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.     

Simultaneous determination of adrenaline,uric acid,and cysteine using bifunctional electrocatalyst of ruthenium oxide nanoparticles

In this study, ruthenium oxide nanoparticles were electrochemically deposited on the surface of a glassy carbon electrode (RuON-GCE). Electrochemical studies indicate that a modified electrode (RuON-GCE) plays the role of an excellent bifunctional electrocatalyst for the oxidation of adrenaline (AD) and uric acid (UA) in two different potentials. The charge transfer coefficient (α) and the heterogeneous charge transfer rate constant (k′) between the analytes and the electrodeposited nanoparticles were determined using cyclic voltammetry experiments. Through a different pulse voltammetric (DPV) method, the plot of the electrocatalytic current versus AD and UA concentrations emerged to be constituted of two linear segments with different sensitivities. Furthermore, the detection limits of AD and UA were estimated. In DPV, RuON-GCE could separate the oxidation peak potentials of AD, UA, and cysteine (Cys) present in the same solution though, at the bare GCE, the peak potentials were indistinguishable. Finally, the modified electrode activity was studied for the electrocatalytic determination of AD in an injection solution and UA in a human urine sample. The results were found satisfactory.     

Uracil Grafted Carbon Electrode:Electrocatalytic Behavior of Tryptophan,Tyrosine, Catecholamine and Related Compounds

基于尿嘧啶作为一种碱基,具备一定的分子识别能力,制备了一种新颖的尿嘧啶共价修饰电极,用X射线光电子能谱和电化学方法进行了表征,并研究了酪氨酸、色氨酸、儿茶酚胺（如多巴胺,肾上腺素,去甲肾上腺素）及相关的化合物尿酸、抗坏血酸在该电极上的电化学行为,获得相应的氧化电位、电流灵敏度、线性范围和检测限等信息。其中,色氨酸检测线性范围：1.8 - 120 mM,检测限（s/n=3）：0.8 mM;酪氨酸检测线性范围：1.8 - 89mM,检测限（s/n=3）：0.8 mM。实验表明,尿嘧啶修饰电极能催化氧化上述电活性物质,但催化能力不同,据此,我们讨论了尿嘧啶与上述物质的相互作用,详细探讨了催化机理,扩展了对基于分子识别的传感器的研究。     

2,2‐Bis(3‐Amino‐4‐hydroxyphenyl)hexafluoropropane Modified Glassy Carbon Electrodes as Selective and Sensitive Voltammetric Sensors. Selective Detection of Dopamine and Uric Acid

2,2‐bis(3‐Amino‐4‐hydroxyphenyl)hexafluoropropane (BAHHFP) was electro‐polymerized oxidatively on glassy carbon by cyclic voltammetry. The activity of the modified electrode towards ascorbic acid (AA), uric acid (UA) and dopamine (DA) was characterized with cyclic voltammetry and differential puls voltammetry (DPV). The findings showed that the electrode modification drastically suppresses the response of AA and shifts it towards more negative potentials. Simultaneously an enhancement of reaction reversibility is seen for DA and UA. Unusual, selective preconcentration features are observed for DA when the polymer‐modified electrode is polarized at negative potential. In a ternary mixture containing the three analytes studied, three baseline resolved peaks are observed in DPV mode. At physiological pH 7.4, after 5 min preconcentration at ?300 mV, peaks positions were ?0.073, 0.131 and 0.280 V (vs. Ag/AgCl) for AA, DA and UA, respectively. Relative selectivities DA/AA and UA/AA were over 4000 : 1 and 700 : 1, respectively. DA response was linear in the range 0.05–3 μM with sensitivity of 138 μA μM^?1 cm^?2 and detection limit (3σ) of 5 nM. Sensitive quantification of UA was possible in acidic solution (pH 1.8). Under such conditions a very sharp peak appeared at 630 mV (DPV). The response was linear in the range 0.5–100 μM with sensitivity of 4.67 μA μM^?1 cm^?2 and detection limit (3σ) of 0.1 μM. Practical utility was illustrated by selective determination of UA in human urine.     

