Study on electrochemical oxidation behaviors and the diffusion mechanism of hydroquinone at pre-anodized carbon paste electrode by cyclic voltammetry

A functional pre-anodized carbon paste electrode (PACPE) was constructed by using successive cyclic voltammetry. The electrochemical oxidation behaviors of hydroquinone (HQ) were carefully investigated by various electrochemical techniques. The diffusion mechanism of HQ has been put forward for the first time. The driving force for the HQ transport towards anode not only related to the concentration diffusion but also depended on the transport of H(+) in the feed phase along a concentration gradient towards the cathode. The results indicated that the PACPE exhibited excellent electrocatalytic activity towards the oxidation of HQ. Compared with the bare carbon paste electrode, the oxidation and reduction peak separation (ΔE(p)) of HQ at the PACPE has been decreased from 578 to 83 mV. Under the optimum conditions, the oxidation peak current was linear with HQ concentration in the range of 4 × 10(-7) to 1.0 × 10(-4) M with the linear correlation coefficient of 0.9986. The detection limit was 1.05 × 10(-7) M. This method can be successfully applied to the determination of HQ in wastewater.     

Electro-oxidation and determination of antihistamine drug, cetirizine dihydrochloride at glassy carbon electrode modified with multi-walled carbon nanotubes

A multi-walled carbon nanotube (MWCNT) film-modified glassy carbon electrode (GCE) was constructed for the determination of an antihistamine drug, cetirizine dihydrochloride (CTZH) using cyclic voltammetry (CV). Owing to the unique structure and extraordinary properties of MWCNT, the MWCNT film has shown an obvious electrocatalytic activity towards oxidation of CTZH, since it facilitates the electron transfer and significantly enhances the oxidation peak current of CTZH. All experimental parameters have been optimized. Under the optimum conditions, the oxidation peak current was linearly proportional to the concentration of CTZH in the range from 5.0×10(-7) to 1.0×10(-5)M. The detection limit was 7.07×10(-8)M with 180s accumulation. Finally, the proposed sensitive and simple electrochemical method was successfully applied to CTZH determination in pharmaceutical and urine samples.     

Electropolymerisation of L-arginine at carbon paste electrode and its application to the detection of dopamine, ascorbic and uric acid

L-arginine was electropolymerised on a carbon paste electrode (CPE) to form the biopolymer by free radical formation in the electro oxidation process of the amino and carboxylic group containing compound by cyclic voltammetric technique. The modified electrode shows an excellent electrocatalytic activity towards the oxidation of both dopamine (DA) and ascorbic acid (AA). It was demonstrated that the deposited biopolymer has positive charges over the bare carbon electrode surface, which leads to the formation of electrical double layer made the fast electron transfer process could leads to the diffusion of dopamine, ascorbic acid and uric acid on their charge gradient by cyclic voltammetric technique. The response of the sensor was tested towards the different dopamine concentration. The catalytic peak current obtained was linearly related to DA concentrations in the ranges of 5×10(-5) to 1×10(-4)M L(-1) with correlation co-efficient of 0.9924 which reveals the adsorption controlled process. The detection limit for dopamine was 5×10(-7)M L(-1). The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of ascorbic acid (AA) and response is fast stable, reliable, resistant to biofouling and can be applied for the real sample analysis in medical, pharmaceutical and biotechnological sectors. The adsorption-controlled process and kinetic parameters of the poly(L-arginine) were determined using electrochemical approaches.     

Poly-glutamic acid modified carbon nanotube-doped carbon paste electrode for sensitive detection of L-tryptophan

A novel poly-glutamic acid (PGA) film modified carbon paste electrode (CPE) incorporating carbon nanotubes (CNTs) was first prepared for the determination of l-tryptophan (l-Trp). Scanning electron microscopy and Fourier transform infrared spectroscopy were applied for characterization of the surface morphology of the modified electrodes and cyclic voltammetry was used to investigate the electrochemical properties of the proposed electrode towards the oxidation of l-Trp. Optimization of the experimental parameters was performed with regard to pH, ratio of CNTs, concentration of glutamic acid, electro-polymerization cycles, accumulation time and concentration of sodium dodecylbenzene sulfonate. The linearity between the oxidation peak current and the l-Trp concentration was obtained in the range of 5.0×10(-8) to 1.0×10(-4)M with a detection limit of 1.0×10(-8)M (S/N=3) and the sensitivity was calculated to be 1143.79μA?mM(-1)?cm(-2). In addition, the PGA modified CPE incorporating CNTs displayed high selectivity, good stability and reproducibility, making it suitable for the routine analysis of l-Trp in clinical use.     

