电化学分析电极的应用研究进展

为了提高工作电极的灵敏度、选择性和稳定性,经常采用滴镀、电化学聚合和电化学沉积等方法对其进行表面改性。综述了工作电极的表面修饰方法和表面修饰电极的应用,最后展望了表面修饰电极在电化学分析中的发展趋势。     

普鲁士蓝修饰玻碳电极测定2,6-二甲基苯酚

利用电化学方法在玻碳电极表面聚合一层普鲁士蓝,制备普鲁士蓝修饰玻碳电极,运用循环伏安法研究了2,6-二甲基苯酚在该修饰电极上的电化学行为。结果表明,该修饰电极对2,6-二甲基苯酚显示出较好的电化学响应和电催化活性,在pH为4.0的HAc-NaAc缓冲溶液中,2,6-二甲基苯酚浓度与其峰电流在2.0×10-5~1.0×10-2 mol/L范围内呈现良好的线性关系。     

尿酸在聚直接蓝-71/碳纳米管复合膜修饰电极上的电化学行为

通过在碳纳米管修饰玻碳电极表面电聚合的方法制备了直接蓝-71/碳纳米管复合膜修饰电极（SD-71/MWCNT/GCE）,运用循环伏安法研究了尿酸（UA）在该修饰电极上的电化学行为。在pH 7.0的PBS中,UA在0.32 V处产生灵敏氧化峰,与其在玻碳电极电极上的电化学行为相比,两者的氧化峰电流显著增加,峰电位差（ΔEpa）达到0.20 V。     

对乙酰氨基酚在聚L-赖氨酸膜修饰电极上的电化学行为及测定

利用循环伏安法(CV)将L-赖氨酸电聚合修饰于玻碳电极表面,制备出对对乙酰氨基酚(ACOP)具有良好电催化作用的聚L-赖氨酸薄膜修饰电极,优化了底液、pH值、聚合圈数等测定条件,建立了一种直接测定ACOP的高灵敏度电分析方法.该方法测定ACOP的线性范围为5.0×10-7～1.0×10-4mol·L-1,R=0.9996;检出限可达1.0×10-7mol·L-1.对1.0×10-4mol·L-1的ACOP平行测定5次的相对标准偏差不大于3%.样品回收率在98.40%～100.80%之间.可用于实际样品的定量分析.     

聚γ-氨基丁酸修饰电极测定丹皮酚的电化学研究

用电化学方法将γ-氨基丁酸聚合在玻碳电极（GCE）表面,制备了聚γ-氨基丁酸修饰电极（poly γ-aminobutyric acid modified electrode, P-γ-ABA/GCE）。探究了丹皮酚（paeonol, Pae）在此修饰电极上的电化学行为,建立了测定丹皮酚的新方法。结果表明,在pH=7.0的Na₂HPO₄-NaH₂PO₄缓冲溶液（PBS）中,Pae的浓度与氧化峰电流在2.0×10^-7～8.0×10^-5 mol/L范围内有良好的线性关系,相关系数R为0.992 7,检出限为8.0×10^-8 mol/L。在样品Pae的测定中,回收率为96.3%～103.7%。该方法可用于实际样品的测定。     

桑色素修饰电极的制作及其应用于二丁基锡的测定

采用电化学聚合方式将桑色素修饰到玻碳电极表面,研究了该修饰电极阳极溶出伏安法测定二丁基锡(DBT)的机理和实验条件。结果表明:在0.05mol/LHAcNaAc底液中,修饰电极对DBT有良好的配合性。DBT的溶出峰电流与其浓度在2～38ng/mL范围内呈良好的线性关系,定量下限可达2ng/mL,方法的相对标准偏差为1.8%。     

铬蓝K电聚合膜修饰电极检测吲哚美辛

运用循环伏安法将酸性铬蓝K聚合在玻碳电极表面形成聚合膜制备修饰电极。运用电化学交流阻抗和循环伏安法研究吲哚美辛在酸性铬蓝K电聚合膜修饰电极上的电化学行为。经对溶液的pH和扫描速率等条件进行优化处理。在最佳实验条件下,吲哚美辛的峰电流值与其浓度在3×10~(-7)~4×10~(-5)mol/L范围内呈良好的线性关系,检出限为9.77×10~(-8)mol/L,该方法可进一步应用于吲哚美辛肠溶片和吲哚美辛胶囊吲哚美辛含量检测,回收率在99.44%~101.39%之间。     

