对硝基苯酚在多壁碳纳米管修饰玻碳电极上的电化学行为及分析测定

水中对硝基苯酚主要来源于化工、制药行业,它有致癌作用。人们已对它的测定方法进行了大量的研究,最早采用的测定方法是分光光度法,其检测限偏高;色谱法测定对硝基苯酚,操作繁琐,仪器昂贵,分析成本高。后来又发展了一种操作更方便的直接用于测定的电化学方法。本文旨在利用碳纳米管对对硝基苯酚的吸附性能,研究对硝基苯酚在多壁碳纳米管修饰电极上的电化学行为。     

Study on the inclusion interaction of ethyl violet with cyclodextrins by MWNTs/Nafion modified glassy carbon electrode

The interactions of ethyl violet (EV) with cyclodextrins (CDs) were investigated by Multi-wall carbon nanotubes/Nafion composite film modified glassy carbon electrode (MWNTs/Nafion/GCE). It was found that the MWNTs/Nafion composite film can effectively catalyze the electrode reaction of EV. The variation of the electrochemical behavior of EV upon the addition of CDs indicated the formation of the inclusion complexes of EV with β-CD, heptakis (2,3,6-tri-O-methyl)-β-CD (TM-β-CD), heptakis (2,6-di-O-methyl)-β-CD (DM-β-CD), hydroxypropyl-β-CD (HP-β-CD), and carboxymethyl-β-CD (CM-β-CD). The stoichiometry ratios of EV and the above five CDs were found to be 1:1. The inclusion ability obeyed the order: CM-β-CD > HP-β-CD > TM-β-CD > DM-β-CD > β-CD. The results showed that the modified β-CDs exhibited stronger binding ability than native β-CD, especially the charged CM-β-CD, which implied that the inclusion capacity depends on not only size matching and hydrophobicity but also electrostatic interaction. ¹HNMR spectra and molecule mechanics calculations suggested that EV was included into the cavity of β-CD from the wider side.     

Electrochemical behavior and voltammetric determination of norfloxacin at glassy carbon electrode modified with multi walled carbon nanotubes/Nafion

A simple and rapid electrochemical method is developed for the determination of trace-level norfloxacin, based on the excellent properties of multi-walled carbon nanotubes (MWCNTs). The MWCNTs/Nafion film-coated glassy carbon electrode (GCE) is constructed and the electrochemical behavior of norfloxacin at the electrode is investigated in detail. The results indicate that MWCNTs modified glassy carbon electrode exhibited efficiently electrocatalytic oxidation for norfloxacin (NFX) with relatively high sensitivity, stability and life time. Under conditions of cyclic voltammetry, the current for oxidation of selected analyte is enhanced significantly in comparison to the bare GCE. The electrocatalytic behavior is further exploited as a sensitive detection scheme for the analyte determinations by linear sweep voltammetry (LSV). Under optimized condition in voltammetric method the concentration calibration range and detection limit (S/N=3) are 0.1-100 micromol/L and 5 x 10(-8)mol/L for NFX. The proposed method was successfully applied to NFX determination in tablets. The analytical performance of this sensor has been evaluated for detection of the analyte in urine as a real sample.     

多壁碳纳米管修饰电极上阿替洛尔电化学行为的研究及其测定

基于多壁碳纳米管修饰玻碳电极对阿替洛尔的催化作用,建立了测定阿替洛尔的电化学分析方法。多壁碳纳米管修饰玻碳电极与裸玻碳电极相比,显著提高了阿替洛尔的氧化峰电流,降低了氧化峰电位,提高了测定的灵敏度。该电极测定阿替洛尔的线性范围为4.9×10-6~6.3×10-4mol/L,检出限为2×10-6mol/L。对1.3×10-4mol/L阿替洛尔进行11次平行测定,相对标准偏差为4.4%。此法可用于阿替洛尔片剂中阿替洛尔的测定。     

对氯酚在碳纳米管修饰玻碳电极上的电化学行为研究

研究了对氯酚在多壁碳纳米管修饰玻碳电极（MWNTs/GC）上的电化学行为。MWNTs/GC电极对对氯酚具有良好的电催化作用,相比玻碳电极对氯酚的氧化峰电位负移76 mV,峰电流达到玻碳电极上的8倍。通过线性扫描伏安法研究了富集时间、溶液pH和扫描速率对对氯酚氧化的影响。并采用计时电流法研究了氧化峰电流与对氯酚的浓度关系,结果显示峰电流与对氯酚的浓度在2.0×10^-7-2.0×10^-4mol/L范围内呈良好线性关系,检出限为8.8×10-8mol/L（S/N=3）。放置7 d后,对氯酚在碳纳米管上的峰电流仍能达到最初电流的96.2%,表明电极的稳定性较好。     

The electrochemical behavior of dopamine at glassy carbon electrode modified by Nafion multiwalled carbon nanotubes

