GCE/DNA/PFS/RTIL/HRP修饰电极的制备及其电催化行为

将辣根过氧化物酶（HRP）固定在室温离子液体（RTIL）/聚二茂铁硅烷（PFS）/DNA复合材料修饰的玻碳电极（GCE）表面,构建了GCE/DNA/PFS/RTIL/HRP修饰电极,详细地研究了该修饰电极的电催化行为,优化了电解质溶液的pH值和RTIL的体积对催化过氧化氢（H2O2）的影响。 电化学实验结果表明,DNA、PFS和RTIL复合膜既为HRP提供了一个生物兼容的微环境;又有效地促进了电子在HRP和电极表面之间的传递。 在最优实验条件下,该修饰电极对H2O2具有快速的催化响应,在2 s内即可达到稳态电流的95%,其响应在3.25 μmol/L~1.47 mmol/L（r=0.999,n=10）和1.86~5.35 mmol/L（r=0.996,n=12）范围内呈良好的线性关系,检出限为0.86 μmol/L。 该传感器灵敏度高、重现性和稳定性好。 此外,该修饰电极还能催化O2还原。     

抗坏血酸在聚对羟基苯甲酸(poly-PHB)修饰玻碳上的电催化

过循环伏安制备了聚对羟基苯甲酸修饰的玻碳电极。考察了该电极对抗坏血酸的电催化性能。结果显示,聚对羟基苯甲酸修饰玻碳电极对抗坏血酸有很好的电催化作用。在修饰后的电极上产生的峰电流比修饰前的电极产生的峰电流大4倍,氧化峰电位负移189 mV。其氧化峰电流与抗坏血酸浓度在2.6×10-5~3.68 ×10-4mol/L范围内呈线性关系,相关性系数为0.9984,检测限为5×10-6 mol/L(S /N = 3)。在AA与UA共存的体系中,能排除多巴胺对抗坏血酸测定的干扰。     

苯胺在邻-氨基苯磺酸功能化的玻碳电极上聚合及其对抗坏血酸的电催化氧化

通过电氧化法将ABS分子以CN键共价键合在玻碳电极(GCE)表面,形成ABS分子单层膜修饰的GCE(ABS/GCE),在此电极上对AN进行电聚合,从而制备了聚苯胺/邻氨基苯磺酸复合膜修饰电极(PAN-ABS/GCE/CME).由于ABS中磺酸基功能团对PAN的掺杂作用使PAN在中性或碱性介质中都能呈现出较好的电化学活性.研究表明,PAN-ABS/GCE/CME在PBS(pH 6.8)中对AA的电氧化具有催化作用,其氧化峰电位为0.17 V,比在裸GCE上(0.39 V)负移了0.22 V,峰电流明显升高.AA在修饰电极上的氧化峰电流与其浓度在0.5～16.5 mmol/L范围内呈良好的线性关系,其线性回归方程为ipa(μA)=20.2+6.20CAA,r=0.9973; 检出限(3δ)为7.2 μmol/L,电极具有较好的稳定性和重现性.并采用计时电流法对AA催化氧化的扩散系数和催化速率常数进行了研究.     

Amperometric Ascorbic Acid Sensor Based on Disposable Facial Tissues Derived Carbon Aerogels

In this study,the disposable facial tissues derived carbon aerogels(DFTs-CAs)were synthesized using disposable facial tissues as the raw material for fabricating a sensitive amperometric ascorbic acid(AA)sensor.The experimental results indicated that compared to glassy carbon electrode(GCE)and the popular carbon nanotubes modified GCE(CNTs/GCE),DFTs-CAs modified GCE(DFTs-CAs/GCE)exhibited better electrocatalytic activity(i.e.,lower peak potential and higher peak current)for AA electrooxidation and higher analytical performance for AA determination(i.e.,wider linear range,higher sensitivity and lower detection limit),which could be most likely due to the high density of defective sites and large specific surface area of DFTs-CAs.Especially,the DFTs-CAs/GCE was used for evaluating the AA level in real samples(i.e.,medical injection dose,vitamin C tablets,fresh orange juice and human urine)and the results are satisfactory.     

