聚次甲基蓝-多壁碳纳米管修饰玻碳电极测定叶酸

利用电聚合方法制备了聚次甲基蓝/多壁碳纳米管修饰玻碳(PMB/MWCNTs/GC)电极,该修饰电极对叶酸(FA)具有良好的电催化作用。结果表明,在最佳实验条件下,叶酸在-0.51V处的还原峰电流与其浓度在3.4×10-6～1.1×10-4 mol/L之间呈良好线性关系,检出限为1.6×10-6 mol/L。用标准加入法做了回收实验,回收率在90.8%～101%之间。该电极制备简单,有良好的稳定性。     

聚甲苯胺蓝-(多壁碳纳米管/PDDA)n杂化膜修饰电极的制备及其对NADH的催化氧化

导电聚合物修饰电极由于聚合物结构致密,限制了底物在聚合物膜中的渗透,且随着膜厚的增加其导电能力逐渐减弱.碳纳米管在导电聚合物中的掺杂明显改善了导电聚合物的导电性~([1]).但是碳纳米管的水溶性差及纳米尺寸带来的聚集效应,使得通过主体聚合制备杂化膜的过程中容易出现相分离进而影响到杂化膜的性质~([2]).     

普鲁士蓝-多壁碳纳米管复合材料修饰电极测定过氧化氢

利用电化学方法在多壁碳纳米管(MWCNT)修饰的玻碳电极表面聚合一层普鲁士蓝(PB)(PB/MWCNT/GCE),制备了一种新型的过氧化氢(H2O2)传感器。研究了该传感器对H2O2的电催化作用。讨论了支持电解质种类、酸度、修饰层厚度、电位和扫速等对H2O2响应的影响。研究表明,该传感器在以1.0mol/L KCl为支持电解质的磷酸盐溶液(pH=2.0)中,对H2O2具有明显的催化效应,测定的线性范围变宽,在2.9×10-6~8.8×10-2mol/L范围内还原峰电流与H2O2的浓度呈良好的线性关系,相关系数为0.9949;检出限为1.4×10-6mol/L。该电极用于医用消毒水中H2O2的测定,结果令人满意。     

普鲁士蓝/多壁碳纳米管修饰电极测定维生素C

利用电化学方法在多壁碳纳米管修饰的玻碳电极表面聚合一层普鲁士蓝,制备普鲁士蓝/多壁碳纳米管修饰玻碳电极,运用循环伏安法研究了维生素C(vc)在该修饰电极上的电化学行为.该修饰电极对Vc显示出快速的电化学响应和较好的电催化活性,在pH为4.0的磷酸盐溶液中,Ve浓度与其氧化峰电流在8.0×10-4～1.0×10-2 mol/L范围内呈现良好的线性关系,相关系数为0.9993,检测限为6.4×10-5mol/L.该电极具有较好的稳定性和重现性.     

多壁碳纳米管-聚茜素红膜修饰电极测定多菌灵

制备了多壁碳纳米管-聚茜素红膜(MWNT-PAR)修饰电极,用循环伏安法和线性扫描伏安法、计时电量法等研究多菌灵在修饰电极上的电化学行为.结果表明,多菌灵在MWNT-PAR修饰电极上是扩散控制的不可逆电氧化过程.实验测定了部分电极过程参数,并发现多菌灵氧化峰电流的一阶导数值与其浓度在5.0×10~(-6)～1.0×10~(-4) mol/L范围内呈线性关系,回归方程为:I_p ′(A)=-3.112×10~(-6)-1.198c(mol/L),R=-0.9953,其检出限为2.0×10~(-7) mol/L,回收率为99.0%～105.6%.     

阿魏酸聚合修饰玻碳电极的制备及其对NADH的催化氧化

研究了阿魏酸修饰电极的制备、性质及对NADH的电催化作用.该电极在0.1mol/L磷酸缓冲溶液(pH=6.60)中,于-0.1～+0.50V(vs.Ag/AgCl)电位范围内呈现一对氧化还原峰,其式量电位E₀为+0.188V(vs.Ag/AgCl),且E₀随pH增加而负向移动.电子转移系数为0.496,表观电极反应速率常数(ks)为6.6s^-1.电极反应的电子数为1且有1个质子参与.该修饰电极对NADH氧化具有很好的催化作用.在NADH存在下,电极过程由扩散控制,扩散系数为1.76×10^-6cm²/s.NADH浓度在0.01～5.0mmol/L范围内与峰电流呈现良好的线性关系.通过计时安培法测得催化速率常数为6.82×10³mol^-1·L·s^-1.     