Electropolymerization of Thin Film Conducting Polymer and Its Application for Simultaneous Determination of Ascorbic Acid,Dopamine and Uric Acid

In this paper electropolymerization of a thin film of para‐phenylenediamine (PPD) is studied at glassy carbon electrode (GCE) in sulfuric acid media by cyclic voltammetry. The results showed that this polymer was conducting and had a reproducible redox couple in the potential region from 0.0 to 0.4 V in phosphate buffer solution. This modified GCE (p‐PPD‐GCE) was applied for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) using differential pulse voltammetry (DPV). The p‐PPD‐GCE in 0.1 M phosphate buffer solution (pH 5.0) separated the DPV signals of AA, DA and UA with sufficient potential differences between AA–DA and DA–UA and also enhanced their oxidation peak currents. The oxidation currents were increased from 2.0 to 2000.0 µM for AA, 10.0 to 1250.0 µM for DA and 50.0 to 1600.0 µM for UA. The detection limits were evaluated as 0.4, 1.0 and 2.5 µM for AA, DA and UA, respectively (S/N=3).     

在抗坏血酸存在下用L-赖氨酸修饰玻碳电极测定多巴胺

采用电化学氧化法制备了L-广赖氮酸单分子层修饰玻碳电极,研究了多巴胺（DA）和抗坏血酸（AA）在该电极上的电化学行为。结果表明,L-广赖氨酸单分子层修饰玻碳电极不仅能改善多巴胺和抗坏血酸的电化学行为,而且能将多巴胺和抗坏血酸二者在裸电极上的完全重叠的单氧化峰分开成为两个完全独立的氧化峰,循环伏安（CV）图上峰间距为507mV,差分脉冲伏安（DPV）图上峰间距为460mV,由此可实现在AA的共存下对样品中的DA进行选择性测定。     

Preparation and characterization of PtAu hybrid film modified electrodes and their use in simultaneous determination of dopamine, ascorbic acid and uric acid

A novel biosensor was fabricated by electrochemical deposition of platinum and gold nanoparticles (nanoAu) with l-Cysteine on glassy carbon electrode. It was found that the nanoAu particle size distribution range was (50-80 nm), and the platinum particle size range was (200-300 nm). The hybrid film could be produced on gold and transparent indium tin oxide electrodes for different kind of studies such as electrochemical quartz crystal microbalance (EQCM), scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) and electrochemical studies. The PtAu hybrid film was applied to the electro catalytic oxidation of dopamine (DA), ascorbic acid (AA) and uric acid (UA) at pH 4.0 using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The modified electrode was quite effective not only to detect DA, AA and UA individually but also in simultaneous determination of these species in a mixture. The overlapping anodic peaks of DA, AA and UA were resolved into three well-defined voltammetric peaks in CV and DPV. The catalytic peak currents obtained from CV and DPV increased linearly with concentration. The relative standard deviation (% R.S.D., n = 10) for AA, DA and UA were less than 2.0% and DA, AA and UA can be determined in the ranges of 0.103-1.65, 0.024-0.384 and 0.021-0.336 mM, respectively. In addition, the modified electrode also shows good sensitivity, and stability. Satisfactory results were achieved for the determination of DA, AA and UA in dopamine injection solution, vitamin C tablets and human urine samples.     