顺序化学沉积法制备PB/MWNTs复合修饰电极及电化学性能研究

利用Fe3+和[Fe(CN)6]4-溶液,采用顺序化学沉积法制得普鲁士蓝/多壁碳纳米管(PB/MWNTs)修饰电极.FTIR、SEM等结构表征表明普鲁士蓝(PB)直接沉积在多壁碳纳米管(MWNTs)的表面.电化学研究表明PB/MWNTs修饰电极上的电子传递过程受支持电解液中K+、H+浓度影响.在pH=5.6、K+浓度为0.2 mol/L的KOH-KH2PO4-KCl支持电解液中,电极表现出优异的电化学稳定性,且可用于定量测定H2O2浓度.     

聚对苯二酚修饰电极测定多巴胺和L-色氨酸的电化学研究

制备了对苯二酚聚合膜修饰玻碳电极(PHQ/GCE),研究了多巴胺(DA)和L-色氨酸(L-Trp)在该电极上的电化学行为,以及支持电解质、溶液pH、扫描速率等对DA和L-Trp伏安响应的影响.实验发现,在pH 5.5的NaH2PO4-Na2HPO4缓冲溶液中,可用PHQ/GCE测定溶液中的DA和L-Trp,两者氧化峰电流均与浓度在1×10-3～5×10-6 mol/L范围内呈良好线性关系,相关系数分别为0.998 3和0.996 5,检出限分别为1×10-6 mol/L和5×10-7 mol/L,该方法简便快捷.     

5-羟色胺在碳纳米管修饰电极上的电化学行为及检测

研究了5-羟色胺在碳纳米管修饰电极上的电化学行为。结果表明,在0.1 mol·L-1磷酸盐(pH=8.0)缓冲溶液中,5-羟色胺在碳纳米管修饰电极上的氧化峰峰电位为0.23 V;5-羟色胺吸附在电极表面,电化学反应由表面控制;根据5-羟色胺氧化过程中失去4个电子和4个质子,讨论了反应机理。5-羟色胺浓度在1.36～16...     

酰基吡唑啉酮修饰玻碳电极对维生素C组分的电化学分析

制备了呋喃甲酰基吡唑啉酮修饰玻碳电极,通过循环伏安法用该电极对维生素C组分进行分析。考察了支持体系的pH值、配体修饰量、扫描起始电位、扫描速度等对电极反应的影响。实验结果表明,在NaH2PO4-Na2HPO(4pH=5.5)缓冲溶液中,测定体系于0.5V(vs.SCE)处出现一尖锐、灵敏的修饰吸附峰。其浓度线性形范围关系:Y=6.70137+19.9381XR=0.99833。采用标准加入法对实际样品进行了检测,结果满意。     

Selective oxidation of serotonin and norepinephrine over eriochrome cyanine R film modified glassy carbon electrode

A novel ECR-modified electrode is fabricated by electrodeposition of Eriochrome Cyanine R (ECR) at a glassy carbon (GC) electrode by cyclic voltammetry (CV) in double-distilled water. The characterization of the ECR film modified electrode is carried out by atomic force microscopy (AFM), infrared spectra (IR), spectroelectrochemistry and cyclic voltammetry. The results show that a slightly heterogeneous film formed on the surface of the modified electrode, and the calculated surface concentration of ECR is 2 × 10⁻¹⁰ mol/cm⁻². The ECR film modified GC electrode shows excellent electrocatalytic activities toward the oxidation of serotonin (5-HT) and norepinephrine (NE). Furthermore, the modified electrode can separately detect 5-HT and NE, even in the presence of 200-fold concentration of ascorbic acid (AA) and 25-fold concentration of uric acid (UA). Using differential pulse voltammetry (DPV), the peak currents of 5-HT and NE recorded in pH 7 solution are linearly dependent on their concentrations in the range of 0.05-5 μM and 2-50 μM, respectively. The limits of detection are 0.05 and 1.5 μM for 5-HT and NE, respectively. The ECR film modified electrode can be stored stable for at least 1 week in 0.05 M PBS (pH 7) at 4 °C in a refrigerator. Owing to its excellent selectivity and sensitivity, the modified electrode could provide a promising tool for the simultaneous determination of 5-HT and NE in complex biosamples.     