百里香酚在聚甲苯胺蓝/多壁碳纳米管修饰电极上的电催化氧化动力学研究

采用电聚合、滴涂及多层修饰方法制备了4种修饰电极,百里香酚在几种修饰电极上均是不可逆电氧化反应,其中聚甲苯胺蓝/多壁碳纳米管修饰电极的电催化效果最佳,过电位降低了111mV,氧化峰电流增大了5倍。在pH为7.69的PBS溶液中,百里香酚在聚甲苯胺蓝/多壁碳纳米管修饰电极上是电子转移数和质子数均为1的扩散控制不可逆电氧化过程,扩散系数D=4.8470×10-4cm2/s,电极有效面积A=0.0383cm2。氧化峰电流ip与浓度c在9.0×10-6～5.0×10-4mol/L范围内呈良好的线性关系:ip(A)=-3.781×10-5-0.0491c(mol/L),相关系数R=-0.9958,样品测定回收率为96.88%～101.50%。     

电催化测定烟酰胺腺嘌呤二核苷酸——以聚亚甲基蓝一碳纳米管修饰电极作为工作电极

制备了聚亚甲蓝一碳纳米管修饰的玻碳电极(PMB-SWCNT's/GCE),并研究了烟酰胺腺嘌呤二核苷酸(NADH)在此电极上的电化学行为.结果表明:此修饰电极对NADH表现出协同电催化作用和较好的响应性能.在pH 7.0的磷酸盐缓冲溶液中可观察到NADH氧化峰电位的正移及其峰电流的增加,当NADH的浓度在5.0×10-6～7.0×10-4mol·L-1范围内,与相应的氧化峰电流值之间存在线性关系.方法的检出限(3S/N)为1.4×10-6mol·L-1,所提出的方法应用于生物材料样品中NADH的直接测定,测得方法的平均回收率为99.5%.     

多壁碳纳米管固载亚甲基蓝复合膜修饰玻碳电极测定己烯雌酚

提出了多壁碳纳米管-聚亚甲基蓝(MWNT/PMB)复合膜修饰玻碳电极检测己烯雌酚(DES)的方法,考察了缓冲液、pH、扫描速度等实验参数对测定的影响。在0.2 mol/L的磷酸缓冲液(pH7.0)中,DES在复合膜电极上出现了一个明显的氧化峰,峰电位在0.197 V处。与裸电极相比较,修饰后的电极能显著提高DES的氧化峰电流并降低其氧化电位,表明MWNT/PMB复合膜对DES有电催化作用。峰电流与己烯雌酚浓度在3.73×10-11~3.73×10-8mol/L范围内呈线性关系,检出限为2×10-11mol/L;用此法对己烯雌酚药片的含量进行了测定,测定结果与标示相符。     

1,2-萘醌修饰的碳纳米管对β-烟酰胺腺嘌呤二核苷酸电化学氧化的催化作用

将具有电活性的1,2-萘醌(1,2-naphthoqu inone,Nq)分子修饰到碳纳米管(CNT)表面形成Nq-CNT纳米复合体,用紫外可见(UV-V is)和红外光谱等方法对Nq-CNT进行了表征,结果表明Nq不仅能快速、有效地修饰到CNT表面,而且还能有效地改善CNT在水溶液中的分散性能。循环伏安结果显示,与GC电极相比,CNT能显著提高Nq的氧化还原峰电流,其伏安曲线上表现出一对几乎对称的氧化还原峰,式量电位E0′几乎不随扫速而变化。进一步的实验结果表明,Nq和CNT对β-烟酰胺腺嘌呤二核苷酸(NADH)的电化学氧化具有协同催化作用,与CNT或Nq相比,Nq-CNT具有较高的电催化活性,能使其氧化过电位降低超过510 mV。本研究对碳纳米管功能化方法具有简单、电极制作容易以及催化效率高等优点。     

