金纳米颗粒在玻碳电极表面的固载及其对抗坏血酸的电催化氧化

采用电化学方法先在玻碳电极(GCE)表面共价键合一末端带有巯基的2-氨基乙硫醇(AET)单层,通过硫-金相互作用将金纳米颗粒(GNP)固载在玻碳电极表面,制备了GNP修饰的GNP-AET/GCE电极.采用X射线光电子能谱和循环伏安法对固载纳米金的玻碳电极的结构和性能进行表征.研究发现:GNP-AET/GCE电极不仅对抗坏血酸具有良好的催化性能,使其氧化过电位由玻碳电极上的0.53V负移到0.33V,氧化峰电流明显增加,而且能将多巴胺和抗坏血酸在玻碳电极上重叠的氧化波分成两个独立的氧化峰,峰间电位差为0.29V,提出了用差分脉冲伏安法在多巴胺共存在测定抗坏血酸的选择性方法.峰电流与抗坏血酸浓度在8.5×10-6～1.0×10-4 mol·L-1之间呈线性关系,其检出限为4.7×10-6 mol·L-1.     

聚L-精氨酸/纳米金修饰电极测定多巴胺

利用多电位脉冲沉积法制备纳米金修饰电极(AuNPs/GCE),再将L-精氨酸电聚合在AuNPs/GCE表面,制备出一种新型的聚L-精氨酸/AuNPs/GCE。采用原子力显微镜对上述电极进行了表征,并研究了多巴胺在其上的电化学行为。结果表明:在pH 5.7的磷酸盐缓冲溶液中,聚L-精氨酸/AuNPs/GCE对多巴胺的氧化有良好的电催化作用,多巴胺的氧化还原反应是受吸附控制的准可逆过程。多巴胺的浓度在8.0×10-7~1.0×10-4 mol·L-1范围内与其氧化峰电流呈线性关系,检出限(3S/N)为1.0×10-7 mol·L-1。加标回收率在96.5%~104%之间。对3.0×10-5 mol·L-1多巴胺溶液连续测定7次,峰电流的相对标准偏差为2.6%。     

聚对氨基苯磺酸/氧化石墨烯修饰电极同时测定多巴胺和抗坏血酸

用循环伏安法制备了聚对氨基苯磺酸/氧化石墨烯修饰玻碳电极(PABSA/GO/GCE),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,并建立了同时测定多巴胺和抗坏血酸电化学分析新方法,相对于裸玻碳电极,该电极测定DA和AA的峰电流明显增加。实验结果表明:在实验条件下,DA测定的线性范围为0.50～300μmol/L;检出限为5.0μmol/L。AA测定的线性范围是0.10～2.4 mmol/L,检出限为0.50μmol/L。     

聚钙羧酸修饰玻碳电极差分脉冲伏安法同时测定多巴胺和尿酸

采用电化学方法将钙羧酸(CCA)聚合修饰在玻碳电极(GCE)表面制备了聚钙羧酸指示剂修饰玻碳电极(PCCA/GCE),并用循环伏安法和交流阻抗法研究了电极的电化学性能。结果表明:在pH 6.0的磷酸盐缓冲溶液中,多巴胺(DA)和尿酸(UA)在聚钙羧酸修饰电极上的氧化峰得以分开,峰电位差为0.14V,据此提出了聚钙羧酸修饰电极差分脉冲伏安法同时测定多巴胺和尿酸的方法。DA和UA的浓度分别在5.0～43.8μmol.L-1和5.0～50.0μmol.L-1范围内与其氧化峰电流呈线性关系,检出限(3S/N)分别为0.2μmol.L-1和0.5μmol.L-1。方法可用于多巴胺注射液样品中DA和UA的测定,测定值的相对标准偏差(n=5)依次为2.43%和2.35%。     