Voltammetric Determination of Folic Acid Using Adsorption of Methylene Blue onto Electrodeposited of Reduced Graphene Oxide Film Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of folic acid by adsorbing methylene blue onto electrodeposited reduced graphene oxide film modified glassy carbon electrode (MB/ERGO/GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology of the MB/ERGO/GCE modified electrode was characterized using scanning electron microscopy, displays that both MB and ERGO distributed homogeneously on the surface of GCE. The MB/ERGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE, MB/GCE, and ERGO/GCE. The electrochemical behaviors of folic acid at MB/ERGO/GCE were investigated by cyclic voltammetry, suggesting that the modified electrode exhibited excellent electrocatalytic activity towards folic acid compared with other electrodes. Under physiological condition, the MB/ERGO/GCE modified electrode showed a linear voltammetric response from 4.0 μM to 167 μM for folic acid, and with the detection limit of 0.5 μM (S/N=3). The stability, reproducibility and anti‐interference ability of the modified electrode were examined. The developed method has been successfully applied to determination of FA in tablets with a satisfactory recovery from 96 % to 100 %. The work demonstrated that the electroactive MB adsorbing onto graphene modified electrode showed an enhanced electron transfer property and a high resolution capacity to FA.     

电聚合烟酰胺制备电化学传感器：同时测定多巴胺、尿酸和抗坏血酸

用循环伏安法（CV）选择不同电位区间来电聚合烟酰胺（NA）得到了两种聚合物膜修饰电极：poly-niacinamide/GCE (poly-NA/GCE)和poly- nicotinic acid /GCE (poly-NC/GCE)。这两电极都具有显著电化学催化作用,能明显地降低多巴胺（DA）、尿酸（UA）和抗坏血酸(AA)的氧化过电位,并在混合溶液中使这些物质的氧化峰电位距离足够大,可进行三物质的同时测定。poly-NC/GCE的电催化性能更好一些,用差分脉冲伏安法（DPV）测定抗坏血酸,线性范围为75–3000 µmol L-1,电流灵敏度为5.6 mA•L•mol-1;测定多巴胺,线性范围为0.37 – 16 µmol L-1,电流灵敏度为1140 mA•L•mol-1; 测定尿酸,线性范围为0.74 – 230 µmol L-1,电流灵敏度为102 mA•L•mol-1。该电极具有很高的灵敏度、选择性和抗污染能力。     

Preparation of polyaniline modified electrode in novel ionic liquid and its application in ion chromatography

In this work, a promising electrochemical detector has been fabricated by immersing a glass carbon electrode (GCE) in aniline containing novel ionic liquid and scanning between -1.0 and 1.0 V for 40 cycles, and was used in ion chromatography (IC) system. The morphology of the modified electrode surface was characterized by scanning electron microscope (SEM). The polyaniline (PANI) film showed excellent electrocatalytic activity than bare GCE and provided enhanced selectivity and stability for the detection of ascorbic acid (AA). Separated by IC with phosphate buffer solution (pH = 5.2) as eluent, AA could be determined by the PANI/GCE successfully at the working potential of 0.3 V. The retention time of AA was approximately 5.75 min, and the peak shape of AA was satisfactory. The calibration curve of AA was linear (r > 0.99), in the range between 0.05 mg/L and 1000 mg/L and the detection limit was 23.41 μg/L (S/N = 3). The proposed method was successfully applied in the detection of AA in four beverage samples. The recoveries of AA in these samples were from 92.32% to 110.57%.     

Electrocatalytic activities of Nafion/CdSe/Self-doped polyaniline composites to dopamine,uric acid,and ascorbic acid

Composites of Nafion, COOH-capped CdSe, and self-doped polyaniline (SPAN) were used to prepare novel chemical modified glassy carbon electrodes (Nafion/CdSe/SPAN/GCE). The electrocatalytic activities of the modified GCE to the redox reactions of dopamine (DA), uric acid (UA), and ascorbic acid (AA) were investigated by cyclic voltammetry (CV). CV curves revealed that the electrocatalytic activities of Nafion/CdSe/SPAN/GCE to oxidations of the analytes in solution of pH 7 were in the order of DA?>?UA?>?AA. This order was consistent with the strong-to-low extent of interactions between the modified GCE and the analytes. These interactions were consistent with the observations that the oxidation rate of DA followed a diffusion-controlled process whereas that of UA followed a surface adsorption-controlled process. The composites of casting at higher pH levels were found to exhibit better CdSe and SPAN dispersions in films and higher electrocatalytic activities. CdSe and SPAN exhibited insignificant synergistic effects on the oxidations of DA when cast from Nafion solutions of both low and high pHs whereas CdSe and SPAN exhibited much synergistic effects on the oxidations of UA when cast from the Nafion solution of high pH at 12.     

