金纳米粒子/碳纳米管修饰电极吸附伏安法测定微量间苯二胺

运用循环伏安法及线性扫描伏安法研究了间苯二胺在金纳米粒子/碳纳米管修饰玻碳电极上的电化学行为,优化并建立了一种直接测定间苯二胺的电化学分析方法。结果表明,与裸玻碳电极相比,金纳米粒子/碳纳米管修饰电极能显著提高间苯二胺的氧化峰电流。在优化条件下,氧化峰电流与间苯二胺浓度在3.0×10-8~1.0×10-6mol/L范围内呈现良好的线性关系,检出限为1.0×10-8mol/L,对1.0×10-7mol/L的间苯二胺溶液平行测定10次的RSD为4.2%。测定了实验室废水中的间苯二胺含量,3次测定结果的平均回收率为99.7%,RSD为2.1%。     

聚苯胺-石墨烯修饰玻碳电极同时测定邻苯二酚和对苯二酚

本文制备了聚苯胺-石墨烯修饰玻碳电极,并用循环伏安(CV)法和微分脉冲伏安(DPV)法研究了邻苯二酚(CC)和对苯二酚(HQ)在该修饰电极上的电化学行为。实验结果表明,相对于裸玻碳电极,HQ和CC在聚苯胺-石墨烯修饰电极上的氧化峰电流显著提高,氧化峰电位相差104.8mV,实现了CC和HQ的选择性测定。DPV法同时测定二酚时,HQ和CC分别在1.0×10-6~8.0×10-4 mol/L浓度范围内与其峰电流呈良好的线性关系,相关系数R分别为0.998、0.997,检出限(S/N=3)分别为1.0×10-7、8.0×10-8mol/L。将该方法用于模拟水样分析,回收率为95.3%~103.5%。     

纳米金/石墨烯修饰电极的制备及其对多巴胺的测定

利用电化学还原方法制备纳米金/石墨烯修饰玻碳电极,研究了多巴胺(DA)在该修饰电极上的电化学行为,建立了电化学测定多巴胺的新方法。结果表明,在磷酸盐缓冲溶液中,此修饰电极对多巴胺的电化学响应具有很好的催化作用。利用差示脉冲伏安技术对多巴胺的电化学氧化进行定量分析,多巴胺的氧化峰电流与其浓度在1.0×10-7～1.0×10-5mol/L范围内呈良好的线性关系,检测限低至4.0×10-8mol/L。该修饰电极适于多巴胺的分析检测。     

聚L-白氨酸-碳纳米管修饰电极同时检测对苯二酚和邻苯二酚

用Nafion将单壁碳纳米管(SWCNT)固定到玻碳电极(GCE)上,再利用电化学聚合方法将L-白氨酸(L-LEU)聚合到SWCNT/GCE上,制备得到poly L-LEU/SWCNT/GCE修饰电极。采用循环伏安法(CV)、差分脉冲伏安法(DPV)和电化学交流阻抗法(EIS)研究了对苯二酚(HQ)、邻苯二酚(CC)共存时,二者在修饰电极上的电化学行为。结果表明:此修饰电极对HQ和CC有很好的电催化和分离作用。二者在修饰电极上的氧化还原峰电流与GCE相比显著增强,HQ和CC的氧化峰电位差和还原峰电位差分别为124 mV和131 mV。HQ和CC的检测线性范围分别为2.0×10-7~1.0×10-4、5.0×10-7~1.0×10-4mol/L。检出限分别为8.0×10-8、1.0×10-7mol/L。制备的修饰电极重现性、稳定性良好。在模拟废水中采用该修饰电极对HQ和CC进行检测,结果满意。     

纳米铂直接修饰玻碳电极的制备及在半胱氨酸中的电化学行为

采用一步化学原位还原法将球形纳米铂颗粒直接修饰在玻碳电极上,用SEM、EDS和电化学方法对该电极进行表征并与铂片电极、裸玻碳电极进行了对比。结果表明,纳米铂修饰电极的峰电流与扫描速度呈线性关系,纳米铂在电极表面覆盖率为1.28×10-7mol/cm2。循环伏安法研究结果表明纳米铂修饰电极对半胱氨酸的催化氧化作用和铂片电极相比提高了数倍,且峰电位负移了0.3V。在纳米铂修饰的玻碳电极上,半胱氨酸的浓度在1.0×10-7mol/L到1.0×10-5mol/L范围内和催化电流呈线性关系。     

