyridine) decreased the sensitivity.     

Selective and Simultaneous Voltammetric Determination of Glutathione,Uric Acid and Penicillamine by a Modified Carbon Nanotube Paste Electrode

In this paper, the use of a carbon paste electrode (CPE) modified by (E)‐3‐((2‐(2,4‐dinitrophenyl)hydrazono)methyl)benzene‐1,2‐diol (DHB) and carbon nanotubes (CNTs) for the determination of glutathione (GSH), uric acid (UA) and penicillamine (PA) is described. Initially, cyclic voltammetry was used to investigate the redox properties of the modified electrode in phosphate buffer. Next, the electrocatalytic oxidation of GSH via EC′ mechanism at the modified electrode was described. At the optimum pH of 7.0, the oxidation of GSH occurs at a potential that is 530 mV less positive than that of an unmodified carbon paste electrode. The values of the diffusion coefficient (D=2.5×10^?6 cm² s^?1) and the catalytic rate constant (k=1.7×10³ M^?1 s^?1) were calculated for GSH, using chronoamperometry. Based on differential pulse voltammetry, the oxidation of GSH exhibited a dynamic range between 0.4 and 700.0 µM and a detection limit (3σ) of 70.0 nM. Also, simultaneous determination of GSH, UA and PA was described at the modified electrode. Finally, this method was used for the determination of these substances in synthetic solutions and blood serum samples.     

Glassy carbon electrodes modified by multiwalled carbon nanotubes and poly(neutral red): A comparative study of different brands and application to electrocatalytic ascorbate determination

The electrochemical behaviour of glassy carbon electrodes coated with multiwalled carbon nanotubes (MWCNT) from three different sources and with different loadings has been compared, with a view to sensor applications. Additionally, poly(neutral red) (PNR) was electrosynthesised by potential cycling on bare glassy carbon and on MWCNT-modified glassy carbon electrodes, and characterised by cyclic voltammetry and scanning electron microscopy. Well-defined voltammetric responses were observed for hexacyanoferrate (II) oxidation with differences between the MWCNT types as well as from loading. The MWCNT and PNR/MWCNT-modified electrodes were applied to the oxidative determination of ascorbate, the electrocatalytic effects observed varying according to the type of nanotubes. Comparison was made with electrodes surface-modified by graphite powder. All modified electrode configurations with and without PNR were successfully employed for ascorbate oxidation at +0.05 V vs saturated calomel electrode with detection limits down to 4 μM; good operational stability and storage stability were also obtained.     

PCA/GC电极同时测定尿酸(UA)和抗坏血酸(AA)

制备聚肉桂酸(PCA)修饰电极(PCA/GC),研究尿酸(UA)和抗坏血酸(AA)在该电极上的电化学行为.结果表明,在UA和AA共存体系中,UA、AA在PCA/GC电极上氧化峰电流增大且峰电位分别负移至50mV、330mV,二者相差280mV,据此可同时检测UA和AA.在pH6.0磷酸盐缓冲液中,UA、AA的氧化峰电流与其浓度分别在2.0×10-6～1.0×10-4mol·L-1、2.0×10-5～6.0×10-4mol·L-1范围内呈线性关系.该电极重现性好,适用于尿样中UA的检测.     

碳纳米管修饰电极-人工神经网络同时检测一氯酚三种异构体

建立了碳纳米管修饰电极-人工神经网络同时检测-氯酚三种异构体的方法.在pH=7.0的磷酸盐缓冲溶液中,邻氯酚、间氯酚和对氯酚在碳纳米管修饰电极上均有一灵敏的不可逆氧化峰.采用微分脉冲溶出伏安法,在优化的实验条件下,邻氯酚、间氯酚和对氯酚的峰电位分别为624 mV、712 mV和632 mV,且浓度分别在2.07～103...     

自组装纳米金的多壁碳纳米管微电极的制备及其在测定多巴胺中的应用

通过羧基化多壁碳纳米管(MWCNT′s-COOH)与巯基乙胺反应制得巯基化多壁碳纳米管(MWCNT′s-SH),将MWCNT′s-SH加入含有硼氢化钠的氯金酸溶液中,使生成的纳米金颗粒(AuNP′s)自组装到MWCNT′s-SH上,制得MWCNT′s-SH/AuNP′s粉末。将MWCNT′s-SH/AuNP′s粉末与微电极(ME)反复磨压使粉末进入ME顶端小孔内,烘干后即得MWCNT′s-SH/AuNP′s/ME。采用循环伏安法研究了多巴胺在修饰电极上的电化学行为。结果表明:多巴胺在该修饰电极上出现了一对氧化还原峰。多巴胺线性范围为5.0×10-6～6.4×10-4 mol.L-1,检出限(3S/N)为5.1×10-9 mol.L-1。修饰电极用于盐酸多巴胺注射液中多巴胺的测定,测定值与标示值相符,加标回收率在98.0%～103.0%之间。     

