Co(salen)/Nafion修饰电极对天然海水中一氧化氮的催化氧化及其测定

用Co(salen)/Nafion修饰铂电极对天然海水介质中的一氧化氮进行了测定,在最佳实验条件下,确定了Co(salen)/Nafion修饰电极的检出限是0.1 μmol/L,线性范围分别为0.1～1.0和1.0～9.9 μmol/L,相对标准偏差为0.24%,并且探讨了Co(salen)对NO的催化机理.     

Amperometric determination of H2O2 at nano-TiO2/DNA/thionin nanocomposite modified electrode

We report electrochemical preparation and characterization of a new biosensor made of nanostructured titanium dioxide (nano-TiO(2)) particles and deoxyribonucleic acid (DNA). Thionin (TN) redox mediator was electrochemically deposited onto DNA/nano-TiO(2) modified glassy carbon electrode (GCE). The X-ray diffraction analysis, atomic force microscope (AFM) and scanning electron microscope (SEM) were used for surface analysis of TN/DNA/nano-TiO(2) film. In neutral buffer solution, TN/DNA/nano-TiO(2)/GCE biosensor exhibited excellent electrocatalytic activity towards the reduction of hydrogen peroxide (H(2)O(2)) and oxygen (O(2)). The biosensor shows excellent analytical performance for amperometric determination of H(2)O(2), at reduced overpotential (-0.2V). The detection limit and liner calibration range were found to be 0.05mM (S/N=3) and 0.05-22.3mM, respectively. In addition, determination of H(2)O(2) in real samples was carried out using the new biosensor with satisfactory results. The TN/DNA/nano-TiO(2)/GCE showed stable and reproducible analytical performance towards the reduction of H(2)O(2). This biosensor can be used as an amperometric biosensor for the determination of H(2)O(2) in real samples.     

溶胶-凝胶-钴-邻菲啰啉修饰电极对一氧化氮的电催化氧化及其测定

报道了溶胶 凝胶 钴 邻菲口罗啉膜修饰电极的制备方法及其在一氧化氮(NO)检测中的应用,采用循环伏安法(CV)研究修饰电极的电化学特性,差示脉冲伏安法(DPV)对NO进行检测。该修饰电极对NO的电化学氧化具有很好的催化作用,使其氧化电位负移了210mV,氧化峰电流与NO浓度在5.6×10-8～2.8×10-5mol/L范围内呈良好的线性关系,相关系数r=0.999,检测限为1.4×10-8mol/L,且生物体内常见的干扰物质如抗坏血酸、NO2-和儿茶酚胺类神经递质的代谢物等不干扰测定。     

Electrocatalytic oxidation of glucose at a Ni-curcumin modified glassy carbon electrode

The electrocatalytic oxidation of glucose was investigated on a nickel-basedchemically modified electrode (Ni(II)-curcumin) prepared by electropolymerization of Ni-curcumin complex (curcumin=1,7-bis[4-hydroxy-3-methoxyphenyl]-1,6-heptadiene-3,5-dione) in alkaline solution. Reaction kinetic and mechanism were investigated by using cyclic voltammetry (CV) and chronoamperometry (CA) techniques and steady-state polarization measurements. Cyclic voltammetry studies indicated that in the presence of glucose the anodic peak current of surface redox mediator was increased, followed by decrease in the corresponding cathodic current. This indicates that glucose was oxidized at the surface of this modified electrode. The results were explained based on the concept of electrocatalytic reactions that occur in this chemically modified electrode. The diffusion coefficient of glucose and the rate constant of the catalytic oxidation of glucose were found to be 6.7×10⁻⁶ cm² s⁻¹ and 6.5×10³ M⁻¹ s⁻¹, respectively. It has shown that by using the Ni-curcumin modified electrode, glucose can be determined with good response and low detection limit.     

