Sensitive Electrochemical Detection of Horseradish Peroxidase at Disposable Screen‐Printed Carbon Electrode

A rapid, simple and sensitive electrochemical assay of horseradish peroxidase (HRP) performed on disposable screen‐printed carbon electrode was developed. HRP activities were monitored by square‐wave voltammetric (SWV) measuring the electroactive enzymatic product in the presence of o‐aminophenol and hydrogen peroxide substrate solution. SWV analysis demonstrated a greater sensitivity and shorter analysis time than the widely used amperometric and differential‐pulsed voltammetric methods. The voltammetric characteristics of substrate and enzymatic product as well as the parameters of SWV analysis were optimized. Under optimized conditions, a linear response for HRP from 0.003 to 0.1 U/mL and a detection limit of 0.002 U/mL (1.25×10^?15 mol in 25 μL) were obtained with a good precision (RSD=8%; n=6). This rapid and sensitive HRP assay with microliter‐assay volume could be readily integrated to portable devices and point‐of‐care (POC) diagnosis applications.     

Electrochemical Detection of Steroid Hormones Using a Nickel‐Modified Glassy Carbon Electrode

This paper demonstrates the development of an analytical method for detecting steroid hormones by coupling HPLC to electrochemical detection, using a nickel‐modified glassy carbon electrode. The method was evaluated in terms of sensitivity, linear dynamic range, limit of detection, and response stability. The developed method exhibited good figures of merit for the steroid hormones studied with no evidence of electrode fouling. As an example, the limit of detection (S/N=3) for E3 was 0.10 µM and the response precision (n=5) was 0.6 %. The application of the method for the analysis of a real river water sample is demonstrated.     

单壁碳纳米管-氨基二茂铁复合物修饰玻碳电极对对硝基苯酚的电化学检测

本研究用氨基二茂铁(Aminoferrocene,AFc)经重氮化反应后修饰单壁碳纳米管(SWNTs),制备SWNTs-AFc复合物,并以该复合物修饰玻碳电极(GCE),通过循环伏安法(CV)和差分脉冲伏安法(DPV)等电化学方法检测对硝基苯酚(p-NP)。结果表明,与裸玻碳电极相比,SWNTs-AFc/GCE对p-NP响应的还原过电位显著减小,峰电流大大增强,p-NP的检测线性范围为1~850μmol/L(R2=0.997),检测限为1μmol/L。该方法电流响应快、灵敏度高、检测限低,具有良好的应用前景。     

Catalysis‐Electrochemical Detection of Horseradish Peroxidase at Zeptomole Level in Capillary Zone Electrophoresis

Capillary zone electrophoresis with catalysis‐electrochemical detection has been developed and applied to determining horseradish peroxidase (HRP) at zeptomole levels. In this method, an on‐line enzyme catalysis reactor with a reaction capillary was designed. Isoenzymes of HRP were separated by capillary zone electrophoresis, and then they catalyzed the enzyme substrate 3,3′,5,5′‐tetramethylbenzide (TMB(Red)) and H₂O₂ in the reaction capillary. The reaction product, TMB(Ox), could be determined using amperometric detection on a carbon fiber microdisk bundle electrode at the outlet of the reaction capillary. Because of enzyme amplification, a significant amount of TMB(Ox) could be produced for detection. Therefore, the limit of detection (LOD) of HRP is very low. The optimum conditions of the method are 1.5×10^?2 mol/L borate (pH 7.4) for the run buffer, 2×10^?3 mol/L for the concentration of H₂O₂, 2×10^?4 mol/L TMB(Red)+2.0×10^?2 mol/L citrate‐phosphate (pH 5.0) for the substrate solution, 40 cm for the liquid pressure height, 20 kV for the separation voltage, 100 mV for the detection potential. HRP could be measured with a detection limit of 4.8×10^?12 mol/L or 47.5 zmol (S/N=3). The linear range is from 2.40×10^?11 to 2.40×10^?8 mol/L. Using this method, commercial HRP was measured at zeptomole within ten minutes.     