乙酸锌改性稻壳生物炭电容及电吸附Cu2+性能

以稻壳为原料制备生物炭,利用不同浓度的乙酸锌对稻壳炭改性,制得产物分别命名为RHC和MRHC。通过SEM、BET、XRD对制备的生物炭理化特性进行表征。分析表明,改性炭孔隙结构丰富,比表面积较大,且锌以氧化物颗粒状存在于生物炭表面。将改性前后的稻壳生物炭制成电极,测试其电化学性能。结果表明,与未改性生物炭相比,改性后的炭电极比电容大大提高,电阻显著减小,循环性能和倍率性能均有提升。MRHC-0.3（乙酸锌浓度为0.3 mol/L时的改性生物炭）比表面积为495 m2/g,孔容为0.214 cm3/g,该电极在2 A/g下充放电2000次后,其电容保持率为92.16%。将MRHC-0.3电极用于电吸附Cu2+实验,发现在0.9 V,pH为5时吸附效果最好,吸附量为9.57 mg/g。在0.9 V,pH为5,Cu2+初始质量浓度为50 mg/L时,去除率可达63.82%。     

The effect of polypyrrole-bound anthraquinonedisulphonate dianion on cathodic reduction of oxygen

Functionalized polypyrrole (PPy) films were prepared by incorporation of anthraquinonedisulphonate (AQDS) as doping anion during the electropolymerization of pyrrole (Py) monomer at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the PPy-bound AQDS modified electrode and cathodic reduction of oxygen on the resulting polymer film were studied. An obvious surface redox reaction corresponding to AQ/H₂AQ was observed and the dependence of this reaction on the solution pH was also illustrated. The electrocatalytic ability of the PPy-bound AQDS modified electrode was demonstrated by the electroreduction of oxygen at the optimized pH of 6.3 in a phosphate buffer. The reduced AQDS (H₂AQ) is responsible for the extraordinary catalytic activity to the oxygen reduction reaction. The PPy layers not only act as an electron mediator, but also facilitate the stability of the modified electrode. It was found that the catalytic reaction occurred in the presence of the bound AQDS and O₂ is in agreement with an electrochemical–chemical (EC) mechanism. The kinetic parameters of oxygen reduction were determined using Koutecky–Levich equation and Tafel polarization technique.     

Development of a disposable electrode modified with carbonized,graphene‐loaded nanofiber for the detection of dopamine in human serum

A one‐step electrode surface modification is proposed in which a disposable, screen‐printed carbon electrode is functionalized with carbonized, electrospun polyacrylonitrile (PAN)‐loaded graphene (G) nanoparticles to form a composite, CPAN5G‐4x. The electrochemical behavior of the CPAN5G‐4x electrode was examined by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy and X‐ray diffraction were used to characterize the surface morphology and physical properties of the carbonized composite nanofibers before and after modification. The modified electrode was found to be effective for the detection of dopamine (DA) using square‐wave voltammetry (SWV) in the presence of interfering substances such as ascorbic acid and uric acid. With the addition of sodium dodecyl sulfate (SDS) to an optimized solution of phosphate‐buffered saline (PBS) at a pH of 2, the fabricated electrode exhibited enhanced electrocatalytic activity toward the oxidation of DA relative to PBS without SDS at a pH of 7.4. The SWV current displayed a linear response to DA concentrations ranging from 0.5 to 100 μM, with a limit of detection of 70 nM (S/N = 3) and a sensitivity of 1.4258 μA μM^?1 cm^?2. Finally, the CPAN5G‐4x electrode was used to determine DA levels in human serum. The modified electrode can potentially be harnessed for further electrochemical biosensor applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40858.     

Preparation and electrochemistry of cadmium pentacyanonitrosylferrate film modified glassy carbon electrode

A glassy carbon (GC) electrode surface was modified with a cadmium pentacyanonitrosylferrate (CdPCNF) film as a novel electrode material. The modification procedure of the GC surface includes two consecutive procedures: (i) the electrodeposition of metallic cadmium on the GC electrode surface from a CdCl₂ solution and (ii) the chemical transformation of the deposited cadmium to the CdPCNF films in 0.05 M Na₂[Fe(CN)₅NO] + 0.5 M KNO₃ solution. The modified GC electrode showed a well-defined redox couple due to [Cd^IIFe^III/II(CN)₅NO]^0/−1 system. The effects of supporting electrolytes and solution pH were studied on the electrochemical behavior of the modified electrode. The diffusion coefficients of alkali-metal cations in the film (D), the transfer coefficient (α) and the charge transfer rate constant at the modifying film | electrode interface (k_s), were calculated in the presence of various alkali-metal cations. The stability of the modified electrode was investigated under various experimental conditions.     