聚L-赖氨酸修饰电极对去甲肾上腺素的电催化氧化

研究了L 赖氨酸在玻碳电极上电化学聚合的条件及修饰电极的电化学特性,发现该聚合膜对去甲肾上腺素(NE)的电氧化有显著的催化作用,在磷酸盐缓冲溶液(pH7)中,恒电位-0.2V富集2.0min后,用方波溶出伏安法对NE进行了测定,线性范围为1.0×10-8～5.0×10-4mol L,检出限(信噪比=3)为8 2×10-10mol L。对1.0×10-7mol LNE平行测定8次相对标准偏差为2 4%。     

苦参碱在多壁碳纳米管修饰玻碳电极上的电催化氧化及其电分析方法

研究了苦参碱(Matrine, MT) 在多壁碳纳米管修饰玻碳电极(MWCNT/GCE)上的电化学行为. 与GCE相比, MT在MWCNT/GCE上峰电位负移120 mV, 峰电流增大约2.5倍, 表明MWCNT/GCE对MT的电化学氧化具有良好的催化作用. 同时测定并计算了MT在MWCNT/GCE上的电极过程动力学参数: 电子转移系数α、电极反应速率常数ks、扩散系数D. 运用差分脉冲伏安法对苦参碱样品含量进行测定, 相对标准偏差为0.12%～2.9%, 加标回收率为98.4%～99.0%. 该方法可用于MT的电化学定量测定.     

多巴胺在牛磺酸修饰玻碳电极上的电化学行为及其分析应用

采用电化学聚合法制备了牛磺酸修饰玻碳电极,研究了多巴胺在聚牛磺酸修饰电极上的电化学行为,建立了测定痕量多巴胺的新方法.在pH 7.2的磷酸盐缓冲溶液中,多巴胺在修饰电极上产生一对灵敏的氧化还原峰,采用差分脉冲伏安法测定,其氧化峰电流与多巴胺浓度在8.0×10-8～1.0×10-4 mol/L范围内呈良好的线性关系,检出限为1.0×10-8 mol/L.     

二苯氨基碳酰肼在多壁碳纳米管修饰电极上的电催化氧化及电化学动力学研究

肼及其衍生物被广泛应用于医药,农药,水处理,军事,航天,光稳定剂以及化工生产助剂等诸多领域。因此对肼及其衍生物的研究有着极其重要的意义。二苯氨基碳酰肼(二苯氨基脲,又名二苯卡巴肼,D iphenyl Carbazide,DPC)广泛用于重金属离子的检测分析[1-4]。但是,目前关于DPC的电化学     

Electrocatalytic oxidation of methanol at platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes

<正>The electrocatalytic oxidation of methanol at the platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes (Eu-Fe film) was investigated for the first time by cyclic voltammetry.Compared with the bare platinum electrode,the results showed that the modified electrode had excellent electrocatalytic activity for the oxidation of methanol;the oxidation peak potential shifted more negatively and the peak current increased about twenty times.The electrooxidation of methanol at the modified electrode with Eu-Fe cyanide-bridged binuclear complexes material exhibited the better tolerance capacity to poison of intermediate species;the peak current was proportional to the concentration of methanol in the range of 0.5-2.0mol/L (R~2 = 0.9991,n =7),which was a comparatively wider linear range.Moreover,based on the linear relationship between the peak current and the square root of scan rate,electrocatalytic oxidation process of methanol was confirmed to be a diffusion control process.Furthermore,according to the counting of electron transfer number(n_α) in the rate-limiting step and the slope of linear equation between acidity of electrolyte and the oxidation peak potential(E_p),the possible mechanism of the electrooxidation of methanol at the modified electrode was primarily discussed.     