Electrochemical Detection of Methimazole by Capillary Electrophoresis at a Carbon Fiber Microdisk Electrode

We developed a sensitive, simple and low cost method to determine methimazole based on capillary electrophoresis with electrochemical detection (CE‐EC) at a carbon fiber microdisk electrode (CFE). We investigated the effects of detection potential, the concentration and pH value of the phosphate buffer, and injection time as well as separation voltage on the detection of methimazole. Under the optimized conditions: the detection potential at 1.30 V, 10 mmol/L phosphate buffer (pH 7.0), injection time 30 s at a height of 20 centimeter and separation voltage at 15 kV, the linear range was obtained from 1.0×10^?7 to 2.0×10^?4 mol/L, covering 3 orders of magnitude with a correlation coefficient of 0.9995. The LOD (S/N=3) obtained was 5.0×10^?8 mol/L. The RSD of migration time and peak current for 2.0×10^?4 mol/L methimazole was 1.04% and 1.54% (n=10), respectively. The method was also used to analyze methimazole tablets and human urine sample.     

中空介孔碳球修饰的丝网印刷碳电极用于尼古丁的电化学检测

将一步法合成的中空介孔碳球(HMCS)修饰在丝网印刷碳电极(SPCE)上,得到了用于尼古丁电化学检测的新型电极(HMCS/SPCE)。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、粉末X射线衍射(XRD)、X射线光电子能谱(XPS)以及拉曼光谱等方法对HMCS及修饰电极HMCS/SPCE进行表征。由于HMCS具有较大的电化学活性面积和良好的导电性,修饰电极HMCS/SPCE对尼古丁表现出良好的电催化活性。在优化实验条件下,电极HMCS/SPCE对尼古丁的检测线性范围为0~500μmol/L,灵敏度为0.850 m A/(cm~2·mmol·L~(-1)),检出限为0.058μmol/L。制备的传感器具有重复性好、稳定性高等特点,可用于实际烟草样品中尼古丁的检测。     

Enhanced Electron Transfer Properties of Carbon Spheres Chains via Electrochemical Functionalization

Electrochemical functionalization via electrochemical oxidation in nitric acid of various concentrations (0.1 M, 0.2 M and 2 M) was employed to enrich the surface of carbon sphere chains (CSCs) with some useful physico‐chemical properties such as hydrophilicity, oxygen functionalities and electron transfer properties. The functionalization process in 2 M HNO₃ solution led to the creation of an original hybrid material made of carbon sphere chains‐carbon nanobuds. This material displayed a prominent response towards the electrocatalytic oxidation of ferrocyanide with a peak current three times and twice superior to those delivered by pristine CSC and multiwalled carbon nanotubes (MWCNTs) electrodes, respectively.     

Electrochemical Sensor for Arabinose Based on Template‐free Pb/Cd Branched Nanorods on Glassy Carbon Electrode

In this paper, the electrochemical behavior of glassy carbon electrodes modified with Cd/Pb (GC/Cd/Pb) branched nanorodes (NRs) was studied using cyclic voltammetry technique. The obtained results showed that the branched nanorods of Cd/Pb can be readily prepared without any templates. The modified electrode was characterized using scanning electron microscopy (SEM), energy dispersive X‐ray analysis (EDAX) and electrochemical impedance spectroscopy (EIS) techniques. The electrocatalytic behavior of GC/Cd/Pb electrode showed an increase in oxidation signal of arabinose by increasing its concentration. The catalytic current was linearly related to arabinose concentration in the range of 0.6 to 6.8 μM with a limit of detection 0.2 μM.     

Electrochemical Determination of Fenitrothion Organophosphorus Pesticide Using Polyzincon Modified‐glassy Carbon Electrode

In this paper, a glassy carbon electrode (GCE) was modified with polyzincon. The modified electrode was used as a simple, inexpensive and highly sensitive electrochemical sensor for the determination of organophosphorus pesticide fenitrothion. To fabricate the electrochemical sensor, GCE was immersed in 0.10 mmol L⁻¹ zincon solutions at pH 7.0 and then successively scanned between −1.00 to 2.20 V (vs . Ag/AgCl) at a scan rate of 70 mV s⁻¹ for six cycles. The morphology and structure of the polyzincon were studied with atomic force microscopy and scanning electron microscopy. A comparison of the electrochemical behavior of fenitrothion on the unmodified and polyzincon modified‐GCE showed that in the modified electrode not only the oxidation peak current increased, but also the overpotential shifted to lower one. The experimental conditions such as sample solution pH, accumulation potential, and time were optimized. The differential pulse voltammetric responses of fenitrothion at potential about −0.60 V was used for the determination of fenitrothion. The peak current increased with increasing the concentration of fenitrothion in the range of 5 to 8600 nmol L⁻¹ with a detection limit of 1.5 nmol L⁻¹. Finally, the electrochemical sensor was used for the analysis of fenitrothion in water and fruit samples.     