电聚合烟酰胺制备电化学传感器：同时测定多巴胺、尿酸和抗坏血酸

用循环伏安法（CV）选择不同电位区间来电聚合烟酰胺（NA）得到了两种聚合物膜修饰电极：poly-niacinamide/GCE (poly-NA/GCE)和poly- nicotinic acid /GCE (poly-NC/GCE)。这两电极都具有显著电化学催化作用,能明显地降低多巴胺（DA）、尿酸（UA）和抗坏血酸(AA)的氧化过电位,并在混合溶液中使这些物质的氧化峰电位距离足够大,可进行三物质的同时测定。poly-NC/GCE的电催化性能更好一些,用差分脉冲伏安法（DPV）测定抗坏血酸,线性范围为75–3000 µmol L-1,电流灵敏度为5.6 mA•L•mol-1;测定多巴胺,线性范围为0.37 – 16 µmol L-1,电流灵敏度为1140 mA•L•mol-1; 测定尿酸,线性范围为0.74 – 230 µmol L-1,电流灵敏度为102 mA•L•mol-1。该电极具有很高的灵敏度、选择性和抗污染能力。     

Polystyrene sulphonate wrapped multiwalled carbon nanotubes modified graphite electrode for simultaneous determination of ascorbic acid, dopamine and uric acid

Graphite electrode is modified by casting multi-walled carbon nanotubes (MWCNTs) wrapped with polystyrene sulphonate (PSS) onto the surface of the bare graphite electrode. The modified electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The behavior of the modified electrode towards the oxidation of ascorbic acid (AA), dopamine (DA) and uric acid (UA) has been determined by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry (CA). The modified electrode showed better electrocatalytic activity towards AA, DA and UA compared to bare graphite electrode. The electrochemical oxidation signals of AA, DA and UA are well separated into three distinct peaks with peak potential difference of 222, 128 and 350 mV between AA-DA, DA-UA and AA-UA respectively in CV studies and corresponding peak potential separation in DPV are 228, 120 and 348 mV. This modified electrode was successfully used for simultaneous determination of AA, DA and UA in ternary mixture.     

Selective Detection of Uric Acid in the Presence of Ascorbic Acid and Dopamine Using Polymerized Luminol Film Modified Glassy Carbon Electrode

Electrochemically polymerized luminol film on a glassy carbon electrode (GCE) surface has been used as a sensor for selective detection of uric acid (UA) in the presence of ascorbic acid (AA) and dopamine (DA). Cyclic voltammetry was used to evaluate the electrochemical properties of the poly(luminol) film modified electrode. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) have been used for surface characterizations. The bare GCE failed to distinguish the oxidation peaks of AA, DA and UA in phosphate buffer solution (pH 7.0), while the poly(luminol) modified electrode could separate them efficiently. In differential pulse voltammetric (DPV) measurements, the modified GCE could separate AA and DA signals from UA, allowing the selective determination of UA. Using DPV, the linear range (3.0×10^?5 to 1.0×10^?3 M) and the detection limit (2.0×10^?6 M) were estimated for measurement of UA in physiological condition. The applicability of the prepared electrode was demonstrated by measuring UA in human urine samples.     

Electrocatalytic Oxidation and Simultaneous Determination of Uric Acid,Xanthine, Hypoxanthine and Dopamine Based on β-Cyclodextrin Modified Glassy Carbon Electrode

A novel covalently modified glassy carbon electrode with β-cyclodextrin was prepared via electropolymerization technique for the simultaneous determination of uric acid(UA), xanthine(XA), hypoxanthine(HX) and dopamine(DA). This new electrode presented an excellent electrocatalytic activity towards the oxidation of UA, XA, HX and DA by cyclic voltammetry(CV) method. The oxidation peaks of the four compounds were well defined and had the enhanced peak currents. The separation potentials of the oxidation peaks for DA-UA, UA-XA and XA-HX were 150, 390 and 360 mV in CV, respectively. By means of differential pulse voltammetry(DPV) method, the calibration curves in the ranges of 10-225, 5-105, 10-170 and 5-150 μmol/L were obtained for UA, XA, HX and DA, respectively. The lowest detection limits(S/N=3) were 5, 1.25, 5 and 1.5 μmol/L for UA, XA, HX and DA, respectively. The practical application of the modified electrode was demonstrated by the determination of DA in hydrochloride injection and UA, XA, HX in human urine samples.     