Low potential detection of nicotine at multiwalled carbon nanotube–alumina-coated silica nanocomposite

Electrocatalytic oxidation of nicotine at multiwalled carbon nanotube (MWCNT)–alumina-coated silica (ACS) nanocomposite modified glassy carbon electrode are described. The sensing performance of the MWCNT–ACS nanocomposite modified glassy carbon electrode for the electrooxidation of nicotine was investigated using cyclic voltammetry and amperometry in 0.1 M phosphate buffer solution (pH 8). The MWCNT–ACS nanocomposite modified glassy carbon electrode exhibited the abilities to decrease the electrooxidation potential, to prevent the electrode surface fouling, and to raise the current responses. The MWCNT–ACS nanocomposite responded rapidly to nicotine with a sensitivity of 1.786 A M^?1 cm^?2 and a detection limit of 1.42 μM (according to 3σ criterion). A signal almost 180 times more sensitive was obtained at MWCNT–ACS nanocomposite modified glassy carbon electrodes as compared to bare glassy carbon electrode. The nicotine oxidation potential obtained in this study is much lower than that at boron-doped diamond electrodes.     

Electroanalysis of some common pesticides using conducting polymer/multiwalled carbon nanotubes modified glassy carbon electrode

The cyclic voltammetric behaviour of three common pesticides such as isoproturon (ISO), voltage (VOL) and dicofol (DCF) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNTs/GCE), polyaniline (PANI) and polypyrrole (PPY) deposited MWCNT/GCE. The modified electrode film was characterized by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The electroactive behaviour of the pesticides was realized from the cyclic voltammetric studies. The differential pulse voltammetric principle was used to analyze the above-mentioned pesticides using MWCNT/GCE, PANI/MWCNT/GCE and PPY/MWCNT/GCE. Effects of accumulation potential, accumulation time, Initial scan potential, amplitude and pulse width were examined for the optimization of stripping conditions. The PANI/MWCNT/GCE performed well among the three electrode systems and the determination range obtained was 0.01-100 mgL(-1) for ISO, VOL and DCF respectively. The limit of detection (LOD) was 0.1 microgL(-1) for ISO, 0.01 microgL(-1) for VOL and 0.05 microgL(-1) for DCF on PANI/MWCNT/GCE modified system. It is significant to note that the PANI/MWCNT/GCE modified system results in the lowest LOD in comparison with the earlier reports. Suitability of this method for the trace determination of pesticide in spiked samples was also realized.     

The promotion effect of titania nanoparticles on the direct electrochemistry of lactate dehydrogenase sol-gel modified gold electrode

The promotion effect of titania nanoparticles (nano-TiO(2)) on the direct electron transfer between lactate dehydrogenase (LDH) and the silica sol-gel modified gold electrode was investigated by adding nano-TiO(2) (50 nm) in the modification process. This nano-TiO(2)-LDH electrode showed a pair of quasi-reversible cyclic voltammetry peaks with the formal potential of 70 mV (vs. SCE). Compared to the previous result of LDH modified electrode with only an irreversible cathodic peak, an anodic peak appeared and the cathodic peak potential shifted to the positive direction on this nano-TiO(2)-LDH electrode, which demonstrated that the direct electrochemistry of LDH was enhanced by nano-TiO(2). We supposed that the direct electrochemistry of LDH may be due to the redox reaction of some electroactive amino acids in the LDH molecule. The surface morphologies of electrodes characterized by SEM indicated that LDH was successfully immobilized on the sol-gel matrix and also had some interactions with nano-TiO(2). This electrode can be used as a biosensor for the determination of lactic acid. The calibration range of lactic acid was from 1.0 to 20 micromolL(-1) and the detection limit was 0.4 micromolL(-1). Meanwhile, the small K(m)(app) value (2.2 micromolL(-1)) suggested that LDH possessed high enzymatic activity and good affinity to lactic acid owing to the promotion effect of nano-TiO(2).     

聚对氨基吡啶化学修饰电极上酚磺乙胺的电化学行为及其溶出伏安法测定

在玻碳电极上制备了聚对氨基吡啶 (POAP)修饰膜电极 ,并用POAP电极研究了酚磺乙胺 (DIC)的电化学行为。POAP修饰电极对DIC的氧化有良好的电催化活性。循环伏安图上出现一对灵敏、可逆的氧化还原峰。在最佳条件下 ,氧化峰电流与DIC浓度在 4.0× 10 -8～ 1.0× 10 -3 mol/L范围内呈良好线性关系 ,开路富集 5min检测限达 7.6× 10 -10 mol/L。用POAP测定DIC具有良好的重现性、灵敏度和稳定性