Electrochemical behavior and determination of L-tryptophan on carbon ionic liquid electrode

A carbon ionic liquid electrode (CILE) was fabricated by mixing N-butylpyridinium hexafluoro-phosphate (BPPF ₆ ) with graphite powder and further used for the investigation on the electrochemical behavior of L-tryptophan (Trp). The fabricated CILE showed good conductivity, inherent electrocatalytic ability and strong promotion to the electron transfer of Trp. On the CILE, an irreversible oxidation peak appeared at 0.948 V (vs. saturated calomel reference electrode). For 5.0 × 10⁻⁵ M Trp the oxidation peak current increased about 5 times and the oxidation peak potential decreased on 0.092 V compared to carbon paste electrode. The results indicated that an electrocatalytic reaction occurred on CILE. The conditions for the electrochemical detection were optimized and the electrochemical parameters of Trp on CILE were carefully investigated. Under the selected conditions, the oxidation peak current showed linear relationship with Trp concentration in the range of 8.0 × 10⁻⁶ ∼1.0 × 10⁻³ M for cyclic voltammetry and the detection limit was estimated as 4.8 × 10⁻⁶ M (3σ). The interferences of other amino acids or metal ions on the determination were tested and the proposed method was successfully applied to the synthetic sample analysis.     

Electrochemical determination of paraquat using a glassy carbon electrode decorated with pillararene-coated nitrogen-doped carbon dots

An electrochemical sensor(carboxylatopillar[5]arene-coated nitrogen-doped carbon dots, namely CCDs)based on carboxylatopillar[5]arene(CP[5]) functionalized nitrogen-doped carbon dots(N-CDs) has been developed in a facile and economic manner. To improve the performance of this electrochemical sensor in pesticide detection, the optimal solution p H(p H 7) and loading amount of CCDs on the electrode(0.50 mg/m L) have been determined. By virtue of the good conductivity of N-CDs and the molecular rec...     

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.     

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     

离子液体BMIMPF6修饰碳糊电极电化学测定维生素E

用疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸([BMIM]PF6)作粘合剂制备了离子液体修饰碳糊电极(IL/CPE)。采用循环伏安法(CV)研究了维生素E(vitamin E,VE)的氧化产物生育酚红在IL/CPE和未修饰碳糊电极(CPE)上的电化学行为,结果表明生育酚红在IL/CPE上氧化过程更易于进行,峰电流响应ip也明显增加,表明IL/CPE对生育酚红的氧化还原反应具有良好的电催化作用。同时测定了电极过程的动力学参数:电荷转移系数α=0.8746,扩散系数D=1.65×10-3cm2/s,电极反应速率常数kf=6.64×10-2cm/s。采用方波伏安法(SWV)发现生育酚红氧化峰电流与其浓度在1.53×10-4mol/L～8.39×10-7mol/L范围内呈线性关系,检出限为1.58×10-8mol/L。该法可用于VE实际样品的分析测定。     

Voltammetric determination of mifepristone at a DNA-modified carbon paste electrode

A new strategy for the preparation of a DNA-modified carbon paste electrode is developed. It is found that the anodic response of mifepristone is greatly enhanced at the dsDNA-modified carbon paste electrode comparing with that obtained at the bare electrode, while the response at a ssDNA-modified electrode is similar to bare electrode. So the dsDNA-modified electrode is employed as a sensitive biosensor for the detection of mifepristone. A linear dependence of the peak currents on the concentration is observed in the range 2.0 x 10(-7) approximately 2.0 x 10(6) mol/L, with a detection limit of 1.0 x 10(-7) mol/L. The relative standard deviation is 4.3% for six successive determinations of 1.0 x 10(6) mol/L mifepristone. The determination of mifepristone tablets is carried out and satisfactory results are obtained.     