Sensitive Detection of NADH by Ferrocenylalkanethiol Functionalized Multiwall Carbon Nanotubes Electrodes

Abstract

The 6-ferrocenylhexanethiol (FcC₆SH) functionalized multiwall carbon nanotubes (MWNTs) modified glassy carbon electrode (FcC₆SH/MWNTs/GCE) was easily fabricated and used for the sensitive detection of NADH. Cyclic voltammetric and amperometric methods were used to study the behavior of NADH on the FcC₆SH/MWNTs/GCE. A broader linear response range to the NADH concentration from 5 µM to 1.5 mM with a correlation coefficient of 0.9982 was obtained. The detection limit was 0.54 µM. The synergetic effects of FcC₆SH and MWNTs make the modified electrode highly sensitive to NADH. In addition, the modified electrode can decrease the fouling of the electrode surface.     

烟酰胺腺嘌呤二核苷酸的聚亚甲基蓝/单壁碳纳米管修饰电极差分脉冲伏安法检测

研究了聚亚甲基蓝/单壁碳纳米管修饰电极的制备、电化学性质,采用差分脉冲伏安法成功应用于烟酰胺腺嘌呤二核苷酸(NADH)的测定.在实验条件下,该修饰电极对NADH氧化具有很好的电催化作用,NADH浓度在2.0～500靘oL/L范围内与峰电流呈良好的线性关系,检出限为0.6 靘ol/L,结果令人满意.     

Direct Modification of a Glassy Carbon Electrode with Toluidine Blue Diazonium Salt: Application to NADH Determination and Biosensing of Ethanol

We describe here the covalent modification of a glassy carbon electrode with toluidine blue (TB) diazonium salt, which is generated in situ from the reaction between the aromatic amino phenyl group of TB and sodium nitrite. TB is attached directly to the electrode surface without any cross‐linking agent or complex matrices. The resulting TB films exhibit excellent electrocatalytic behavior toward NADH oxidation. Low potential detection of NADH is performed at 0.15 V vs. Ag/AgCl. Furthermore, an ethanol biosensor is developed using the TB modified electrode and alcohol dehydrogenase. The great stability and reusability, excellent electrochemical reversibility, technically simple preparation and short preparation time make this method suitable for low‐cost bioelectronical devices.     

层层自组装法制备碳纳米管/酶多层膜电极及其检测酚类物质

将十二烷基硫酸钠（SDS）分散的碳纳米管(CNTs)和辣根过氧化物酶(HRP)通过层层组装方法构筑HRP多层膜酶电极,并将其用于酚类物质的分析检测研究。紫外-可见光谱表明,SDS分散的CNTs可与HRP均匀有效地组装构筑多层酶膜。电化学研究表明,CNTs的引入很好地提高了HRP电极的灵敏度;随着CNTs/HRP组装层数的增加,电极的电化学响应增加。研究结果表明该HRP电极对酚类物质（邻苯二酚、对苯二酚和苯酚）的分析检测具有宽的线性范围、好的灵敏度和抗干扰性。     

Electrochemical Reaction Mechanism of Phenacetin at a Carboxylated Multiwall Carbon Nanotube Modified Electrode and Its Analytical Applications

A novel type of carboxylated multiwalled carbon nanotube modified electrode（c-MWCNTs/GCE） was constructed and the electrochemical properties of phenacetin（PHE） at it were studied. In a buffer solution of 0.1 mol/L HAc-NaAc（pH=5.3）, PHE exhibited a couple of quasi-reversible redox peaks and an anodic peak in the poten- tial range of 0.2--1.2 V at c-MWCNTs/GCE. The peak current was proportional to the concentration of PHE in the range of 4.0× 10^-6_ 1.0 × 10^-4 mol/L with a detection limit of 1.0× 10^-6 mol/L（S/N=3）. The c-MWCNTs/GCE showed excellent repeatability and stability and the electrochemical reaction mechanism of PHE was proposed. This method was used to determine the content of PHE in medical tablets and the recovery was determined to be 96.5%--104.2% by means of a standard addition method.     

