Electrocatalytic oxidation of dopamine at an ionic liquid modified carbon paste electrode and its analytical application

A room-temperature ionic liquid N-butylpyridinium hexafluorophosphate was used as a binder to construct an ionic liquid modified carbon paste electrode, which was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. The ionic liquid carbon paste electrode (IL-CPE) showed enhanced electrochemical response and strong analytical activity towards the electrochemical oxidation of dopamine (DA). A pair of well-defined quasireversible redox peaks of DA appeared, with the redox peaks located at 215 mV (E _pa) and 151 mV (E _pc) (vs. the saturated calomel electrode, SCE) in pH 6.0 phosphate buffer solution. The formal potential (E ^0′) was calculated as 183 mV (vs. SCE) and the peak-to-peak separation as 64 mV. The electrochemical behavior of DA on the IL-CPE was carefully investigated. Under the optimal conditions, the anodic peak currents increased linearly with the concentration of DA in the range 1.0 × 10⁻⁶–8.0 × 10⁻⁴ mol/L and the detection limit was calculated as 7.0 × 10⁻⁷ mol/L (3σ). The interferences of foreign substances were investigated and the proposed method was successfully applied to the determination of DA injection samples. The IL-CPE fabricated was sensitive, selective and showed good ability to distinguish the coexisting ascorbic acid and uric acid.     

Electrochemical oxidation of cisatracurium on carbon paste electrode and its analytical applications

The electrochemical oxidation of cisatracurium was investigated by cyclic voltammetry and differential pulse voltammetry at a carbon paste electrode and the experimental parameters have been optimized in order to obtain the optimum analytical signal. A differential pulse voltammetric method with carbon paste electrode is described for the determination of cisatracurium with detection limit of 0.38 μg/ml and quantitation limit of 1.26 μg/ml. The proposed method was applied to determine the content of cisatracurium in human urine and human serum, obtaining accurate and precise results.     

Electrochemical behaviors of guanosine on carbon ionic liquid electrode and its determination

The electrochemical behaviors of guanosine on the ionic liquid of N-butylpyridinium hexafluorophosphate (BPPF₆) modified carbon paste electrode (CPE) was studied in this paper and further used for guanosine detection. Guanosine showed an adsorption irreversible oxidation process on the carbon ionic liquid electrode (CILE) with the oxidation peak potential located at 1.12 V (vs. SCE) in a pH 4.5 Britton-Robinson (B-R) buffer solution. Compared with that on the traditional carbon paste electrode, small shift of the oxidation peak potentials appeared but with a great increment of the oxidation peak current on the CILE, which was due to the presence of ionic liquid in the modified electrode adsorbed the guanosine on the surface and promoted the electrochemical response. The electrochemical parameters such as the electron transfer coefficient (α), the electron transfer number (n), and the electrode reaction standard rate constant (k_s) were calculated as 0.74, 1.9 and 1.26 × 10⁻⁴ s⁻¹, respectively. Under the optimal conditions the oxidation peak current showed a good linear relationship with the guanosine concentration in the range from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol/L by cyclic voltammetry with the detection limit of 2.61 × 10⁻⁷ mol/L (3σ). The common coexisting substances showed no interferences to the guanosine oxidation. The CILE showed good ability to distinguish the electrochemical response of guanosine and guanine in the mixture solution. The urine samples were further detected by the proposed method with satisfactory results.     

An ionic liquid-type carbon paste electrode and its polyoxometalate-modified properties

The replacement of a non-conductive organic binder with a conductive room temperature ionic liquid in fabricating carbon paste electrode has been made. This new electrode due to its enhanced conductivity presented very large current response from electroactive substrates. The novel carbon paste electrode was bulk-modified via the uniform dispersion of Keggin-type phospho polyoxomolybdate (PMo₁₂) in bulky carbons, which possessed excellent electrocatalytic activity for the reduction of nitrite. The pronounced multi-electron catalytic ability was ascribed to the used hydrophobic ionic liquid which constructed an excellent charge-transfer bridge in the bulk of carbon paste electrode, thus facilitated the intake of electrons from reduced PMo₁₂ mediators. In view of their prominent properties, the carbon paste electrode using ionic liquid binder and its bulk-modified electrode take on good prospects of the application in physical chemistry and electroanalytical chemistry fields.     