Fabrication of poly(orthanilic acid)–multiwalled carbon nanotubes composite film-modified glassy carbon electrode and its use for the simultaneous determination of uric acid and dopamine in the presence of ascorbic acid

A multiwalled carbon nanotubes (MWNT) modified glassy carbon electrode (GCE) coated with poly(orthanilic acid) (PABS) film (PABS–MWNT/GCE) has been fabricated and used for simultaneous determination of dopamine (DA) and uric acid (UA) in the presence of ascorbic acid (AA) by differential pulse voltammetry (DPV). Scanning electron microscopy, Fourier transform infrared spectra, and electrochemical techniques have been used to characterize the surface morphology of the PABS–MWNT composite film and the polymerization of ABS on electrode surface. In comparison with the bare GCE and the MWNT-modified GCE, the PABS–MWNT composite film-modified GCE, which combines the advantages of MWNT and the self-doped PABS, exhibits good selectivity and sensitivity for the simultaneous and selective determination of UA and DA in the presence of AA. Due to the different electrochemical responses of AA, DA, and UA, PABS–MWNT/GCE can resolve the overlapped oxidation peak of DA and UA into two well-defined voltammetric peaks with enhanced current responses using both cyclic voltammetry (CV) and DPV. The peak potential separations between DA and UA are 170 mV using CV and 160 mV using DPV, respectively, which are large enough for the selective and simultaneous determination of these species. In the presence of 0.5 mM AA, the DPV peak currents are linearly dependent on the concentration of UA and DA in the range of 6–55 and 9–48 μM with correlation coefficients of 0.997 and 0.993, respectively. The detection limits (S/N = 3) for detecting UA and DA are 0.44 and 0.21 μM, respectively. The PABS–MWNT/GCE shows good reproducibility and stability and has been used for the simultaneous determination of DA and UA in the presence of AA in samples with satisfactory results.     

Poly(m-ferrocenylaniline) modified carbon nanotubes-paste electrode encapsulated in nafion film for selective and sensitive determination of dopamine and uric acid in the presence of ascorbic acid

A nafion covered carbon nanotubes-paste electrode modified with poly(m-ferrocenylaniline), (Nf/p(FcAni)-CNTsPE), provides a novel voltammetric sensor for the selective determination of dopamine (DA) and uric acid (UA) in the presence of ascorbic acid (AA). We studied the electrochemical activity of Nf/p(FcAni)-CNTsPE toward DA, UA, and AA by differential pulse voltammetry (DPV). DA and UA anodic peaks appear at 0.30 and 0.45 V, respectively while an anodic peak for AA was not observed. DPV oxidation peak values are linearly dependent on DA concentration over the range 1–150 μM (r² = 0.992), and on UA concentration over the range 5–250 μM (r² = 0.997). DA and UA detection limits are estimated to be 0.21 and 0.58 μM, respectively. The modified electrode shows both good selectivity and reproducibility for the selective determination of DA and UA in real samples. Finally, the modified electrode was successfully applied for the determination of DA and UA in pharmaceutical or biological sample fluids.     

多巴胺在聚钙羧酸膜修饰碳糊电极上的电催化及与尿酸的同时测定

采用循环伏安法(CV)制备了聚钙羧酸(PCCA)膜修饰的碳糊电极(CPE)。考察了电极对多巴胺(DA)、尿酸(UA)的电氧化催化性能。结果显示,聚钙羧酸膜修饰碳糊电极(PCCA/CPE)对DA有良好的电催化效果,DA呈现出一对准可逆的氧化还原峰,氧化峰电流与DA浓度在3.0×10-7～1.0×10-4mol/L范围内呈线性关系,检出限为1×10-7mol/L(S/N=3)。使用微分脉冲伏安法(DPV),DA和UA在PCCA/CPE上的氧化峰能完全分离(ΔEp=192 mV),且峰电流与浓度均呈现良好的线性关系,可实现对DA和UA的同时测定。实验还进行了实际样品测定。     