DFT (B3LY/6-31G (d, p) and B3LYP/cc-PVDZ) calculations are performed for deoxidized dopamine (DA_(R)) and its oxidized form (DA_(O)). The electrochemistry of dopamine (DA) was studied by cyclic voltammetry (CV) at a glassy carbon electrode modified by Nafion multiwalled carbon nanotubes (MWNTs) in phosphate buffers at pH 5.4, showing that the standard electrode potential of a half reaction for DA_(O), H⁺/DA_(R) is 0.74 V. This experimental standard electrode potential of the half reaction is consistent with those of 0.65 and 0.69 V calculated using the energies of solvation and the sum of the electronic and thermal free energies of DA_(R) and DA_(O). The frontier orbital theory and Mulliken charges of molecules explain the electrochemical behavior of CV at a modified electrode well. The effects of oxygen on DA_(R) in blood and drug are also discussed according to equilibrium theory. The modified electrode was successful for determination of the content of pharmaceutical DA. The text was submitted by the authors in English.     

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     

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.     

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。     

Mercury-free simultaneous determination of cadmium and lead at a glassy carbon electrode modified with multi-wall carbon nanotubes

A multi-wall carbon nanotube (MWNT) modified glassy carbon electrode (GCE) was described for the simultaneous determination of trace levels of cadmium and lead by anodic stripping voltammetry (ASV). In pH 4.5 NaAc-HAc buffer containing 0.02 mol/l KI, Cd²⁺ and Pb²⁺ first adsorb onto the surface of a MWNT film coated GCE and then reduce at −1.20 V. During the positive potential sweep, reduced cadmium and lead were oxidized, and two well-defined stripping peaks appeared at −0.88 and −0.62 V. Compared with a bare GCE, a MWNT film coated GCE greatly improves the sensitivity of determining cadmium and lead. Low concentration of I⁻ significantly enhances the stripping peak currents since it induces Cd²⁺ and Pb²⁺ to adsorb at the electrode surface. The striping peak currents change linearly with the concentration of Cd²⁺ from 2.5×10⁻⁸ to 1×10⁻⁵ mol/l and with that of Pb²⁺ from 2×10⁻⁸ to 1×10⁻⁵ mol/l. The lowest detectable concentrations of Cd²⁺ and Pb²⁺ are estimated to be 6×10⁻⁹ and 4×10⁻⁹ mol/l, respectively. The high sensitivity, selectivity, and stability of this MWNT film coated electrode demonstrated its practical application for a simple, rapid and economical determination of trace levels of Cd²⁺ and Pb²⁺ in water samples.     

Electrochemical behavior of levodopa at multi-wall carbon nanotubes-quantum dots modified glassy carbon electrodes.

A multi-wall carbon nanotubes (MWNTs)-quantum dots (QDs) composite-modified glassy carbon electrode (GCE) was prepared. The complex was characterized by transmission electron microscopy (TEM). The electrochemical behavior of levodopa at MWNTs and QDs-modified GCEs (MWNTs-QDs/GCE) was studied by cyclic voltammetry (CV) and chronocoulometry (CC). It was found that its electrochemical behavior was a two-charge-two-proton process. The modified electrode had high electrocatalytic activity for levodopa with a standard heterogeneous rate constant of 0.595 cm s(-1), which was greatly increased compared with the values for bare GCE and individual MWNTs modified GCE. The better electrocatalytic activity for levodopa at MWNTs-QDs/GCE may due to a synergistic effect between MWNTs and QDs. This result provides a novel way to promote research on biomicromolecules at nano-dimensions.     

Electrochemical behavior of tryptophan and its derivatives at a glassy carbon electrode modified with hemin

The electrochemical behavior of tryptophan (Trp) and its derivatives, such as indole-3-acetic acid (IAA), 5-hydroxytryptamine (5-HT), 5-hydroxy-indole-3-acetic acid (5-HIAA) and glycyl-tryptophan (Gly-Trp) peptide at a glassy carbon electrode modified with hemin (hemin/GC electrode) by electropolymerization have been investigated in detail. The results showed that the hemin/GC electrode would catalyze the electrochemical oxidation of Trp and its derivatives, based on which a differential pulse voltammetric procedure has been proposed for determination of Trp and its derivatives. Meanwhile, the electrochemical reaction mechanism for these compounds at hemin/GC electrode has been also investigated, and the results indicated that a two electron and two proton transfer was involved in the electrode reaction process.     