Impedimetric Enzyme‐Free Detection of Glucose via a Computation‐Designed Molecularly Imprinted Electrochemical Sensor Fabricated on Porous Ni Foam

Here we report a new molecularly imprinted electrochemical sensor (MIECS) for the impedimetric enzyme‐free analysis of glucose. A computational modeling strategy was first utilized to screen promising functional monomers for imprinting assembly, and simulation data suggested that methacrylic acid (MAA) exhibited a preferable capability to recognize the target molecule compared to other common monomers. Then the MIECS was prepared via introducing MAA‐based recognition sites onto a porous Ni foam with large surface. The fabricated sensor was subtly characterized by Raman spectroscopy, scanning electron microscopy, and cyclic voltammetry, and an impedimetric method was selected to detect the glucose target in a basic medium. Experimental results demonstrated that the proposed MIECS could selectively recognize glucose against coexisting species, with good linear responses of the charge transfer resistance upon the target concentration in the scope of 10∼55 mM. These results indicate its potential applications in the recognization and detection of glucose in complex matrices.     

Electrochemical Detection of Abasic Site‐Containing DNA

A simple and rapid approach for detecting apurinic (AP) sites in DNA, based on direct stripping chronopotentiometric measurements of the adenine and guanine nucleobases at a graphite electrode is described. Tetrahydrofuranyl residues, lacking a nucleobase moiety, were utilized for designing the AP sites and were incorporated in 19‐mer oligonucleotides. The change of adenine‐to‐guanine response ratio (A/G) in one‐, two‐ or three‐substituted adenosine residues for stable analogs of AP sites was exploited for electrochemical measurements of the adenine loss. The resulting A/G response ratio decreases linearly upon increasing the number of AP sites in the oligonucleotides; the values of A/G electrochemical signals were slightly enhanced when compared to the actual purine content. HPLC analysis of the released nucleobases confirmed that the sulfuric acid‐induced oligonucleotide cleavage provides complete apurination and dissolution of the released nucleobases in aqueous solution. Additional experiments with mixtures of free nucleobases and purine nucleosides reveal that the larger A/G ratio observed in the electrochemical analysis of AP‐site‐containing oligomers is attributed to the influence of the acid and/or thermal decomposition products (particularly the sugar fragments). This study represents the first step in developing a simple and direct electrochemical assay of AP sites in single‐stranded DNA.     

PAMAM Dendrimers‐Based DNA Biosensors for Electrochemical Detection of DNA Hybridization

Gold electrodes were modified with submonolayers of mercaptoacetic acid (RSH) and further reacted with poly(amidoamine) (PAMAM) dendrimers (generation 4.0) to obtain thin films, on which DNA probe was later immobilized to afford a stable recognition layers. The characterization of the PAMAM/RSH‐modified electrode was investigated by cyclic voltammetry (CV) and electrochemical impedance measurement. Differential pulse voltammogram (DPV) measurement was used to monitor DNA hybridization with daunomycin (DNR) as indicator. Experiments carried out with these novel materials not only showed an improved DNA attachment quantity on the dendrimers‐modified electrodes compared to DNA sensors with oligonucleotides directly immobilized on Au electrodes, but also exhibited a high selectivity, sensitivity and stability for the measurement of DNA hybridization.     

纳米TiN碳糊电极对青霉素的电化学检测

以纳米氮化钛(TiN)为电活性物质,制备了用于检测青霉素的纳米TiN修饰碳糊电极.研究了该碳糊电极中石墨与纳米TiN的质量比、电极面积、溶液pH值及缓冲容量等因素对青霉素检测效果的影响.结果表明,在优化的条件(石墨与TiN的质量比为2∶1,电极面积为1 mm~2,溶液pH值为7.2以及缓冲容量为20 mmol/L KH_2PO_4)下,该电极检出限为2×10~(-5)mol/L,线性检测范围为4×10~(-5)~3.2×10~(-3)mol/L.利用Zeta电位及交流阻抗的方法,揭示了纳米TiN碳糊电极检测青霉素的机理为纳米TiN对青霉素的特异性吸附.纳米TiN碳糊电极展现出良好的稳定性、选择性和重复性,在青霉素检测领域具有广阔的应用前景.     