基于辣根过氧化物酶/纳米金/L-半胱氨酸/聚邻氨基苯甲酸膜修饰的过氧化氢生物传感器

描述了测定过氧化氢的第三代电流型生物传感器。为了制备生物传感器，邻氨基苯甲酸（oABA）被电聚合到铂电极的表面形成具有抗干扰能力的静电排斥层。辣根过氧化物酶（HRP）通过纳米金（Nano-Au）的吸附固定到修饰了聚邻氨基苯甲酸及L-半胱氨酸的电极上。过氧化氢的测量是在相对于饱和甘汞电极的＋20 mV处进行的。修饰好的电极具有快速的响应，优秀的再现性和灵敏度，宽的线性范围和低的干扰水平等特点。我们研究了温度和pH对电极响应的影响及传感器的稳定性。在优化的条件下，传感器对过氧化氢的线性范围是2.99×10^-6到3.55×10^-3 mol/L，灵敏度和检测下限分别为0.0177 A•L^－1•mol^－1和4.3×10-7 mol/L（S/N＝3）。传感器不到10 s就可以达到响应的95％。     

盐酸吡哆辛在聚L-色氨酸修饰电极上的电化学行为及其分析测定

制备了聚L-色氨酸修饰玻碳电极(PTRP/GCE),用循环伏安法、线性单扫描伏安法、计时电量法等研究了盐酸吡哆辛(VB6)在PTRP/GCE上的电化学行为及电化学动力学性质, 实验表明：VB6在PTRP/GCE上的电极过程为1电子1质子的不可逆氧化反应,在20～400mV/s范围内,峰电流与扫速的平方根呈良好的线性关系,电极活化面积A为0.29cm2,扩散系数D为1.9612×10-4cm2/s。在pH=3的HAc-NaAc缓冲溶液中,VB6在PTRP/GCE电极上氧化峰电流与其浓度在1×10-4～5×10-6mol/L范围内呈良好的线性关系,线性回归方程为：ipa（μA） =7.7399+408.8129c (mmol/L),R=0.9931,检出限为1×10-6mol/L,VB6样品测定平均回收率为100.15%。     

银掺杂聚L-精氨酸修饰电极同时测定芦丁和抗坏血酸

用循环伏安法制备银掺杂聚L-精氨酸修饰玻碳电极(Ag-PA/GCE),研究了芦丁和抗坏血酸在该修饰电极上的电化学行为,建立了芦丁和抗坏血酸同时测定的新方法。在pH=2.5的磷酸盐缓冲溶液(PBS)中,于140mV·s-1的扫速下,芦丁产生一对氧化还原峰,其氧化峰电位为0.552V,还原峰电位为0.491V;抗坏血酸产生一个氧化峰,峰电位为0.281V。芦丁和抗坏血酸的△Epa=0.271V,用氧化峰不需分离可直接对芦丁和抗坏血酸进行同时测定,在最佳条件下,芦丁和抗坏血酸的线性范围分别5.0×10-7~2.0×10-5 mol·L-1和2.5×10-5~5.0×10-3 mol·L-1,检出限分别为1.0×10-7 mol·L-1和1.0×10-5 mol·L-1。方法可用于复方芦丁片中芦丁和抗坏血酸的同时测定。     

单壁碳纳米管Nafion复合膜修饰玻碳电极用于示差脉冲伏安法测定多巴胺

将单壁碳纳米管(SWCNT′s)分散在5%(质量分数)的Nafion溶液中并滴涂在玻碳电极表面,红外灯烘干后,制得了SWCNT′s/Nafion修饰电极。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,其氧化峰峰电位(Epa)为0.408 V(对Ag/AgCl电极,下同),还原峰峰电位(Epc)为0.335 V,且其峰电流与裸玻碳电极比较增大50倍。据此提出了用示差脉冲伏安法测定多巴胺的方法。多巴胺的浓度在120μmol.L-1以内与对应的氧化峰电流呈线性关系,检出限(3S/N)为0.2μmol.L-1。修饰电极用于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96.2%～101.0%之间。     

铜掺杂聚L-酪氨酸修饰电极同时测定尿酸、多巴胺和抗坏血酸

用循环伏安法制备铜掺杂聚L-酪氨酸修饰玻碳电极,研究了尿酸、抗坏血酸和多巴胺在修饰电极上的电化学行为,建立了同时测定尿酸、抗坏血酸和多巴胺的新方法.在pH 3.0磷酸盐缓冲溶液中,扫描速率为140 mV/s,多巴胺在修饰电极上产生一对氧化还原峰,峰电位分别为0.502 V、0.370 V,尿酸和抗坏血酸分别产生一氧化峰...     