Electrochemical oxidation behavior of methotrexate at DNA/SWCNT/Nafion composite film-modified glassy carbon electrode

Glassy carbon electrode modified with DNA-functionalized single-walled carbon nanotube (DNA/SWCNT) and Nafion composite film was developed for the detection of methotrexate. The characteristics of the modified electrode were examined by transmission electron microscopy and cyclic voltammetry. Compared with a bare glassy carbon electrode and Nafion- and SWCNT/Nafion-modified electrodes, the DNA/SWCNT/Nafion-modified one exhibited the more superior ability of detecting methotrexate, including the higher sensitivity and the lower overpotentials, due to the synergetic DNA-functionalized SWCNT and Nafion. Also, the dependence of the current on pH, nature of buffer, instrumental parameters, accumulation time, and potential was investigated to optimize the experimental conditions in the determination of methotrexate. Under the selected conditions, the modified electrode in pH?=?2.78 Britton–Robinson buffer solutions showed a linear voltammetric response to methotrexate within the concentration range of 2.0?×?10^?8–1.5?×?10^?6?mol?L^?1, with the detection limit of 8.0?×?10^?9?mol?L^?1. The method was also applied to detect methotrexate in medicinal tablets and spiked human blood serum samples.     

Electrochemical behavior and voltammetric determination of paracetamol on Nafion/TiO2-graphene modified glassy carbon electrode

A simple and sensitive method was developed for the detection of mercury ions with quartz crystal microbalance (QCM), based on the specific thymine-Hg(2+)-thymine (T-Hg(2+)-T) interaction and gold nanoparticle-mediated signal amplification. To enhance the sensitivity of detection a sandwich hybridization approach was adopted in this work. The QCM gold surface was modified with the probe SH-oligonucleotides (Oligo-1) and 6-Mercapto-1-hexanol to form an active surface for the hybridization of a longer ss-DNA (Oligo-2), and then Oligo-3 hybridazated with an excess and matching part of Oligo-2. In all oligonucleotides, there existed T bases. In the presence of Hg(2+) ions, special T-Hg(2+)-T reaction greatly enhanced the hybridization of oligonucleotides and detection sensitivity. The gold nanoparticle (Au NPs) amplifier method further increased the sensitivity of detection. A detection sensitivity of 5nM Hg(2+) was obtained in the QCM system, whereas other coexisting metal ions (such as Ni(2+), Mg(2+), Co(2+), Cr(3+), Pb(2+), Cd(2+), Mn(2+), Ba(2+)) had no significant interference. This method reveals a new approach for the manufacture of a kind of simple and low cost sensors for the Hg(2+) detection.     

Electrochemical behavior of o-sec-butylphenol at glassy carbon electrode modified with multiwalled carbon nanotubes and 1-butyl-3-methylimidazolium hexafluorophosphate

A sensitive electrochemical sensor based on immobilized multiwalled carbon nanotubes (MWCNTs) and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM·PF(6)) on a glassy carbon electrode (GCE) for o-sec-butylphenol (osBP) was proposed. The electro-oxidation behavior was studied, the experimental conditions were optimized and kinetic parameters were calculated. The results indicated that this electrochemical sensor has the advantages of fast electron-transfer rate, minimal fouling of electrodes, high sensitivity and stability for o-sec-butylphenol. Upon comparison with a glassy carbon electrode, this senor would effectively minimize the over-potential and increase the electrochemical response to o-sec-butylphenol. Under the optimum conditions, the peak current was linear to the osBP concentration range from 1 × 10(-7) to 2.5 × 10(-5) M with the detection limit of 8.65 × 10(-9) M (S/N = 3). The proposed method was applied to the determination of spiked water samples with satisfactory results.     

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.     

阿奇霉素在多壁碳纳米管修饰电极上的电化学行为及其测定

运用循环伏安法与线性扫描伏安法研究了阿奇霉素在多壁碳纳米管修饰玻碳电极上的电化学行为,建立了一种直接测定阿奇霉素的电化学分析方法。结果表明,与裸玻碳电极相比,多壁碳纳米管修饰电极能显著提高阿奇霉素的氧化峰电流,阿奇霉素的电极过程完全不可逆,存在典型的吸附特性。在优化的实验条件下,氧化峰电流与阿奇霉素浓度在3.0×10-7～2.5×10-5 mol/L和2.5×10-5～5.0×10-4 mol/L范围内呈现良好的线性关系,检出限为1.0×10-7 mol/L。     

Voltammetric behavior and determination of 17 beta-estradiol at multi-wall carbon nanotube-Nafion modified glassy carbon electrode.

For the purpose of low cost and sensitive electrochemical detection of 17 beta-estradiol (E2), a multi-wall carbon nanotube (MWNT)-Nafion modified electrode was fabricated. The MWNT modified electrode shows enhancement for the anodic peak current of E2 compared with the value obtained using a bare electrode. The anodic peak current measured by square wave voltammetry after 5 min open-circuit accumulation was proportional to the concentration of E2 over the range of 2.5 x 10(-7) to 10 10(-6) M, and a detection limit of 1 x 10(-8) M was obtained.     

芦丁修饰电极的电化学特性及其催化性能

研究了芦丁修饰玻碳电极的制备及其电化学性质,探讨了电极反应的机理为ECE过程。研究了它对抗坏血酸和KMnO4的电催化作用:在pH6.0的磷酸盐缓冲溶液(PBS)中,此修饰电极对抗坏血酸有良好的催化氧化作用,而对KMnO4有良好的催化还原作用。