介孔炭修饰玻碳电极循环伏安法测定对苯二酚

将介孔炭分散在5g.L-1壳聚糖溶液中并滴涂在玻碳电极表面,烘箱烘干后,制备了介孔炭修饰电极。采用循环伏安法研究了对苯二酚在修饰电极上的电化学行为。结果表明:对苯二酚在该修饰电极上出现了一对灵敏的氧化还原峰,其峰电流比裸玻碳电极增大了很多,据此提出了用循环伏安法测定对苯二酚的方法。对苯二酚的浓度在1.0×10-6～1.0×10-4 mol.L-1范围内与其氧化峰电流呈线性关系,检出限(3S/N)为4.0×10-7 mol.L-1。修饰电极用于模拟水样中对苯二酚的测定,回收率在95.3%～98.7%之间,测定值的相对标准偏差(n=5)在3.8%～4.2%之间。     

纳米金/三聚氰胺修饰电极检测亚硝酸盐

采用电聚合方法制备三聚氰胺(MA)膜修饰玻碳电极(GCE),然后采用原位恒电位沉积法制备金纳米颗粒(Au),并将其修饰于膜电极表面,制得纳米金/三聚氰胺修饰玻碳电极(Au/MA/GCE)。用扫描电子显微镜(SEM)对修饰电极进行表面形貌和元素成分分析。用循环伏安法研究亚硝酸根(NO2-)在该修饰电极上的电化学行为发现,NO2-在0.85 V出现一灵敏的氧化峰。在优化的实验条件下,NO2-在1.0×10-5～1.0×10-3mol/L浓度范围内与其氧化峰电流成线性关系,检测下限为8.9×10-7mol/L。将修饰电极用于实际样品中NO2-的检测,效果良好。     

聚多巴胺-还原氧化石墨烯修饰电极同时测定邻苯二酚和对苯二酚

制备了聚多巴胺-还原氧化石墨烯修饰玻碳电极(PDA-rGO/GCE),以此修饰电极作为工作电极,采用循环伏安法(CV)对邻苯二酚(CC)和对苯二酚(HQ)的电化学行为进行了研究。结果表明CC和HQ在该修饰电极上的峰电流与氧化石墨烯修饰电极相比有了明显增高,并且它们的氧化峰电位差和还原峰电位差均超过110 mV,证明该修饰电极用于两种酚的同时检测是可行的。在优化实验条件下,采用微分脉冲伏安法(DPV)对CC和HQ同时进行检测,CC和HQ的峰电流与其浓度均在1.0×10~(-6)～4.0×10~(-3) mol/L范围内呈良好的线性关系,检出限(S/N=3)分别为2.0×10~(-7) mol/L和3.6×10~(-7) mol/L。以所制备的修饰电极对自来水水样和湖水水样进行了加标回收检测,回收率在97.6%～100.6%范围内。     

一种基于乙炔黑/壳聚糖膜修饰电极的对氨基酚传感研究

制备了一种乙炔黑/壳聚糖薄膜修饰的玻碳电极,用循环伏安法详细研究了对氨基酚在该修饰电极上的电化学行为.结果表明: 对氨基酚在此膜修饰电极上呈现出一对可逆的氧化还原峰.相对于裸玻碳电极,该氧化还原峰的峰电流明显提高,峰电位差减小,可逆性变好,表明乙炔黑/壳聚糖薄膜电极对对氨基酚的电化学氧化具有良好的催化作用.对氨基酚的氧化峰电流与其浓度在1.0×10-7～2.0×10-6 mol/L和2 0×10-6～5.0×10-4 mol/L范围内均呈良好的线性关系; 检出限为5.0×10-8 mol/L(S/N=3).应用此修饰电极测定实际水样,结果较满意.     

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。     

石墨烯/铁氰化钴复合膜修饰玻碳电极同时测定对苯二酚、邻苯二酚和间苯二酚

采用滴涂法和电沉积法制备了石墨烯/铁氰化钴复合膜修饰玻碳电极. 用扫描电镜对该纳米复合膜进行了表征.用循环伏安法研究了对苯二酚(HQ)、邻苯二酚(CT)和间苯二酚(RS)在修饰电极上的电化学行为. 实验结果表明, 相对于裸玻碳电极和石墨烯修饰电极, HQ, CT 和RS 在石墨烯/铁氰化钴修饰电极上的氧化峰电流显著提高. 利用差分脉冲伏安法测定, HQ, CT 和RS 分别在1.0×10^－6～1.5×10^－4 mol/L, 1.0×10^－6～2.0×10^－4 mol/L 和3.5×10^－6～2.5×10^－4 mol/L浓度范围内与氧化峰电流呈良好的线性关系, 相关系数分别为0.991, 0.993 和0.992. 信噪比为3 时, HQ, CT 和RS 检出限分别为2.0×10^－7, 2.1×10^－7 和3.5×10^－7 mol/L. 将该方法用于水样分析, 回收率为95.6%～106.1%.     