Sensitive determination of ATP using a carbon paste electrode modified with a carboxyl functionalized ionic liquid

We report on a new electrode for the determination of adenosine-5??-triphosphate (ATP). It is based on modified carbon paste electrode that contains an ionic liquid (IL) as the binder. The electrode shows strong electrocatalytic oxidative activity towards ATP at pH 4.5 in giving a well-defined single oxidation peak. The oxidation reaction is adsorption-controlled and due to the presence of the highly conductive IL. The electron transfer rate constant was calculated to be 2.04×10^?C3 s^?C1, and the surface coverage is 1.11×10^?C10 mol cm^?C2. Under the selected conditions, the oxidation peak current changes linearly with the concentration of ATP in the range from 5.0 to 1000???mol L^?1 and a detection limit of 1.67???mol L^?1 (3???) as determined by differential pulse voltammetry. The method displays good selectivity and was applied to the determination of ATP injection samples with satisfactory results.

Electrocatalytic determination of paraquat using a nafion film coated glassy carbon electrode

A nafion film coated glassy carbon electrode (NFGCE) was employed for the determination of paraquat. Paraquat was accumulated onto NFGCE by the cation-exchange feature of nafion at open circuit potential in basic medium followed by cathodic differential pulse voltammetric (CDPV) determination in a medium containing permanganate ions. The sensitivity for the determination of paraquat was improved through the electrocatalytic reduction of permanganate by the reduced paraquat. With 3-min accumulation, the analytical signal versus concentration dependence was linear from 1.0 to 100 ppb with a detection limit of 0.5 ppb. The interference from common metal ions was minimized by addition of ethylenediaminetetraacetate (EDTA) into the sample solution. The use of nafion also improves the resistance to interference from surfactants.     

双氯芬酸钠在石墨烯和室温离子液体复合修饰电极上的电化学行为及其测定

运用循环伏安法研究了双氯芬酸钠(DS)在石墨烯(Gene)和室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)复合修饰电极上的电化学行为。DS在该复合电极上于0.65V处有一不可逆氧化峰。在40～200 mV/s范围内,其氧化峰电流与扫描速率平方根(v1/2)呈良好线性关系,表明电极过程是受扩散控制。测定了部分电极过程参数,优化了方波溶出伏安法(SWSV)的实验参数,DS浓度在1.0×10-7～1.0×10-4mol/L范围内与峰电流Ipa呈良好线性关系,检出限为8.0×10-8mol/L(S/N=3),加标回收率为95.7%～101.7%。     

离子液体修饰电极上氧氟沙星的电化学行为及测定

制备了1-丁基-3-甲基咪唑六氟磷酸盐(BM IMPF6)室温离子液体修饰电极,用循环伏安法研究氧氟沙星在该修饰电极上的电化学行为,结果表明该电极过程受吸附控制。计算了电极过程的部分动力学参数:转移电子数n=2,电极有效面积A=0.0502 cm2。用方波溶出伏安法优化了测定参数,测定了浓度与峰电流ipa的线性关系,发现ipa与氧氟沙星浓度在5.0×10-7～6.0×10-5mol/L范围内呈线性关系,检出限为2.8×10-7mol/L,样品回收率为93.2%～108.2%,可直接用于实际样品中氧氟沙星含量的测定。     

Electrochemical determination of 8-hydroxydeoxyguanosine using a carbon nanotube modified electrode

In this work, a multi-wall carbon nanotube (MWNT) film-modified glassy carbon electrode (GCE) was constructed for the determination of 8-hydroxydesoxyguanosine (8-OHdG). The electrochemical behaviors of 8-OHdG were examined using cyclic voltammetry (CV) and linear sweep voltammetry (LSV), suggesting that MWNT film facilitates the electron transfer of 8-OHdG and then significantly enhances the oxidation peak current of 8-OHdG. Finally, a sensitive and simple electrochemical method with a good linear relationship in the range of 8.0 × 10⁻⁸ ∼ 5.0 × 10⁻⁶ mol 1⁻¹, was developed for the determination of 8-OHdG. The detection limit is 9.0 × 10⁻⁹ mol 1⁻¹ for 6-min accumulation. This newly-proposed method was successfully used to detect 8-OHdG in urine samples. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 3, pp. 351–356. The text was submitted by the authors in English.     