石墨烯/十二烷基硫酸钠复合物修饰碳糊电极测定氯霉素

以液体石蜡和硅油为混合粘合剂,与石墨粉混合制备了碳糊电极基底电极,将石墨烯/十二烷基硫酸钠复合物修饰在基底碳糊电极上,得到了基于石墨烯复合物的新型修饰碳糊电极。应用扫描电镜和循环伏安法分别研究了该电极的表面特性和电化学性质,结果表明,石墨烯和十二烷基硫酸钠修饰的碳糊电极增大了比表面积,有利于电子传递。在pH 3.0的HAc-NaAc缓冲溶液中,该修饰碳糊电极对氯霉素具有良好的电化学响应,氧化峰电位为0.194 V,氧化峰电流是基底碳糊电极的10倍。在最优实验条件下,该氧化峰电流与氯霉素的浓度在1.0×10~(-8)~5.0×10~(-4)mol/L范围内呈良好的线性关系,检出限为5.0×10~(-9)mol/L。该方法简便,重现性及选择性好,用于测定氯霉素滴眼液和虾中氯霉素残留,结果满意。     

Simultaneous Voltammetric Determination of Uric Acid and Ascorbic Acid Using a Carbon‐Paste Electrode Modified with Multi‐Walled Carbon Nanotubes/Nafion and Cobalt(II)nitrosalophen

A composition of multiwalled carbon nanotube (MWCNT), Nafion and cobalt(II)‐5‐nitrosalophen (CoNSal) is applied for the modification of carbon‐paste electrode (CPE). The pretreated MWCNT is well dispersed in the alcoholic solution of Nafion under the ultrasonic agitation, and the resulted suspension is used as modifier (with 10% w/w) in the matrix of the paste electrode. The prepared electrode further modified by addition of 3 wt% of CoNSal. The resulted modified electrode is used as a sensitive voltammetric sensor for simultaneous determination of uric acid (UA) and ascorbic acid (AA). The electrode showed efficient electrocatalytic activity in lowering the anodic overpotentials and enhancement of the anodic currents. This electrode is able to completely resolve the voltammetric response of UA and AA. The effects of potential sweep rate and pH of the buffer solution on the response of the electrode, toward UA and AA, and the peak resolution is thoroughly investigated by cyclic and differential pulse voltammetry (CV and DPV). The best peak resolution for these compounds using the modified electrode is obtained in solutions with pH 4. The ΔE_p for UA and AA in these methods is about 315 mV, which is considerably better than previous reports for these compounds. A linear dynamic range of 1×10^?7 to 1×10^?4 M with a detection limit of 6×10^?8 M is resulted for UA in buffered solutions with pH 4.0. The voltammetric response characteristics for AA are obtained as, the linear range of 5×10^?7 to 1×10^?4 M with the detection limit of 1×10^?7 M. The voltammetric detection system was very stable and the reproducibility of the electrode response, based on the six measurements during one month, was less than 3.5% for the slope of the calibration curves of UA and AA. The prepared modified electrode is successfully applied for the determination of AA and UA in mixture samples and reasonable accuracies are resulted.     

Selective Voltammetric Detection of Uric Acid in the Presence of Ascorbic Acid at Well‐Aligned Carbon Nanotube Electrode

The voltammetric behaviors of uric acid (UA) and L ‐ascorbic acid (L ‐AA) were studied at well‐aligned carbon nanotube electrode. Compared to glassy carbon, carbon nanotube electrode catalyzes oxidation of UA and L ‐AA, reducing the overpotentials by about 0.028 V and 0.416 V, respectively. Based on its differential catalytic function toward the oxidation of UA and L ‐AA, the carbon nanotube electrode resolved the overlapping voltammetric response of UA and L ‐AA into two well‐defined voltammetric peaks in applying both cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which can be used for a selective determination of UA in the presence of L ‐AA. The peak current obtained from DPV was linearly dependent on the UA concentration in the range of 0.2 μM to 80 μM with a correlation coefficient of 0.997. The detection limit (3δ) for UA was found to be 0.1 μM. Finally, the carbon nanotube electrode was successfully demonstrated as a electrochemical sensor to the determination of UA in human urine samples by simple dilution without further pretreatment.     