替硝唑在碳糊电极上的电化学性质及电分析方法研究

运用循环伏安法(CV)、方波伏安法(SWV)研究替硝唑(TNZ)在碳糊电极(CPE)上的电化学行为、电化学动力学性质及可能的电极反应机理.TNZ在CPE上的伏安行为是一受扩散控制的不可逆电化学还原过程,还原峰电位(Epc)为-0.557 V.用方波伏安法(SWV)测定TNZ线性范围为1.0×10-5～1.0×10h-3mol/L,检出限3.3×10-7mol/L.RSD 1.3%～2.8%,加样回收率99.2%～100.6%.据此建立了TNZ含量的电化学测定方法.     

An ionic liquid-type carbon paste electrode for electrochemical investigation and determination of calcium dobesilate

An ionic liquid-type carbon paste electrode (IL-CPE) had been fabricated by replacing non-conductive organic binders with a conductive room temperature ionic liquid, 1-pentyl-3-methylimidazolium hexafluorophosphate (PMIMPF₆). The electrochemical responses of calcium dobesilate were investigated at the IL-CPE and the traditional carbon paste electrode (T-CPE) in 0.05 mol L⁻¹ H₂SO₄, respectively. The results showed the superiority of IL-CPE to T-CPE in terms of provision of higher sensitivity, faster electron transfer and better reversibility. A novel method for determination of calcium dobesilate was proposed. The oxidation peak current was rectilinear with calcium dobesilate concentration in the range of 8.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹, with a detection limit of 4.0 × 10⁻⁷ mol L⁻¹(S/N = 3) by differential pulse voltammetry. The proposed method was applied to directly determine calcium dobesilate in capsule and urine samples.     

Sensitive voltammetric determination of rutin at an ionic liquid modified carbon paste electrode

An ionic liquid modified carbon paste electrode (IL/CPE) had been fabricated by using hydrophilic ionic liquid 1-amyl-3-methylimidazolium bromide ([AMIM]Br) as a modifier. The IL/CPE was characterized by scanning electron microscope and voltammetry. Electrochemical behavior of rutin at the IL/CPE had been investigated in pH 3.29 Britton-Robinson (B-R) buffer solution by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results suggested that the modified electrode exhibited an electrocatalytic activity toward the redox of rutin. The electron transfer coefficient (α) and the standard rate constant (k_s) of rutin at the modified electrode were calculated. Under the selected conditions, the reduction peak current was linearly dependent on the concentration of rutin in the range of 4.0 × 10⁻⁸ to 1.0 × 10⁻⁵ mol L⁻¹ (r = 0.9998), with a detection limit of 1.0 × 10⁻⁸ mol L⁻¹ (S/N = 3). The relative standard deviation (R.S.D.) for six times successful determination of 8.0 × 10⁻⁷ mol L⁻¹ rutin was 1.2%. The proposed method was applied to determine rutin in tablet and urine sample. In addition, the IL/CPE exhibited a distinct advantage of simple preparation, surface renewal, good reproducibility and good stability.     

吡啶类碳离子液体电极对酚磺乙胺的电化学行为及其分析应用

用离子液体1-丁基吡啶六氟磷酸盐(BuPyPF6)作为粘合剂构置了碳离子液体修饰电极(BuPyPF6-CILE).在0.05 mol/L H2SO4溶液中,用循环伏安法研究了在BuPyPF6-CILE和传统碳糊电极(TCPE)上酚磺乙胺(ESL)的电化学行为,建立了测定尿样和血清样品中ESL含量的新方法.ESL在BuPyPF6-CILE上的氧化峰电流响应是其在TCPE上的8.7倍,峰电位差降低到0.101 V,电子转移速率常数Ks=0.544 s-1,电极表面平均吸附量为1.66×10-9 mol·cm2.ESL的氧化电流与其浓度在8.0×10-8～2.0×10-6mol/L和5.0×10-6～1.0×10-4mol/L范围内呈线性关系,检出限为3×10-8mol/L(S/N=3).连续5次测定2.0×10-6mol/L ESL溶液的RSD为1.5%.     