纳米金/双氢氧化物膜修饰电极制备及对肾上腺素的测定

研究了纳米金/双氢氧化物膜修饰玻碳电极(AuNPs/LDHs/GCE)的制备,通过循环伏安法、扫描电镜和电化学阻抗对修饰电极进行了表征;详细讨论了电极的性能,找出了制备该修饰电极的实验条件,并将此电极用于生物体系中肾上腺素(Adrenaline,AD)的电化学测定.在选定的实验条件下,修饰电极在磷酸盐缓冲溶液(pH=7.0)中进行循环伏安扫描时,氧化峰电流和肾上腺素浓度在9.0×10-8～1.0×10-4mol/L范围内呈良好的线性关系,相关系数为0.9982,其检出限(S/N=3)可达3.1×10-8 mol/L.据此建立了一种新的测定肾上腺素的分析方法,可用于实际样品的检测.     

鸟嘌呤在聚L-甲硫氨酸/石墨烯修饰电极上的电化学行为及测定

制备了聚L-甲硫氨酸/石墨烯修饰的玻碳电极,该电极在0.1 mol/L的磷酸盐缓冲溶液(p H 7.0)中对鸟嘌呤的氧化具有明显的电催化作用。采用循环伏安法(CV)考察了p H值、扫描速率对鸟嘌呤电化学行为的影响。利用示差脉冲伏安法(DPV)对鸟嘌呤进行测定,结果表明在3.6×10-7~4.0×10-5mol/L浓度范围内鸟嘌呤的氧化峰电流与其浓度呈良好的线性关系,相关系数为0.990 4,检出限(S/N=3)为5.0×10-8mol/L。该修饰电极还具有较好的稳定性和重现性。     

还原氧化石墨烯-多壁碳纳米管复合膜负载金纳米粒子修饰玻碳电极检测双酚A

以水合肼为还原剂,采用均相还原法制备还原氧化石墨烯-多壁碳纳米管复合材料(rGO-MWCNTs),通过滴涂法将其修饰到玻碳电极(GCE)表面.以此复合材料为载体,采用电化学方法制备了金纳米粒子-还原氧化石墨烯-多壁碳纳米管复合膜修饰电极(AuNPs-rGO-MWCNTs/GCE).通过扫描电镜(SEM)、EDS能谱技术和电化学方法对此电极进行了表征.研究了双酚A在修饰电极上的电化学行为.结果表明,此电极对双酚A的电极过程具有良好的电化学活性,在0.10 mol/L PBS溶液(pH 7.0)中,微分脉冲伏安法测定双酚A的线性范围为5.0 × 10-9~1.0 × 10-7 mol/L和1.0 × 10-7~2.0 × 10-5 mol/L,检出限为1.0 ×10-9 mol/L(S/N=3). 将此电极用于模拟水样和超市购物小票样品中双酚A含量的测定,加标回收率分别为97%~110%和98%~104%.     

Electrochemical Oxidation of Tryptophan and Its Analysis in Pharmaceutical Formulations at a Poly(Methyl Red) Film-Modified Electrode

A poly(methyl red) film-modified glassy carbon electrode was fabricated and the oxidation behavior of tryptophan at the modified electrode was investigated by cyclic and linear sweep voltammetry. The oxidation peak current of tryptophan at the modified electrode increased significantly, and the oxidation process was irreversible and adsorption-controlled. An analytical method was developed for the determination of tryptophan in a phosphate buffer solution at pH 3.5. The anodic peak current varied linearly with a tryptophan concentration in the range 1.0 × 10^?7 to 1.0 × 10^?4 mol/L with a limit of detection of 4.0 × 10^?8 mol/L. The proposed method was successfully applied to determine tryptophan in composite amino acid injections.     

Electrochemical behaviors of ofloxacin and its voltammetric determination at carbon nanotubes film modified electrode

A multi-wall carbon nanotubes (MWNTs)-Nafion film-coated glassy carbon electrode (GCE) was fabricated and the electrochemical behavior of ofloxacin on the MWNTs-Nafion film-coated GCE were investigated by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The oxidation peak current of ofloxacin increased significantly on the MWNTs-Nafion film modified GCE compared with that using a bare GCE. This nano-structured film electrode exhibited excellent enhancement effects on the electrochemical oxidation of ofloxacin. A well-defined oxidation peak attributed to ofloxacin was observed at 0.97 V and was applied to the determination of ofloxacin. The oxidation peak current was proportional to ofloxacin concentration in the ranges 1.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol/L and 1.0 × 10⁻⁶ to 2.0 × 10⁻⁵ mol/L. A detection limit of 8.0 × 10⁻⁹ mol/L was obtained for 400 s accumulation at open circuit (S/N = 3). This method for the detection of ofloxacin in human urine was satisfactory. __________ Translated from Chinese Journal of Applied Chemistry, 2007, 24(5): 540–545 [译自: 应用化学]     