Electrochemically selective determination of dopamine in the presence of ascorbic and uric acids on the surface of the modified Nafion/single wall carbon nanotube/poly(3-methylthiophene) glassy carbon electrodes

A voltammetric method based on a combination of incorporated Nafion, single-walled carbon nanotubes and poly(3-methylthiophene) film-modified glassy carbon electrode (NF/SWCNT/PMT/GCE) has been successfully developed for selective determination of dopamine (DA) in the ternary mixture of dopamine, ascorbic acid (AA) and uric acid (UA) in 0.1M phosphate buffer solution (PBS) pH 4. It was shown that to detect DA from binary DA-AA mixture, the use of NF/PMT/GCE was sufficient, but to detect DA from ternary DA-AA-UA mixture NF/SWCNT/PMT/GCE was required. The later modified electrode exhibits superior electrocatalytic activity towards AA, DA and UA thanks to synergic effect of NF/SWCNT (combining unique properties of SWCNT such as high specific surface area, electrocatalytic and adsorptive properties, with the cation selectivity of NF). On the surface of NF/SWCNT/PMT/GCE AA, DA, UA were oxidized respectively at distinguishable potentials of 0.15, 0.37 and 0.53 V (vs. Ag/AgCl), to form well-defined and sharp peaks, making possible simultaneous determination of each compound. Also, it has several advantages, such as simple preparation method, high sensitivity, low detection limit and excellent reproducibility. Thus, the proposed NF/SWCNT/PMT/GCE could be advantageously employed for the determination of DA in real pharmaceutical formulations.     

多巴胺在聚亚甲基蓝/石墨烯修饰电极上的电化学行为研究

利用电聚合方法在石墨烯修饰的玻碳电极表面制备了聚亚甲基蓝/石墨烯修饰电极(PMB/GH/GCE)。采用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了多巴胺(DA)和抗坏血酸(AA)在该修饰电极上的电化学行为。在pH 6.9的磷酸盐缓冲溶液中,DA和AA分别在0.208 V和-0.108 V处产生灵敏的氧化峰,与其在聚亚甲基蓝和石墨烯单层修饰电极上的电化学行为相比,两者的峰电流明显增加,峰电位差达316 mV。研究表明,电聚合方法使亚甲基蓝牢固地非共价修饰到石墨烯上,并产生协同增效作用,较好地提高了电极的灵敏度和分子识别性能,有利于在大量AA存在下实现对DA的选择性测定。在1.00×10-3mol/L AA的存在下,DA的差分脉冲伏安法峰电流与其浓度在1.00×10-7～5.00×10-3mol/L范围内呈良好的线性关系,检出限达1.00×10-8mol/L。将该方法用于盐酸多巴胺注射液的测定,结果满意。     

Enhanced sensing of dopamine in the present of ascorbic acid based on graphene/poly(p-aminobenzoic acid) composite film

Graphene/p-aminobenzoic acid composite film modified glassy carbon electrode (Gr/p-ABA/GCE) was first employed for the sensitive determination of dopamine (DA). The electrochemical behavior of DA at the modified electrode was investigated by cyclic voltametry (CV), differential pulse voltametry (DPV) and amperometric curve. The oxidation peak currents of DA increased dramatically at Gr/p-ABA/GCE. The modified electrode was used to electrochemically detect dopamine (DA) in the presence of ascorbic acid (AA). The Gr/p-ABA composite film showed excellent electrocatalytic activity for the oxidation of DA in phosphate buffer solution (pH 6.5). The peak separation between DA and AA was large up to 220 mV. Using DPV technique, the calibration curve for DA determination was obtained in the range of 0.05-10 μM. The detection limit for DA was 20 nM. AA did not interfere with the determination of DA because of the very distinct attractive interaction between DA cations and the negatively Gr/p-ABA composite film. The proposed method exhibited good stability and reproducibility.     

Stable and Sensitive Amperometric Determination of Endocrine Disruptor Bisphenol A at Residual Metal Impurities Within SWCNT

A simple and attentive method was attempted for the determination of endocrine disruptor molecule, Bisphenol A (BPA) using residual metal impurity act as a reactant present in as received SWCNT. The electrochemical behavior of BPA oxidation and its reaction mechanism was investigated by cyclic voltammetry using “as received SWCNT modified on glassy carbon electrode” (SWCNT/GCE) and the obtained results were compared with bare GCE. The SWCNT/GCE showed high electrocatalytic activity, sensitivity, stability and more importantly not much surface fouling compared with bare GCE. This is because of the formation of electroactive quinone and catechol as byproducts on SWCNT/GCE during electro‐oxidation of BPA. More interestingly, the electrochemically acid treated SWCNT/GCE not showed any characteristic oxidation and reduction peaks during electro‐oxidation of BPA which indicates that the presence of a residual metal impurity in SWCNT plays a vital role in electro‐oxidation of BPA. The amperometric detection of BPA oxidation on SWCNT/GCE showed excellent stability and good linear response from the wide range of concentration of 10–100 μM. The limit of detection and sensitivity of BPA electro‐oxidation on SWCNT/GCE is to be 7.3 μM (S/N=3) and 0.6494 μA/μM cm² respectively. Finally, the fabricated sensor using SWCNT/GCE was successfully applied for the detection of BPA in plastic water bottles with excellent recovery range from 98–102 %.     