聚色氨酸／镍复合膜修饰电极测定抗坏血酸的研究

采用电化学聚合法制备了聚色氨酸／镍复合膜修饰玻碳电极,研究了抗坏血酸在该修饰电极上的电化学行为,建立了测定痕量抗坏血酸的新方法。在pH6．2的磷酸盐缓冲溶液中,抗坏血酸在修饰电极上产生一个灵敏的氧化峰,采用线性扫描伏安法测定,其氧化峰电流与抗坏血酸浓度在2．0×10^-6 -1．0×10^-3mol／L范围内呈良好的线性关系,检出限为5．0×10^-7mol／L。对1．0×10^-4mol／L抗坏血酸溶液平行测定6次,测定结果的相对标准偏差为1．9％。该法用于片剂中抗坏血酸含量的测定,加标回收率为97．8％～101．2％。     

Electrochemical behavior of ascorbic acid at a 2,2'-[3,6-Dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone carbon paste electrode

Electrocatalytic oxidation of ascorbic acid (AA) at a carbon paste electrode, chemically modified 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone, was thoroughly investigated. The results of cyclic voltammetry, double potential-step chronoamperometry, linear sweep voltammetry and differential pulse voltammetry (DPV) studies were used for the prediction of the mechanism of electrochemical oxidation of AA mediated with 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone at the surface of the modified electrode. The diffusion coefficient (D = 2.45 x 10(-5) cm(2) s(-1)) and the kinetic parameters such as the electron transfer coefficient (alpha = 0.34) were also determined. The results of DPV using the 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone-modified electrode were applied in a highly sensitive determination of AA in drug samples. A linear range of 3.0 x 10(-6) - 1.2 x 10(-4) M and the detection limit (3sigma) 3.8 x 10(-7) M were obtained for DPV determination of AA in buffered pH 7.00 solutions (0.1 M phosphate buffer).     

Determination of nitrite based on mediated oxidation at a carbon paste electrode modified with a ruthenium polymer

The use of carbon paste electrodes modified with [Ru(bpy)(2)(PVP)(10)Cl]Cl for the mediated detection of nitrite is described. This surface modifier substantially lowers the overpotential for nitrite oxidation, hence permitting its determination at a lower potential. Various electrode characteristics were optimized, including the modifier loading and the monitoring potential, using batch amperometry. Standard calibration curves yielded slopes of 0.30 microA/microM over the linear range 5 x 10(-8)-5 x 10(-4)M nitrite with a detection limit of 3 x 10(-8)M (1.38 ppb) nitrite. The modified electrode response was shown to be relatively stable over a period of 5 days with a signal diminution of 8%. Electrode-to-electrode precision was measured as 11.4%. Flow-injection studies indicated the suitability of this electrode as a detector in flowing streams.     

Selective determination of 3,4-dihydroxyphenylacetic acid in the presence of ascorbic acid using 4-(dimethylamino)pyridine capped gold nanoparticles immobilized on gold electrode

4-(Dimethylamino)pyridine capped gold nanoparticles (DMAP-AuNPs) were synthesized in aqueous medium and then immobilized on 1,6-hexanedithiol (HDT) modified Au electrode for the selective determination of 3,4-dihydroxyphenylacetic acid (DOPAC) in the presence of ascorbic acid (AA). The synthesized DMAP-AuNPs were characterized by UV-visible spectroscopy and high resolution-transmission electron microscopy (HR-TEM). The HR-TEM images showed that the nanoparticles are spherical in shape with a diameter of ～12 nm. The DMAP-AuNPs immobilized on HDT modified electrode was characterized by cyclic voltammetry and impedance spectroscopy. Impedance spectra show that the electron transfer reaction was more facile at the AuNPs modified electrode when compared to bare and HDT modified Au electrodes. The application of DMAP-AuNPs modified electrode was demonstrated by selective determination of DOPAC in the presence of high concentration of AA at pH 4. Using amperometry method, 40 nM detection of each AA and DOPAC was achieved. The current response was increased linearly with increasing AA and DOPAC in the concentration range of 40×10(-9) to 10×10(-5) M and a detection limit was found to be 5.6×10(-10) M and 3.7×10(-10) M (S/N=3) for AA and DOPAC, respectively. The present modified electrode was also successfully used for the determination of 40 nM DOPAC in the presence of 2500-fold excess of common interferents such as Na(+), Mg(2+), Cu(2+), Ca(2+), NH(4)(+) urea and glucose.     