Detection of Uric Acid in the Presence of Dopamine and High Concentration of Ascorbic Acid Using PDDA Modified Graphite Electrode

The properties of graphite electrode (Gr) modified with poly(diallyl dimethyl ammonium chloride) (PDDA) for the detection of uric acid (UA) in the presence of dopamine (DA) and high concentration of ascorbic acid (AA) have been investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The polymer modified graphite electrode was prepared by a very simple method just by immersing the graphite electrode in PDDA solution for 20 minutes. The PDDA/Gr modified electrode displayed excellent electrocatalytic activity towards the oxidation of UA, DA and AA compared to that at the bare graphite electrode. The electrochemical oxidation signals of UA, DA and AA are well resolved into three distinct peaks with peak potential separations of 220 mV, 168 mV and 387 mV between AA‐DA, DA‐UA and AA‐UA respectively in cyclic voltammetry studies and the corresponding peak potential separations are 230 mV, 130 mV and 354 mV respectively in differential pulse voltammetry. The lowest detection limits obtained for UA, DA and AA were 1×10^?7 M, 2×10^?7 M and 800×10^?9 M respectively. The PDDA/Gr electrode efficiently eliminated the interference of DA and a high concentration of AA in the determination of UA with good selectivity, sensitivity and reproducibility. The modified electrode was also successfully applied for simultaneous determination of UA, DA and AA in their ternary mixture.     

Application of 2-(3,4-dihydroxyphenyl)-1,3-dithialone self-assembled monolayer on gold electrode as a nanosensor for electrocatalytic determination of dopamine and uric acid

The electrooxidation of dopamine (DA), uric acid (UA) and their mixture on a gold electrode modified by a self-assembled monolayer of 2-(3,4-dihydroxyphenyl)-1,3-dithialone has been studied by cyclic voltammetry (CV), chronoamperometry and differential pulse voltammetry (DPV). CV was used to investigate the redox properties of the modified electrode at various scan rates and the apparent charge transfer rate constant (k(s)), and transfer coefficient (α) were calculated. The mediated oxidation of DA at the modified electrode under the optimum condition (pH = 7.0) in CV occurs at a potential about 220 mV less positive than that of the unmodified gold electrode. The values of electron transfer coefficients (α), catalytic rate constant (k) and diffusion coefficient (D) were calculated for DA, using electrochemical methods. DPV exhibited a linear dynamic range over the concentration range of 0.2-250.0 μM and a detection limit (3σ) of 0.07 μM for DA. The modified electrode was used for simultaneous determination of DA and UA by DPV. The results showed that the electrode is highly efficient for the catalytic electrooxidation of DA and UA, leading to a remarkable peak resolution (~350 mV) for two compounds. The electrode was used for the determination of DA in an injection sample.     

聚对氨基苯磺酸/石墨烯复合修饰电极对尿酸的选择性灵敏测定

采用电聚合方法在石墨烯纳米片(GN)的表面聚合一层聚对氨基苯磺酸(PABSA),制备了聚对氨基苯磺酸/石墨烯复合修饰玻碳电极(PABSA/GN/GCE)。研究了尿酸(UA)和抗坏血酸(AA)在该修饰电极上的电化学行为。与聚对氨基苯磺酸修饰电极(PABSA/GCE)及石墨烯单层膜修饰电极(GN/GCE)相比,复合修饰电极PABSA/GN/GCE显著提高了对UA和AA的检测灵敏度和分离度。在0.1 mol/L磷酸盐缓冲溶液(pH7.0)中,UA和AA的峰电位差达344 mV,表明PABSA/GN/GCE能实现对UA的选择性测定。UA的峰电流与其浓度呈良好的线性关系,线性范围为1.0×10-7～8.0×10-4mol/L,检出限为4.5×10-8mol/L。该复合修饰电极用于尿样中尿酸的测定,结果满意。     