Electroanalytical quantification of total dsDNA extracted from human sample using,an ionic liquid modified,carbon nanotubes paste electrode

Direct electrochemistry of dsDNA has been achieved by using an ionic liquid 1-butyl-4-methylpyridinium hexafluorophosphate modified carbon nanotubes paste electrode (IL-CNTPE). Oxidation peaks appeared at 0.93 and 1.26 V (vs. Ag/AgCl) on the IL- CNTPE after preconcentration of dsDNA in pH 5.0 acetate buffer, which were attributed to the oxidation of guanine and adenine residues on the dsDNA molecule structure. Based on the signal of guanine, under the optimal conditions, very low levels of dsDNA can be detected after 60 s accumulation with detection limits of 0.249 mg L⁻ 16 pM. Additionally, human DNA from a healthy volunteer is determined by use of the IL-CNTPE and it is found to be 40 ± 2, 14 pM.     

Voltammetric sensor for nitrite determination based on its electrocatalytic reduction at the surface of p-duroquinone modified carbon paste electrode

A p-duroquinone (tetramethyl-p-benzoquinone) modified carbon paste electrode (DMCPE) was employed to study the electrocatalytic reduction of nitrite in aqueous solutions using cyclic voltammetry (CV), double potential-step chronoamperometry, and differential pulse voltammetry (DPV). It has found that under an optimum condition (pH 1.00), the reduction of nitrite at the surface of DMCPE occurs at a potential of about 660 mV less negative than that of an unmodified carbon paste electrode (CPE). The catalytic rate constant, k′_h, based on Andrieux and Saveant theoretical model was calculated as for scan rate 10 mV s^-1. Also, the apparent diffusion coefficient, D _app, was found as 2.5 × 10^–10 and 3.61 × 10^–5 cm² s^-1 for p-duroquinone in carbon paste matrix and nitrite in aqueous buffered solution, respectively. The values for αn_α were estimated to be −0.65 and −0.19 for the reduction of nitrite at the surface of DMCPE and CPE, respectively. The electrocatalytic reduction peak currents showed a linear dependence on the nitrite concentration, and a linear analytical curve was obtained in the ranges of 5.0 × 10^–5 M to 8.0 × 10^–3 M and 6.0 × 10^–6 M to 8.0 × 10^–4 M of nitrite concentration with CV and DPV methods, respectively. The detection limits (2σ) were determined as 2.5 × 10^–5 M and 4.3 × 10^–6 M by CV and DPV methods. This method was also applied as a simple, selective and precise method for determination of nitrite in real samples (the weak liquor from the wood and paper factory of Mazandaran province in Iran) by using a standard addition method.     

芬苯达唑在石墨烯与[Bupy]PF_6复合修饰碳糊电极上的电化学性质及电分析方法研究

本文研究了芬苯达唑(Fenbendazole,FBZ)在石墨烯(RGO)与离子液体(N-丁基吡啶六氟磷酸盐)复合修饰碳糊电极上的电催化氧化及电化学动力学性质。同时用CC法(计时库仑法)、计时电流法(CA)测定FBZ在RGO-[Bupy]PF6/CPE上的电极反应动力学参数,并用方波伏安法(SWV)测定FBZ氧化峰电流(Ip)与其浓度c在4.0×10-8~1.0×10-5mol·L-1范围内呈良好线性关系,线性回归方程为Ip(μA)=1.471+5220.78c(10-3mol·L-1),R=0.9995,检测限(S/N=3)为1.4×10-9mol·L-1,在此基础上用SWV法对FBZ片剂中FBZ含量进行了电化学定量测定,RSD在0.2%~0.9%之间,回收率在99.0%~101.4%之间。     

Voltammetric sensor for glutathione determination based on ferrocene-modified carbon paste electrode