抗坏血酸在离子液体修饰玻碳电极上的电化学行为

利用离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)对玻碳电极(GCE)进行修饰,制备了BMI-MBF4/GCE电极.在0.1mol/L的磷酸盐缓冲溶液中,采用循环伏安法研究了抗坏血酸在BMIMBF4/GCE电极和裸玻碳电极(GCE)上的电化学行为.结果表明,pH=5.7的磷酸盐缓冲溶液为最佳测定底液,最佳富集时间为120s;BMIMBF4/GCE对抗坏血酸的氧化反应有很好的电化学催化作用.抗坏血酸的氧化峰电流与其浓度在2.0×10-4～1.0×10-2 mol/L的范围内呈良好的线性关系,相对标准偏差为4.53%(n=5).     

Electrochemical determination of malachite green using a multi-wall carbon nanotube modified glassy carbon electrode

A multi-wall carbon nanotube (MWNT) film-modified electrode is described for the determination of malachite green (MG). The electrochemical profile of MG was examined using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), suggesting that the MWNT film facilitates the electron transfer of MG in terms of a potential shift and then significantly enhances the oxidation peak current of MG. The experimental parameters, such as supporting electrolyte, thickness of MWNT film, scan rate and accumulation time, were optimized. Consequently, a sensitive and convenient electrochemical method is proposed for the determination of MG. The oxidation peak current is proportional to the concentration of MG over the range from 5.0 × 10⁻⁸ to 8.0 × 10⁻⁶ mol L⁻¹ obeying the following equation: i_p = 0.09 + 1.19 × 10⁷ C (r = 0.995, i_p in μA, C in mol L⁻¹). The detection limit is 6.0 × 10⁻⁹ mol L⁻¹ (signal to noise = 3) after 5 min of accumulation. Moreover, this method possesses good reproducibility (RSD is 5.6%, n = 8) as well as long-term stability. Finally, the new method was employed to determine MG in fish samples. Correspondence: W. Huang, Department of Chemistry, Hubei Institute for Nationalities, Enshi 445000, P.R. China     

Electrochemical determination of lead using bismuth modified glassy carbon electrode

Electrochemical application of bismuth film modified glassy carbon electrode was studied with the objective of lead detection. Bismuth film on glassy carbon substrate was formed in a plating solution of 2 mmol/L Bi(NO₃)₃, in 1 mol/L HCl at ?1.1 V (vs. Ag/AgCl) for 300 s. Lead was detected by differential pulse anodic voltammetry in acetate buffer of pH 5.0 in the concentration range of 7.5 nmol/L to 12.5 μmol/L. Factors influencing the anodic stripping performance, including deposition time, solution pH, Bi(III) concentration, potential, pulse amplitude, pulse width, have been optimized. Three linear calibration plots in the range 7.5 nmol/L to 0.1 μmol/L, 0.25 to 1 μmol/L, 2.5 to 12.5 μmol/L with regression coefficients of 0.991, 0.986 and 0.978 respectively were obtained. The theoretical detection limit equivalent to three times standard deviation for 7.5 nmol/L lead (n = 5) was calculated to be 5.25 nmol/L utilizing a 5 min deposition time and sensitivity 83.97 A L/mol. The sensitivity and detection limit of the method was compared with reported voltammetric methods for detection of lead and the result obtained was found to be promising for determination of lead.     