多壁碳纳米管修饰碳黑微电极同时测定多巴胺和抗坏血酸

制备了多壁碳纳米管修饰碳黑微电极,研究了多巴胺(DA)和抗坏血酸(AA)在该修饰电极上的电化学行为.实验表明,在pH 7.0的PBS缓冲溶液中,该修饰电极对DA和从均具有显著的催化氧化作用,AA与DA的氧化电位分别为30 mV和280 mV(vs.SCE).利用二次导数线性扫描伏安法测定,DA与AA的线性范围分别为6.0×10-9～2.0×10-4 mol/L和2.0×10-7～1.0×10-3mol/L,检出限为2.0×10-9mol/L 和1.0×10-7mol/L.方法已用于人工合成样品的分析.     

Electroanalysis and simultaneous determination of 6-thioguanine in the presence of uric acid and folic acid using a modified carbon nanotube paste electrode

The present work describes the preparation and characterization of a carbon nanotube paste electrode modified with 2,7-bis(ferrocenyl ethyl)fluoren-9-one (2,7-BF). This electrode showed an efficient catalytic activity for the electro-oxidation of 6-thioguanine (6-TG), which leads to lowering 6-TG overpotential by more than 610 mV. Also, the values of catalytic rate constant (k = 2.7 × 10(3) mol(-1) L s(-1)), and diffusion coefficient (D = 2.7 × 10(-5) cm(2) s) were calculated. In 0.1 M phosphate buffer solution of pH 7.0, the oxidation current increased linearly with two concentration intervals of 6-TG, one is 0.06 to 10.0 μmol L(-1) and the other is 10.0 to 160.0 μmol L(-1). The detection limit (3σ) obtained by differential pulse voltammetry (DPV) was 22.0 nmol L(-1). DPV was used for simultaneous determination of 6-TG, uric acid (UA) and folic acid (FA) at the modified electrode, and for quantification of 6-TG, UA and FA in some real samples by the standard addition method.     

Electrocatalytic determination of sumatriptan on the surface of carbon-paste electrode modified with a composite of cobalt/Schiff-base complex and carbon nanotube

The electrochemical oxidation of sumatriptan on the surface of carbon paste electrode modified with multi-walled carbon nanotube and cobalt methyl-salophen complex is studied by using cyclic voltammetry and polarization studies. The results indicate that the drug is irreversibly oxidized in a one electron oxidation mechanism. It was found that the peak potential shifted negatively with increasing pH, confirms that H(+) participate in the oxidation process. The electrode is shown to be very effective for the detection of sumatriptan in the presence of other biological reductant compounds. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of sumatriptan, ascorbic acid and uric acid, which makes it suitable for the simultaneous detection of sumatriptan in the presence of these compounds in clinical and pharmaceutical preparations. It can be concluded that multi-walled carbon nanotube and Shiff base complex have synergic effect on electroacatalytic oxidation of sumatriptan. A linear range of 1-1000μM and detection limit of 0.3μM was obtained for sumatriptan from DPV measurements using this electrode in 0.1M acetate buffered solution of pH 5.0. The electrode has been applied successfully for the determination of sumatriptan in synthetic serum and commercial tablets.     

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.     