The electrocatalytic oxidation of glutathione (GSH) has been studied at the surface of ferrocene-modified carbon paste electrode (FMCPE). Cyclic voltammetry (CV), double potential step chronoamperometry, and differential pulse voltammetry (DPV) techniques were used to investigate the suitability of incorporation of ferrocene into FMCPE as a mediator for the electrocatalytic oxidation of GSH in buffered aqueous solution. Results showed that pH 7.00 is the most suitable for this purpose. In the optimum condition (pH 7.00), the electrocatalytic ability of about 480 mV can be found and the heterogeneous rate constant of catalytic reaction was calculated as . Also, the diffusion coefficient of glutathione, D, was found to be 3.61 × 10^–5 cm² s⁻¹. The electrocatalytic oxidation peak current of glutathione at the surface of this modified electrode was linearly dependent on the GSH concentration and the linear analytical curves were obtained in the ranges of 3.2 × 10^–5 M–1.6 × 10^–3 M and 2.2 × 10^–6 M–3.5 × 10^–3 M with cyclic voltammetry and differential pulse voltammetry methods, respectively. The detection limits (3σ) were determined as 1.8 × 10^–5 M and 2.1 × 10^–6 M using CV and DPV, respectively. Finally, the electrocatalytic oxidation of GSH at the surface of this modified electrode can be employed as a new method for the voltammetric determination of glutathione in real samples such as human plasma.     

Investigation of the Role of Ionic Liquids in Imparting Electrocatalytic Behavior to Carbon Paste Electrode

In this paper, a survey has been undertaken to clarify the possible reasons for the electrocatalytic activity obtained by the presence of ionic liquid in carbon paste electrode (CPE). For this purpose, the effect of the addition of traces of ionic liquid to conventional CPE was investigated. Fe(CN)₆^3?/4? was used as a probe and two ionic liquids, namely n‐octylpyridinum hexafluorophosphate and 1‐octyl‐3‐methylimidazolium hexaflourophosphate were tested for their electrocatalytic activity. The reasons for this electrocatalytic behavior were evaluated and it was found that different factors such as increase in the ionic conduction of the binder, decrease in the resistance of the modified electrode, increase in ion exchange properties of the electrode and the inherent catalytic activity of ionic liquids are responsible for the considerable improved electrochemical response obtained in the presence of traces of ionic liquid.     

Electrochemical behavior and voltammetric determination of metol using a multiwall carbon nanotubes modified electrode

Electrochemical behavior of metol, which coexists with p-benzeneiol (HQ) at a glassy-carbon electrode modified with multiwall carbon nanotubes (MWNT/GCE), is studied in the thesis. The results indicate that metol yields a well-defined peak of which two concomitant reductive peaks separate and the potential separation reaches to 178 mV, and that concomitant HQ has almost no interference with the reduction signal of metol. The values of the reductive peak current (I _pc) are found to be linearly related to metol concentration over the range of 8.0 × 10⁻² −1.0 × 10⁻⁵ M, with a detection limit of 5.0 × 10⁻⁶ M. Some common matter has no interference with the determination of metol. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 1, pp. 31–35. The text was submitted by the authors in English.     

Electrochemical behavior and differential pulse voltammetric determination of paracetamol at a carbon ionic liquid electrode

The electrochemical behavior of paracetamol in 0.1 M acetate buffer solution (pH 4.6) was investigated at a traditional carbon paste electrode (TCPE) and a carbon ionic liquid electrode (CILE) fabricated by replacing nonconductive organic binders with a conductive hydrophobic room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF₆). The results showed that the CILE exhibited better reversibility for the electrochemical redox of paracetamol. The oxidation potential of paracetamol at the CILE is +0.462 V, which is approximately 232 mV lower than that at the TCPE; the oxidation peak current response is nine times higher than that at the TCPE. The differential pulse voltammetric determination of paracetamol at the CILE was established based on this behavior. After optimizing several important parameters controlling the performance of paracetamol at the CILE, the oxidation peak current versus paracetamol concentration at the CILE showed linearity in the range from 1.0 μM to 2.0 mM (R ²  = 0.9992) with a detection limit of 0.3 μM (S/N = 3). The method has been applied to the determination of paracetamol in tablets and urine samples and the average recovery of paracetamol was 98.5% and 99.3%, respectively. The proposed CILE showed good sensitivity and reproducible response without influence of interferents commonly existing in pharmaceutical and urine samples. Figure CV curves of paracetamol illustrate the enhanced electrochemical behavior of paracetamol at the CILE (b), which forms the basis for the differential pulse voltammetric determination of paracetamol     