The electrochemical polymerization of <Emphasis Type="Italic">o</Emphasis>-phenylenediamine on <Emphasis Type="SmallCaps">l</Emphasis>-tyrosine functionalized glassy carbon electrode and its application

The polymerization of o-phenylenediamine (OPD) on l-tyrosine (Tyr) functionalized glassy carbon electrode (GCE) and its electro-catalytic oxidation towards ascorbic acid (AA) had been studied in this report. l-Tyrosine was first covalently grafted on GCE surface via electrochemical oxidation, which was followed by the electrochemical polymerization of OPD on the l-tyrosine functionalized GCE. Then, the poly(o-phenylenediamine)/l-tyrosine composite film modified GCE (POPD-Tyr/GCE) was obtained. X-ray photo-electron spectroscopy (XPS), field emission scanning electron microscope (SEM), and electrochemical techniques have been used to characterize the grafting of l-tyrosine and the polymerization and morphology of OPD film on GCE surface. Due to the doping of the carboxylic functionalities in l-tyrosine molecules, the POPD film showed good redox activity in neutral medium, and thus, the POPD-Tyr/GCE exhibited excellent electrocatalytic response to AA in 0.1 mol l⁻¹ phosphate buffer solution (PBS, pH 6.8). The anode peak potential of AA shifted from 0.58 V at GCE to 0.35 V at POPD-Tyr/GCE with a greatly enhanced current response. A linear calibration graph was obtained over the AA concentration range of 2.5 × 10⁻⁴–1.5 × 10^–3 mol l⁻¹ with a correlation coefficient of 0.9998. The detection limit (3δ) for AA was 9.2 × 10⁻⁵ mol l⁻¹. The modified electrode showed good stability and reproducibility and had been used for the determination of AA content in vitamin C tablet with satisfactory results.     

Electrocatalytic Oxidation of Estrogenic Phenolic Compounds at a Nickel‐Modified Glassy Carbon Electrode

This paper demonstrates for the first time, successful electrocatalytic oxidation of electroactive estrogenic phenolic compounds (EPCs) at a nickel‐modified glassy carbon electrode (Ni‐GCE). The electrode was evaluated in terms of electrocatalytic activity, sensitivity, linear dynamic range, limit of detection, and response stability. In comparison to bare glassy carbon electrode, current amplification was observed for EPCs at Ni‐GCE, for example, for a 40 µM estrone at Ni‐GCE was amplified by a factor of 1224. The Ni‐GCE gave good figures of merit with no evidence of electrode fouling. As an example, the limit of detection (S/N=3) for 17β‐estradiol was 100 nM and the response precision (n=5) was 3.4 %.     

Sensitive Voltammetric Determination of Baicalein at Thermally Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of the flavonoid baicalein by using a thermally reduced graphene oxide (TRGO) modified glassy carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology and structure of TRGO investigated by atomic force microscopy, FT‐IR spectroscopy and Raman spectroscopy reveal that the TRGO prepared maintained as single or bilayer sheets and with significant edge‐plane‐like defect sites. The TRGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE and GO/GCE electrodes. The electrochemical behaviors of baicalein at the TRGO/GCE were investigated by cyclic voltammetry, suggesting that the TRGO/GCE exhibits excellent electrocatalytic activity to baicalein. Under physiological conditions, the modified electrode showed linear voltammetric response from 10 nM to 10 µM for baicalein, with a detection limit of 6.0 nM. This work demonstrates that the graphene‐modified electrode is a promising tool for electrochemical determination of flavonoid drugs.     