苯甲酰肼在多壁碳纳米管修饰玻碳电极上的电催化氧化及其电化学动力学性质

研究了苯甲酰肼(BH)在MWCNT/GCE上的电化学行为。实验结果表明,BH在GCE上的直接电化学氧化十分迟缓,无氧化峰出现,但在MWCNT/GCE上BH在0.20 V处出现了一个不可逆氧化峰,且峰电流大幅度增大,表明MWCNT/GCE对BH电化学氧化具有良好的催化作用。同时用计时库仑法(Chro-nocoulometry,CC)和计时电流法(Chronoamperometry,CA)测定了电极过程动力学参数:扩散系数D=8.73×10-5cm2.s-1,电子转移系数α=0.85,电极反应速率常数kf=1.45×10-3s-1。稳态电流-时间实验结果表明,电流响应信号随其浓度成比例增长,响应时间小于6 s,最低响应浓度为1×10-6mol/L。该方法可用于BH电化学定量测定。     

Electrocatalytic oxidation of NADH at glassy carbon electrodes modified with an electropolymerized film of nile blue A

The kinetic parameters for the electrocatalytic oxidation of di-hydronicotiamide adenine dinucleotide (NADH) at glassy carbon electrodes modified with an electropolymerized film of nile blue A (PNB) have been determined based on rotating disk electrode measurements. The rate constant for the chemical reaction between NADH and PNB is strongly influenced by NADH concentration and the pH value of solution, and it decreases with increasing NADH concentration, indicating that the electrocatalytic process proceeds via the formation of an intermediate of charge-transfer complex between NADH and PNB.     

Determination of nitrite with a nano-gold modified glassy carbon electrode by cyclic voltammetry

Abstract

Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) was employed to determine the concentration of rare earth elements (REEs) in plants and soils. Sample preparation and analytical conditions were investigated to set up a simple routine procedure for measuring rare earth elements. For prompt sample decomposition, a microwave digestion technique was successfully used with an acid mixture of HCl+HNO₃+HF. Detection limits, reproducibility, accuracy and possible interference were also studied. ICP-MS provided extremely low detection limits for REEs (0.6–6ng/l). Precision was typically better than 6% RSD (relative standard deviation) for soil and 10% for plant. The potential of the method was evaluated by analysis of standard reference materials of soils and plants. A good agreement between the experimental results and certified values was observed. The spectroscopic interference of Ba with Eu and light REEs(LREEs, La-Eu) with heavy REEs(HREEs, Gd-Lu) were eliminated by the algebra correction.

The results suggested that REEs in soil samples existed mainly as light REEs, and the same concentration distribution patterns of Oddo-Hakins law were observed, showing negative gradient from La to Lu concentrations. The REE contents in plants were very low, less than 20μg/g and varied with plant species. Apart from rape leaf(Brassica juncea), the REE distribution patterns in other plant leaves were consistent with soils, indicating that these plants generally absorbed REEs from soil without selectivity. Rape leaf showed selective absorption for LREEs, especially for La. The REE concentration distribution in parts of hot pepper(Capsicum annuum) was characteriaed by root>leaf>stem>fruit. The REEs absorbed by hot pepper concentrated mainly in roots and leaves, very little migrated into fruit. Transfer factors(TFs) of REEs in plants were very low. Although the contents of LREEs were relatively more than those of HREEs, no distinct difference of TFs between LREEs and HREEs was observed, meaning that LREEs and HREEs have the same abilities of transportation. However, for rape leaf, the TFs of LREEs were one or two orders of magnitude higher than those of HREEs.     

碳纳米管-TiO_2修饰电极伏安法测定维生素K_3

利用碳纳米管、二氧化钛两种纳米材料制成碳纳米管-TiO2复合膜修饰电极,进行了维生素K3电化学行为的研究。维生素K3在碳纳米管-TiO2复合膜修饰电极的电化学响应优于碳纳米管修饰电极,表明前者具有更好的催化作用。通过条件实验的优化,结果表明维生素K3在pH=9.42的氨水-NH4Cl底液中,富集时间为10s,富集电位于-0.60V,扫描速度为0.1V/s时有稳定的灵敏的氧化还原峰。峰电流与维生素K3浓度在3.0×10-6～8.0×10-5mol/L范围内呈良好的线性关系,检出限为5.0×10-7 mol/L。考查了修饰电极的重现性,5次平行测量的RSD为1.78%。该方法用于片剂药品中维生素K3含量的测定,回收率在97.5%～102%之间。     