对乙酞氨基酚和色氨酸存在下采用改进的碳纳米管糊电极伏安法测定抗坏血酸(英文)

A carbon paste electrode (CPE) modified with carbon nanotubes and 5‐amino‐3’,4’‐dimethyl‐ bi‐ phenyl‐2‐ol (5ADB) is prepared. Under the optimum pH of 7.0, the oxidation of ascorbic acid (AA) on the modified CPE occurs at a potential about 280 mV less positive than that on the unmodified CPE. Some kinetic and thermodynamic parameters for electrocatalytic oxidation of AA, including electron transfer coefficient (α = 0.58) and diffusion coefficient (D = 2.2 × 10-6 cm2/s), are also determined. AA, acetaminophen (AC), and tryptophan (TRP) were detected simultaneously using the modified CPE. The peak potentials recorded using the modified CPE in phosphate‐buffered solution at pH 7.0 were 265, 465, and 780 mV for AA, AC, and TRP, respectively. The modified CPE was successfully used to determine the concentrations of AA, AC, and TRP in real samples.     

双氯芬酸钠在多壁碳纳米管修饰电极上的电化学行为及其应用

应用循环伏安法和线性扫描伏安法研究了双氯芬酸钠在多壁碳纳米管修饰电极上的电化学行为,建立了一种直接测定双氯芬酸钠的电分析方法.在0.1 mol/L HClO4溶液中,双氯芬酸钠的氧化峰电位在0.38 V(vs Ag/AgCl),峰电流与浓度在2.0×10-7 mol/L～7.0 × 10-6 mol/L范围内呈线性关系,开路富集3 min后检出限为9.0×10-8 mol/L.5×10-6 mol/L双氯芬酸钠溶液平行测定10次的相对标准偏差(RSD)为4.5%.已用于扶他林片剂中双氯芬酸钠的测定.     

嵌入式超薄碳糊电极的研究及其应用

在镍铬合金基体上,研制了一种新颖的嵌入式超薄碳糊膜电极。该电极可用作银离子的伏安测定。峰电流与Ag 离子浓度在1.0×10-10～1.0×10-6mol/L范围呈良好的线性关系,检出限为8.0×10-11mol/L。     

pHh-dependent permselectivity of the fibrinogen-modified carbon paste electrode

The modification of carbon paste matrices with fibrinogen is reported. The effect of the pH of the solution on the CV peak currents of positively or negatively charged redox analytes was examined at the fibrinogen-modified carbon paste electrode. In the presence of the coating, pH-dependent selectivity in electrochemical detection of charged species was demonstrated depending on the sign of the supported charge. Above the isoelectric pH attributed to the immobilized protein (5.5), the current response of anionic redox probes [Fe(CN)/Fe(CN)] was impeded while the response was almost totally restored below this pH. Opposite trends were observed with the Ru(NH₃)/Ru(NH₃) cationic redox analytes.     

硫脲在10-甲基吩噻嗪修饰碳糊电极上的电催化氧化及电分析方法研究

研究了硫脲(Thiourea,Tu)在10-甲基吩噻嗪修饰碳糊电极(MPT/CPE)上的电催化氧化行为.结果表明,Tu在裸碳糊电极(CPE)上的直接电化学氧化过程十分迟缓,MPT/CPE对Tu的电化学氧化具有良好的催化作用.用计时电流法(CA)测定了Tu在MPT/CPE上的电极过程动力学参数,测得电荷传递系数α=0.61,电催化氧化反应的速率常数k=(1.96±0.10)×104(mol/L)-1·s-1.用方渡伏安法(SWV)测得催化氧化峰电流与Tu浓度在1.0×10-6～8.0×10-3mol/L范围内呈良好的线性关系,线性回归方程为,Ips(μA)=10.836c(10-3mol/L)+5.326,R=0.9984,检出限为2.2×10-7mol/L(S/N=3).方法可用于Tu的电化学法测定.