多壁碳纳米管修饰玻碳电极伏安法测定氯霉素

研究了氯霉素(CAP)在多壁碳纳米管修饰玻碳电极上的电化学行为.发现在pH=2.0的0.1 mol/LKCl-HCl底液中,CAP在该修饰电极上有一灵敏的还原峰(Ep=-0.36 V vs.Ag/AgCl),峰电流与CAP浓度成正比,线性范围为6.0×10-6~2.7×10-4mol/L,检测限达3.0×10-6mol/L.该方法灵敏、准确,用于模拟样品和实际样品的测定,结果满意.     

Fabrication of CeO2 Nanoparticle Modified Glassy Carbon Electrode for Ultrasensitive Determination of Trace Amounts of Uric Acid in Urine

The preparation of a glassy carbon electrode modified by CeO2 nanoparticles was described, which was characterized by cyclic voltammetry and electrochemical impedance spectroscopy. In pH 6.0 buffer, the CeO2 nanoparticle modified electrode （CeO2 NP/GC） gave an excellent electrocatalytic activity for the oxidation of uric acid （UA）. The catalytic current of UA versus its concentration had a good linear relation in the range of 2.0 × 10^-7-5.0 × 10^- 4 mol/L, with the correlation coefficient of 0.9986 and detection limit of 1.0 ×10^-7 mol/L. The modified electrode can be used for the determination of UA in urine, which can tolerate the interference of ascorbic acid up to 1000-fold. The method was simple, quick and sensitive.     

Amperometric Sensor for Detection of the Reduced Form of Nicotinamide Adenine Dinucleotide Using a Poly(pyronin B) Film Modified Electrode

An electrochemical method for the preparation of poly(pyronin B) film was proposed in this paper. A poly(pyronin B) (poly(PyB)) film modified glassy carbon electrode (GCE) has been fabricated via an electrochemical oxidation procedure and applied to the electrocatalytic oxidation of reduced form of nicotinamide adenine dinucleotide (NADH). The poly(PyB) film modified electrode surface has been characterized by atomic force microscope (AFM), scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), UV‐visible absorption spectrophotometry (UV‐vis) and cyclic voltammetry (CV). These studies have been used to investigate the poly(PyB) film, which demonstrates the formation of the polymer film and the excellent electroactivity of poly(PyB) in neutral and even in alkaline media. Due to its potent catalytic effects towards the electrooxidation of NADH at lower potential (0.0 V), poly(PyB) film modified electrode can be used for the selective determination of NADH in real samples because of dopamine, ascorbic acid and uric acid oxidation can be avoided at this potential. The catalytic peak currents are linearly dependent on the concentrations of NADH in the range of 1.0×10^?6 to 5.0×10^?4 mol/L with correlation coefficients of 0.999. The detection limits for NADH is 0.5×10^?6 mol/L. Poly(PyB) modified electrode also shows good stability and reproducibility due to the irreversible attachment of polymer film at GCE surface.     

Study on Diffusion Mechanisms and Determination of Dihydroxybenzene Isomers at the Pre‐anodized Inlaying Ultrathin Carbon Paste Electrode

In this paper, nichrome was adopted as a substrate, to fabricate the pre‐anodized inlaying ultrathin carbon paste electrode (PAIUCPE). The electrochemical behaviors and diffusion mechanisms of three dihydroxybenzene isomers at the electrode were carefully investigated. The effect of pH on oxidation peak current was also detailedly explained. The results were shown that oxidation peak current not only related to the reaction of electroactive materials at the working electrode, but also depended on the reaction variable of reduction at the auxiliary electrode. The oxidation peaks of hydroquinone (HQ), catechol (CC) and resorcinol (RC) located at 0.181 V, 0.288 V and 0.736 V. For CC, RC and HQ, the oxidation peak currents were linear to the concentrations at the range of 5.0 × 10^?6～5.0 × 10^?4 mol/L, 3.0 × 10^?6～5.0 × 10^?4 mol/L and 4.0 × 10^?6～4.0 × 10^?4 mol/L with the detection limits of 2.0 × 10^?7 mol/L, 1.2 × 10^?7 mol/L and 1.2 × 10^?7 mol/L, respectively. The proposed method was successfully applied in the simultaneous determination of dihydroxybenzene isomers in artificial sewage samples with satisfactory results.