Sensitive voltammetric determination of tyrosine using multi-walled carbon nanotubes/4-aminobenzeresulfonic acid film-coated glassy carbon electrode

A chemically modified electrode is constructed based on the multi-walled carbon nanotubes (MWNTs)/4-aminobenzeresulfonic acid (4-ABSA) film-coated glassy carbon electrode. The electrocatalytic oxidation of tyrosine (Tyr) is investigated on the surface of the MWNTs/4-ABSA-modified electrode using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The prepared modified electrode shows voltammetric responses with high sensitivity and selectivity for Tyr in optimal conditions, which makes it very suitable for sub-micromolar detection of Tyr. A sensitive oxidation peak at +0.64 V is employed to determine Tyr. Good linear relationship between the oxidation peak current and the Tyr concentration in the range of 1 × 10⁻⁷ to 5 × 10⁻⁵ mol/L is obtained in phosphate buffer solution with pH 7.0. By use of modified electrode, the voltammetric detection limit for Tyr in DPV measurements is 8 × 10⁻⁸ mol/L (S/N = 3). Good sensitivity, selectivity and stability of the low-cost modified electrode make it very suitable for the determination of trace amounts of Tyr in pharmaceutical and clinical preparations.     

电活化玻碳电极的制备及其对抗坏血酸、多巴胺、尿酸与亚硝酸盐的同时测定

在1.0 mol·L-1H_2SO_4溶液中,采用循环伏安法(CV)对玻碳电极(GCE)进行电化学处理,得到"活化"的玻碳电极(A-GCE)。在0.1 mol·L-1生理性磷酸盐缓冲溶液(PBS,p H 7.0)中,A-GCE不仅能很好地改善抗坏血酸(AA)、多巴胺(DA)、尿酸(UA)和亚硝酸根(NO_2~-)的电化学行为,而且能将四者的混合溶液在GCE上重叠的弱氧化峰分成4个灵敏的氧化峰,且相邻氧化峰(AA-DA、DA-UA、UA-NO_2~-)之间的电位差(ΔEpa)分别为0.16、0.15、0.45 V,表明A-GCE对AA、DA、UA和NO_2~-具有良好的电催化活性,可用于混合溶液中四者的同时分析。在优化的实验条件下,AA、DA、UA和NO_2~-的差分脉冲伏安(DPV)峰电流与其浓度分别在5~2 100、2~140、1~700、10~1 050μmol·L-1范围内呈良好的线性关系,相关系数分别为0.998 9、0.996 8、0.997 4和0.997 8,检出限分别为0.19、0.45、0.28、0.72μmol·L-1。将A-GCE应用于血清中AA、DA、UA和NO_2~-的同时电化学分析,结果满意。     

A New Sensor for Simultaneous Determination of Tyrosine and Dopamine Using Iron(III) Doped Zeolite Modified Carbon Paste Electrode

A new chemically modified electrode is constructed based on iron(III) doped zeolite modified carbon paste electrode (Fe³⁺Y/ZMCPE). The new sensor could be used for the simultaneous determination of the biologically important compounds dopamine (DA) and tyrosine (Tyr). The measurements are carried out using differential pulse voltammetric (DPV) method. The prepared modified electrode shows voltammetric responses of high sensitivity, selectivity and stability for DA and Tyr under optimal conditions, which makes it a suitable sensor for simultaneous trace detection of DA and Tyr in solution. Application of the DPV method demonstrates that in the Briton Robinson buffer solutions (pH=5) containing 50 µmol/L Tyr, there is a linear relationship between the oxidation peaks and the concentrations of DA over the range of 0.1–200 µmol/L, with a detection limit of 0.05 µmol/L (S/N=3). For Tyr a linear correlation between oxidation peak current and concentration of Tyr over the range of 0.5–200 µmol/L (containing 50 µmol/L DA), with a detection limit of 0.08 µmol/L is obtained. The analytical performances of this sensor are evaluated for the detection of DA and Tyr in human serum and a medicine.