Electrocatalytic Oxidation and Ion Chromatography Detection of S2O32-, SO32-, I- and SCN- at Glassy Carbon Electrode with Functionalized Multi-Wall Carbon Nanotubes Film

In this research, a glassy carbon electrode modified with the functionalized multi-wall carbon nanotubes (MWNT-COOHs) film was used as an amperometric sensor for the determination of S2O32-, SO23-, I- and SCN-. The electrochemical behavior of those oxidizable inorganic anions at this modified electrode was studied by means of cyclic voltammetry(CV). The experimental results indicate that the modified electrode exhibits a high electrocatalytic activity towards the oxidation of those anions with a relatively high sensitivity, a good stability and a long-life. Separated by ion chromatography(IC) with 1.25 mmol/L H2SO4 as an eluent,those oxidizable anions can be determined by the MWNT-COOHs modified electrode successfully. Under the optimal chromatographic conditions, the detection limits are 1.5 × 10-7 mol/L for S2O23-, 2. 5 × 10-7 mol/L for SO32-, 1.2 × 10-7 mol/L for I- and 2. 0 × 10-7 mol/L for SCN-, respectively. The method was applied successfully to the determination of those anions in environmental water.     

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。     

多巴胺在聚亚甲基蓝/石墨烯修饰电极上的电化学行为研究

利用电聚合方法在石墨烯修饰的玻碳电极表面制备了聚亚甲基蓝/石墨烯修饰电极(PMB/GH/GCE)。采用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了多巴胺(DA)和抗坏血酸(AA)在该修饰电极上的电化学行为。在pH 6.9的磷酸盐缓冲溶液中,DA和AA分别在0.208 V和-0.108 V处产生灵敏的氧化峰,与其在聚亚甲基蓝和石墨烯单层修饰电极上的电化学行为相比,两者的峰电流明显增加,峰电位差达316 mV。研究表明,电聚合方法使亚甲基蓝牢固地非共价修饰到石墨烯上,并产生协同增效作用,较好地提高了电极的灵敏度和分子识别性能,有利于在大量AA存在下实现对DA的选择性测定。在1.00×10-3mol/L AA的存在下,DA的差分脉冲伏安法峰电流与其浓度在1.00×10-7～5.00×10-3mol/L范围内呈良好的线性关系,检出限达1.00×10-8mol/L。将该方法用于盐酸多巴胺注射液的测定,结果满意。     

Simultaneous determination of sugars and ascorbic acid by capillary zone electrophoresis with amperometric detection at a carbon paste electrode modified with polyethylene glycol and Cu(2)O

In this paper, a kind of novel carbon paste electrode modified with double modifiers-polyethylene glycol (PEG) and Cu(2)O (PEG/Cu(2)O CPME) in capillary zone electrophoresis with amperometric detection (CZE-AD) was applied to simultaneously determine three sugars: glucose, sucrose, fructose and ascorbic acid (AA). The catalytic electrochemical properties of PEG/Cu(2)O CPME could enhance sensitivity obviously compared with carbon paste electrode modified with only PEG or Cu(2)O at a relatively lower detection potential (+0.3 V versus SCE). Especially, the electrochemical detection response of AA increased obviously to the same level of saccharides by adding PEG into the Cu(2)O carbon paste modified electrode. The four analytes could be perfectly separated within 22 min, the linear ranges were from 1.0 x 10 (-6) to 5.0 x 10(-5) mol L(-1) and the detection limits were at 10(-7) mol L(-1) magnitude (S/N=3). The present working electrode was successfully employed to analyse beverage samples with recoveries in the range 93-107% and RSDs less than 4%. Above results demonstrated that capillary zone electrophoresis coupled with the PEG/Cu(2)O carbon paste modified electrode was of convenient preparation, high sensitivity, good repeatability and could be used in the rapid determination of practical samples.     

多巴胺和抗坏血酸在十六烷基三甲基溴化铵/碳纳米管电极上的检测

研究了十六烷基三甲基溴化铵(CTMAB)/多壁碳纳米管修饰玻碳电极的制备以及多巴胺和抗坏血酸在该修饰电极上的电化学行为。在CTMAB和多壁碳纳米管的协同作用下,该修饰电极对多巴胺和抗坏血酸均具有显著的催化氧化作用,多巴胺和抗坏血酸的氧化峰电位分别为223mV和15mV,实现了在抗坏血酸共存时测定多巴胺。在pH7.0的磷酸盐缓冲溶液中,多巴胺和抗坏血酸的线性范围分别为2.0×10-6～2.0×10-3mol/L和4.0×10-5～1.0×10-2mol/L,检出限分别为6.0×10-7mol/L和1.0×10-5mol/L。