肾上腺素在对氨基苯磺酸修饰玻碳电极上的电化学行为

采用电化学聚合法首次制备了对氨基苯磺酸修饰玻碳电极。实验表明,该修饰电极对肾上腺素(EP)有明显的电催化特性。在pH 7.6的磷酸盐缓冲溶液(PBS)中,抗坏血酸(AA)和EP在修饰电极上的电位分别为-0.124 V和0.192V。电位差达到300 mV,且在高浓度的AA的存在下可以实现对EP的测定。EP在该电极上检测的线性范围是5.0×10-7~1.0×10-4mol/L,检出限为3.6×10-8。此法已用于针剂样品的测定。     

一氧化氮在Nafion—钴席夫碱膜修饰电极上的电催化氧化及其测定

将一种杂环席夫碱N,N′－2,6－二乙酰吡啶缩双苯胺和Nafion修饰在铂电极上,然后与钴（Ⅱ）反应,得到Nafion－钴席夫碱膜修饰电极。实验结果表明,该修饰电极具有良好的机械、化学和电化学稳定性,对生物分子一氧化氮的电化学氧化有显著的催化作用。以1.5次微分线性扫描伏安法测定一氧化氮,当浓度在2.8×10     

CeO2纳米晶包裹碳纳米管修饰电极对特布他林的电催化测定

制备出CeO2纳米晶包裹碳纳米管修饰玻碳电极,并运用循环伏安法、交流阻抗谱探讨了该电极的电化学特性。研究了特布他林在该修饰电极上的直接电化学行为。实验结果表明,特布他林在该修饰电极上具有良好的电流响应,与裸玻碳电极相比在pH 7.0缓冲溶液中氧化峰电位负移314 mV。采用计时电流法测定特布他林,其氧化峰电流与浓度在5.0×10-7~1.0×10-4mol/L范围呈良好线性关系,线性方程为:Ip(μA)=4.952-0.04724c(μmol/L),线性相关系数为0.9920,检出限为5.0×10-8mol/L(信噪比为3)。该电极已用于特布他林片剂中特布他林的测定。     

肾上腺素在对甲苯磺酸修饰电极上的电化学行为

研究了对甲苯磺酸在玻碳电极上电化学聚合的条件及修饰电极的电化学特性, 发现该聚合膜对肾上腺素的电氧化有显著的催化作用, 在pH 7.0的磷酸盐缓冲溶液中, 搅拌富集40 s后, 用循环伏安法对肾上腺素进行了测定, 线性范围: 4.05×10-7～9.45×10-6 mol/L, 检出限为3.2×10-8 mol/L. 对2.0×10-6 mol/L肾上腺素平行测定7次相对标准偏差为2.4%. 该电极有效地排除了抗坏血酸的干扰, 具有良好的稳定性和重现性.     

对硝基苯酚在铕离子掺杂类普鲁士蓝化学修饰玻碳电极上的电化学行为及分析测定

利用电化学沉积法制备了稀土Eu(Ⅲ)离子掺杂的类普鲁士蓝化学修饰玻碳电极,与裸玻碳电极相比,该修饰电极使对硝基苯酚的还原电位大大降低,峰电流显著增大,线性范围明显变宽。讨论了酸度、沉积量、扫速、底液等条件对对硝基苯酚在修饰电极上催化还原的影响。分别用循环伏安法和示差脉冲伏安法进行定量分析,对硝基苯酚的还原电流与浓度在2.0×10-5~2.0×10-3mol/L和2.0×10-7~8.0×10-6mol/L范围内呈良好的线性关系,检出限(3σ)为6.0×10-8mol/L。该电极可用于环境水样检测。