Electrochemical property and electroanalytical application of large mesoporous carbons

This article reports on the electrochemical property of large mesoporous carbons (LMC) synthesized using nano-CaCO₃ as a template and sucrose as a carbon precursor. Though a simple preparation method for LMC, the LMC modified glassy carbon electrode (LMC/GCE) exhibited good electrochemical activity for some common electroactive compounds, such as ascorbic acid (AA), uric acid (UA), epinephrine (EP) and tryptophan (Trp). The unique properties of LMC were also compared with those of carbon nanotubes (CNT), and the results showed that the LMC possessed a much better property than CNT. In addition, the LMC/GCE was also used to analyze the β-nicotinamide adenine dinucleotide (NADH) and hydrogen peroxide (H₂O₂) and showed a high sensitivity and low detection limit. Based on a simple preparation method and good electrochemical property, the LMC represents a new class of carbon electrode for electrochemical sensor applications.     

Electrochemical Studies of Pirarubicin and Its Interaction with DNA at a Co／GC Ion Implantation Modified Electrode

IntroductionIon implantation is a new material surfacemodification technique.It has been also applied tostudying the electrochemical behaviors of organicdrugs and biological materials as well as their de-terminations. This method offers good stability,reproductivity and catalytic activity[1] .Pirarubicin( THP) is an active highly effective and new antitu-moral anthracycline antibiotic,which has gainedwidespread clinical use in the chemotherapeutictreatment of a variety of human cancers.The d…     

Selective Electroanalysis of Ascorbic Acid Using a Nickel Hexacyanoferrate and Poly(3,4‐ethylenedioxythiophene) Hybrid Film Modified Electrode

The mixed‐valent nickel hexacyanoferrate (NiHCF) and poly(3,4‐ethylenedioxythiophene) (PEDOT) hybrid film (NiHCF‐PEDOT) was prepared on a glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. The films were characterized using atomic force microscopy, field emission scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and electrochemical impedance spectroscopy (AC impedance). The advantages of these films were demonstrated for the detection of ascorbic acid (AA) using cyclic voltammetry and amperometric techniques. The electrocatalytic oxidation of AA at different electrode surfaces, such as the bare GCE, the NiHCF/GCE, and the NiHCF‐PEDOT/GCE modified electrodes, was determined in phosphate buffer solution (pH 7). The AA electrochemical sensor exhibited a linear response from 5×10⁻⁶ to 1.5×10⁻⁴ M (R²=0.9973) and from 1.55×10⁻⁴ to 3×10⁻⁴ M (R²=0.9983), detection limit=1×10⁻⁶ M, with a fast response time (3 s) for AA determination. In addition, the NiHCF‐PEDOT/GCE was advantageous in terms of its simple preparation, specificity, stability and reproducibility.     

Selective determination of epinephrine in the presence of ascorbic acid and uric acid by electrocatalytic oxidation at poly(eriochrome black T) film-modified glassy carbon electrode.

An electropolymerized film of eriochrome black T (EBT) has been prepared at a glassy carbon electrode (GCE) by cyclic voltammetry (CV). The poly(EBT) membrane at GCE exhibits an excellent electrocatalytic activity towards the oxidation of epinephrine (EP), ascorbic acid (AA) and uric acid (UA) in acidic solution and reduced the overpotential for the oxidation of EP. The poly(EBT)-coated electrode could separately detect EP, AA and UA in their mixture with the potential differences of 180 and 160 mV for EP-AA and UA-EP, respectively, which are large enough to allow for determination of EP in the presence of AA and UA. Using differential pulse voltammetry, the peak current of EP recorded in pH 3.5 solution was linearly dependent on EP's concentration in the range of 2.5 - 50 microM. Due to its good selectivity and stability, the polymer-coated GCE was successfully applied to the determination of EP in real samples.     

Fabrication,Characterization, and Application of ‘Sandwich‐Type’ Electrode Based on Single‐Walled Carbon Nanotubes and Room Temperature Ionic Liquid

The much‐enhanced electrochemical responses of potassium ferricyanide and methylene blue (MB) were firstly explored at the glassy carbon electrode modified with single‐walled carbon nanotubes (SWNT/GCE), indicating the distinct electrochemical activity of SWNTs towards electroactive molecules. A hydrophobic room temperature ionic liquid (RTIL), 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆), was used as electrode modification material, which presented wide electrochemical windows, proton permeation and selective extraction ability. In consideration with the advantages of SWNTs and RTIL in detecting target molecules (TMs), a novel strategy of ‘sandwich–type’ electrode was established with TMs confined by RTIL between the SWNT/GCE and the RTIL membrane. The strategy was used for electrochemical detection of ascorbic acid (AA) and dopamine (DA), and detection limits of 400 and 80 fmol could be obtained, respectively. The selective detection of DA in the presence of high amount of AA could also be realized. This protocol presented many attractive advantages towards voltammetric detection of TMs, such as low sample demand, low cost, high sensitivity, and good stability.