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。     

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).     

Selective Determination of Dopamine in the Presence of Ascorbic Acid at Porous‐Carbon‐Modified Glassy Carbon Electrodes

Selective dopamine (DA) determinations using porous‐carbon‐modified glassy carbon electrodes (GCE) in the presence of ascorbic acid (AA) were studied. The effects of structure textures and surface functional groups of the porous carbons on the electrochemical behavior of DA was analyzed based on both cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements. The differential pulse voltammetry of DA on the modified GCE was determined in the presence of 400‐fold excess of AA, and the linear determination ranges of 0.05–0.99, 0.20–1.96, and 0.6–12.60 μM with the lowest detected concentrations of 4.5×10^?3, 4.4×10^?2, and 0.33 μM were obtained on the mesoporous carbon, mesoporous carbon with carboxylic and amino groups modified electrodes, respectively.     

RNA Modified Electrodes for Simultaneous Determination of Dopamine and Uric Acid in the Presence of High Amounts of Ascorbic Acid

A promising electrochemical biosensor was fabricated by electrochemical grafting of ribonucleic acid (RNA) at 1.8 V (vs. SCE) on glassy carbon electrode (GCE) (denoted as RNA/GCE), for simultaneous detection of dopamine (DA) and uric acid (UA) with coexistence of excess amount of ascorbic acid (AA). The electrode was characterized by X‐ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The RNA modified layer on GCE exhibited superior catalytic ability and anionic exclusive ability in comparison with the DNA modified electrode. Three separated anodic DPV peaks were obtained at 0.312, 0.168 and ?0.016 V for UA, DA and AA, respectively, at the RNA/GCE in pH 7.0 PBS. In the presence of 2.0 mM AA, a linear range of 0.37 to 36 μM with a detection limit of 0.2 μM for DA, and in the range of 0.74 to 73 μM with a detection limit of 0.36 μM for UA were obtained. The co‐existence of 5000 fold AA did not interfere with the detection of DA or UA. The modified electrode shows excellent selectivity, good sensitivity and good stability.     

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.     

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。     

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。     

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.     

柠檬酸修饰电极对抗坏血酸、多巴胺和尿酸的同时检测

研究柠檬酸(CA)修饰玻碳电极(CA/GC)在抗坏血酸(AA)、多巴胺(DA)和尿酸(UA)混合体系中的循环伏安(CV)行为.结果表明,AA、DA和UA在CA/GC电极上氧化峰电流增大,且三者氧化峰电位明显分离(ΔEp(DA,AA)=170 mV,ΔEp(DA,UA)=130 mV,ΔEp(AA,UA)=300 mV).据此,可同时检测AA、DA和UA.在优化的实验条件下,AA、DA和UA的氧化峰电流与其浓度分别在2.0×10-6～1.5×10-3mol.L-1,6.0×10-7～1.0×10-3mol.L-1和6.0×10-7～1.0×10-3mol.L-1范围内呈线性关系.该电极重现性好,可用于盐酸多巴胺针剂DA、VC片剂AA及人体尿液UA的测定.     

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.     

Differential Pulse Voltammetric Determination of Uric Acid on Carbon‐Coated Iron Nanoparticle Modified Glassy Carbon Electrodes

A carbon‐coated iron nanoparticles (CIN, a new style fullerence related nanomaterial) modified glassy carbon electrode (CIN/GCE) has been developed for the determination of uric acid (UA). Electrochemical behaviors of UA on CIN/GCE were explored by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). It was found that the voltammetric response of UA on CIN/GC was enhanced dramatically because of the strong accumulation effect of CIN and the large working area of the CIN/GC electrode. The parameters including the pH of supporting electrolyte, accumulation potential and time, that govern the analytical performance of UA have been studied and optimized. The DPV signal of UA on CIN/GCE increased linearly with its concentration in the range from 5.0×10^?7 to 2.0×10^?5 M, with a detection limit of 1.5×10^?7 M (S/N=3). The CIN/GCE was used for the determination of UA in samples with satisfactory results. The proposed CIN/GCE electrochemical sensing platform holds great promise for simple, rapid, and accurate detection of UA.