Direct Electrochemical Oxidation of Dihydronicotiamide AdenineDinucleotide （NADH） at An Ordered Carbon Nanotubes Electrode

With novel structure, extraordinary electronic properties, high chemical stability and extremely high mechanical strength1, carbon nanotubes (CNTs) have found a wide range of potential applications2-6. The subtle electronic properties suggest that CNTs have the ability to promote electron transfer when they are used as an electrode. The disordered CNTs have been used to fabricate electrode7-10. Thus, it is very interesting to fabricate the electrode using the ordered CNTs and to examin…     

Electropolymerization of Acid Chrome Blue K on Glassy Carbon Electrode for the Determination of Curcumin

Acid chrome blue K (ACBK) was electropolymerized on the surface of a glassy carbon electrode (GCE) by cyclic voltammetric sweep in the potential range from –0.2 to 0.9 V. The characteristic of poly‐ACBK film was studied by different methods such as electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. This modified electrode showed excellent electrocatalytic response to curcumin with the increase of the electrochemical responses. Under the optimal conditions a good linear voltammetric response could be obtained over the range of 1.0 × 10^?7‐7.0 × 10^?5 M and the detection limit was got as 4.1 × 10^?8 M (S/N = 3). The method was successfully applied for the determination of curcumin in human urinev samples.     

Electrochemical Polymerization of Azure Blue II and Its Electrocatalytic Activity toward NADH Oxidation

IntroductionOver 30 0dehydrogenasesareknowntobedependentonthenicotiamideadeninedinucleotidecoenzymeinitsreduced (NADH )andoxidized (NAD+)forms ,andamonitoringofenzymaticallygeneratedNADHisthebasisforthedevelopmentofbiosensorsfortheselecteddehydro genase .Hence ,thedetectionofthiscoenzymeisimpor tantinbothpracticalanalysisandbiochemicalsynthesis .ThereportedoverpotentialforoxidationofNADHatpH7 0isabout 1 1Vatcarbonand 1 3Vatplatinumelec trodes .1,2 Itisgenerallyacceptedthatthedirecto…     

甲苯胺蓝修饰石墨电极的电化学性质及对血红蛋白的电催化还原

本文将电子媒体甲苯胺蓝吸附在石墨电极上制备成修饰电极。在＋０．２～０．５Ｖ（ｖｓ．ＳＣＥ）范围内，吸附态的甲苯胺蓝呈现有两质子参与的可逆性两电子氧化还原行为，在ｐＨ５．５醋酸盐缓冲溶液中，其表面式量电位Ｅ＾０为－０．２２Ｖ，表观表面电子传递速率常数ｋ为１．１Ｓ＾－１，甲苯胺蓝修饰电极具有良好的稳定性，它能加速血红蛋白在固体电极上的电子传递，产生很好的电流响应。     

碳纳米管的快速功能化及电催化

将耐尔兰(Nile Blue, NB)分子修饰到碳纳米管(CNT)表面形成NB-CNT纳米复合体, 谱学结果表明, NB不仅能快速、高效地修饰到CNT表面, 而且还能有效地改善CNT在水溶液中的分散性能. 将NB-CNT修饰到玻碳(GC)电极表面制备了NB-CNT/GC电极, 循环伏安结果显示, 其伏安曲线上不仅表现出一对良好的、几乎对称的NB单体的氧化还原峰, 式量电位E⁰'几乎不随扫速而变化[其平均值为(－0.422±0.002) V (vs. SCE, 0.1 mol/L PBS, pH 7.0)]; 而且还显示出NB聚合体分子的氧化还原峰, E⁰'为－0.191 V (100 mV/s时). 进一步的实验结果表明, NB和CNT对NADH(即还原型β-烟酰胺腺嘌呤二核苷酸, 又称还原型辅酶I)的电化学氧化具有协同催化作用, 能使其氧化过电位降低多于560 mV; NB-CNT/GC电极还能较好地响应脱氢酶催化底物氧化过程中体系内NADH浓度的变化. 本文对碳纳米管功能化方法具有简单快速、电极制作容易以及催化效率高等优点, NB-CNT/GC电极有望在制作脱氢酶传感器方面得到应用.