Electrochemical sensors for the simultaneous determination of zinc,cadmium and lead using a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode

A simple, low cost, and highly sensitive electrochemical sensor, based on a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode (N/IL/G/SPCE) was developed to determine zinc (Zn(II)), cadmium (Cd(II)), and lead (Pb(II)) simultaneously. This disposable electrode shows excellent conductivity and fast electron transfer kinetics. By in situ plating with a bismuth film (BiF), the developed electrode exhibited well-defined and separate peaks for Zn(II), Cd(II), and Pb(II) by square wave anodic stripping voltammetry (SWASV). Analytical characteristics of the BiF/N/IL/G/SPCE were explored with calibration curves which were found to be linear for Zn(II), Cd(II), and Pb(II) concentrations over the range from 0.1 to 100.0 ng L⁻¹. With an accumulation period of 120 s detection limits of 0.09 ng mL⁻¹, 0.06 ng L⁻¹ and 0.08 ng L⁻¹ were obtained for Zn(II), Cd(II) and Pb(II), respectively using the BiF/N/IL/G/SPCE sensor, calculated as 3σ value of the blank. In addition, the developed electrode displayed a good repeatability and reproducibility. The interference from other common ions associated with Zn(II), Cd(II) and Pb(II) detection could be effectively avoided. Finally, the proposed analytical procedure was applied to detect the trace metal ions in drinking water samples with satisfactory results which demonstrates the suitability of the BiF/N/IL/G/SPCE to detect heavy metals in water samples and the results agreed well with those obtained by inductively coupled plasma mass spectrometry.     

Modification of carbon electrode in ionic liquid through the reduction of phenyl diazonium salt. Electrochemical evidence in ionic liquid

Electrochemical reduction of the 4-nitrophenyl diazonium salt in ionic liquid media has been investigated at carbon electrode. The ionic liquid chosen for this study was 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The cyclic voltammetry study demonstrated the possibility of the electrochemical grafting of the nitrophenyl groups onto carbon electrode after the reduction of its corresponding diazonium in ionic liquid. The electrochemical characterization of the modified electrode achieved on ionic liquid displays the presence of the nitrophenyl group at the carbon surface. Moreover, the surface concentration of the attached group obtained in this media was found to be around 1.7 × 10⁻¹⁰ mol cm⁻², this value may suggest the possibility of the formation of monolayer. Furthermore, the characterization of the modified electrode in [EMIM][TFSI] showed the conversion of some NO₂-phenyl groups to NHOH-phenyl. This observation could indicate the presence of surface interaction between the reduced NO₂-phenyl and the ionic liquid cation, thanks to the presence of acidic proton in the ionic liquid cation.     

Electrochemical determination of hydroquinone using hydrophobic ionic liquid-type carbon paste electrodes

Three types of carbon paste electrodes (CPEs) with different liquid binders were fabricated, and their electrochemical behavior was characterized via a potassium hexacyanoferrate(II) probe. 1-Octyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) as a hydrophobic conductive pasting binder showed better electrochemical performance compared with the commonly employed binder. The IL-contained CPEs demonstrated excellent electroactivity for oxidation of hydroquinone. A diffusion control mechanism was confirmed and the diffusion coefficient (D) of 5.05 × 10^-4 cm² s^-1 was obtained. The hydrophobic IL-CPE is promising for the determination of hydroquinone in terms of high sensitivity, easy operation, and good durability.     

Highly sensitive determination of promazine in pharmaceutical and biological samples using a ZnO nanoparticle-modified ionic liquid carbon paste electrode

In this work we describe the first report for the determination of promazine using a nanostructuremodified ionic liquid carbon paste electrode in aqueous solutions. To achieve this goal, a novel modified carbon paste electrode using ZnO nanoparticles and 1-methyl-3-butylimidazolium bromide as a binder(ZnO/NPs/ILs/CPE) was fabricated. The oxidation peak potential of promazine at the surface of the ZnO/NPs/ILs/CPE appeared at 685 m V, which was about 65 m V lower than the oxidation potential at the surface of CPE under similar conditions. Also, the peak current was increased to about 4.0 times higher at the surface of ZnO/NPs/ILs/CPE compared to that of CPE. The linear response range and detection limit were found to be 0.08–450 and 0.04 mmol/L, respectively. The modified electrode was successfully used for the determination of promazine in real samples with satisfactory results.