基于Cu-Mg-Al三元类水滑石修饰玻碳电极对食品中亚硝酸根的检测

制备了Cu-Mg-Al三元类水滑石修饰玻碳电极,研究了亚硝酸根在修饰电极上的电化学行为,Cu-Mg-Al三元类水滑石对亚硝酸根的电化学氧化具有明显的催化活性,评估了溶液pH值、扫描速率和施加电位对亚硝酸盐电流响应的影响,计算了电机有效表面积和NO2-在修饰电极表面的吸附容量,并初步探讨了催化机理,在优化的实验条件下,该修饰电极对NO2-的测定线性范围为0.1~10.42μmol/L,检测限为0.08μmol/L(S/N=3)。将该传感器用于食品中亚硝酸根离子的测定,结果满意。     

Voltammetric characterization of the self-assembled monolayer (SAM) of octabutylthiophthalocyaninatoiron(II): a potential electrochemical sensor

The fabrication of a self-assembled monolayer (SAM) of 2,3,9,10,16,17,23,24-octa (butylthio)-phthalocyaninatoiron(II) [FePc(SBu)₈] on gold electrode is described. The integrity of the SAM, with respect to its ability to block certain Faradaic processes, is interrogated using cyclic voltammetric experiments in aqueous solutions. The experiments show that this SAM provide an excellent blocking capability to the Faradaic processes emanating from gold surface oxidation, underpotential deposition (UPD) of copper and redox chemistry of Fe(NH₄)(SO₄)₂ in HClO₄. It is revealed by cyclic voltammetry that an ill-defined reversible couple of the SAM of FePc(SBu)₈ can be greatly improved by a simple repetitive cycling of the modified electrode in a DMF solution containing TBAP within a short space of time (ca. 2 min). This ‘activation’ process provides good information concerning the surface coverage and orientation of the monolayer. The reversible redox wave shows a potential shift of about −57 mV per pH in the pH range of 2-9. A preliminary investigation indicates that FePc(SBu)₈-SAM modified gold electrode shows electrocatalytic activity toward the oxidation of l-cysteine in acidic medium. The monolayer is stable and easily reproducible. However, due to its susceptibility to destruction via oxidative and reductive desorptions, its potential application as an electrochemical sensor would be much better in acidic and neutral than alkaline environments.     

DNA与（S）-2-（5-氟尿嘧啶-1-基-乙酰基）氨基-1，4-丁二酸相互作用的电化学和光谱学研究

以自组装制得的DNA修饰电极为工作电极,采用循环伏安研究了抗癌药物（S）-2-（5-氟尿嘧啶-1-基-乙酰基）氨基-1,4-丁二酸（5FUASP）与DNA的相互作用,还结合紫外-可见光谱进一步研究了这种相互作用。循环伏安测试结果表明：5FUASP与DNA在pH=6．86的缓冲溶液中有强烈的相互作用,在电极表面反应的过程为准可逆电化学反应一化学反应偶合（Ec）过程。当扫描速度较低时,EC反应是扩散控制过程;紫外吸收光谱表明抗癌药物5FUASP与DNA通过插入作用相互结合。     

Electrochemical behavior of a novel palladium pentacyanonitrosylferrate modified aluminum electrode

Novel inorganic film modified electrodes have been prepared by chemical deposition of a thin palladium pentacyanonitrosylferrate (PdPCNF) film on the surface of aluminum substrate. The modification process including the electroless deposition of metallic palladium on the aluminum electrode surface from PdCl₂+25% ammonia solution and chemical derivatization of deposited palladium to the PdPCNF film in 0.1 M Na₂[Fe(CN)₅NO]+0.5 M KNO₃+HNO₃ solution (pH 1.5-2.5), are described. The aluminum-based modified electrodes exhibit, one pair of well-defined voltammetric peaks which correspond to the Fe(III)/Fe(II) transition in complex structure. The effect of pH, ammonium, alkali metal and alkaline earth metal cations of supporting electrolyte on the electrochemical characteristics of the modified electrode was studied in detail. Diffusion coefficients of hydrated ammonium and alkali metal cations in the film (D), transfer coefficient (α) and transfer rate constant for electron (k_s), were determined. The high stability of this modified electrode makes it attractive in practical application.