Sensitive Electrochemical Detection of Oxalate at a Positively Charged Boron‐Doped Diamond Surface

Allyltriethylammonium bromide (ATAB) was covalently attached to the surface of hydrogen‐terminated boron‐doped diamond (BDD) thin films using a photochemical method to fabricate positively charged electrode surfaces. The anodic current for oxalate oxidation both in cyclic voltammetry and in flow‐injection analysis with amperometry was found to be up to two times larger at ATAB‐modified BDD (ATAB‐BDD) than at an unmodified BDD electrode, which may be based on the electrostatic interaction between the oxalate anion and the electrode surface. In addition, the stability of the electrochemical detection of oxalate was improved at the ATAB‐BDD electrode compared to the unmodified electrode.     

Sequence Specific Electrochemical DNA Detection Based on Solution‐Phase Competitive Hybridization

We report a novel electrochemical method for detecting sequence‐specific DNA based on competitive hybridization that occurs in a homogeneous solution phase instead of on a solution‐electrode interface as in previously reported competition‐based electrochemical DNA detection schemes. The method utilizes the competition between the target DNA (t‐DNA) and a ferrocene‐labeled peptide nucleic acid probe (Fc‐PNA) to hybridize with a probe DNA (p‐DNA) in solution. The neutral PNA backbone and the electrostatic repulsion between the negatively‐charged DNA backbone and the negatively‐charged electrode surface are then exploited to determine the result of the competition through measurement of the electrochemical signal of Fc. Upon the introduction of the t‐DNA, the stronger hybridization affinity between the t‐DNA and p‐DNA releases the Fc‐PNA from the Fc‐PNA/p‐DNA hybrid, allowing it to freely diffuse to the negatively charged electrode to produce a significantly enhanced electrochemical signal of Fc. Therefore, the presence of the t‐DNA is indicated by the appearance or enhancement of the electrochemical signal, rendering a signal‐on DNA detection, which is less susceptible to false positive and can produce more reliable results than signal‐off detection methods. All the competitive hybridizations occur in a homogeneous solution phase, resulting in very high hybridization efficiency and therefore extremely short assay time. This simple and fast signal‐on solution‐competition‐based electrochemical DNA detection strategy has promising potential to find application in fields such as nucleic acid‐based point‐of‐care testing.     

Reduced Graphene Oxide/Carbon Nanotube/Gold Nanoparticles Nanocomposite Functionalized Screen‐Printed Electrode for Sensitive Electrochemical Detection of Endocrine Disruptor Bisphenol A

We fabricated a highly sensitive electrochemical sensor for the determination of bisphenol A (BPA) in aqueous solution by using reduced graphene oxide (RGO), carbon nanotubes (CNT), and gold nanoparticles (AuNPs)‐modified screen‐printed electrode (SPE). GO/CNT nanocomposite was directly reduced to RGO/CNT on SPE at room temperature. AuNPs were then electrochemically deposited in situ on RGO/CNT‐modified SPE. Under optimized conditions, differential pulse voltammetry (DPV) produced linear current responses for BPA concentrations of 1.45 to 20 and 20 to 1,490 nM, with a calculated detection limit of an ultralow 800 pM. The sensor response was unaffected by the presence of interferents such as phenol, p‐nitrophenol, pyrocatechol, 2,4‐dinitrophenol, and hydroquinone.     

Electrochemically Prepared Three‐dimensional Porous Nitrogen‐doped Graphene Modified Electrode for Non‐enzymatic Detection of Hydrogen Peroxide

A facile and green electrochemical method for the fabrication of three‐dimensional porous nitrogen‐doped graphene (3DNG) modified electrode was reported. This method embraces two consecutive steps: First, 3D graphene/polypyrrole (ERGO/PPy) composite was prepared by electrochemical co‐deposition of graphene and polypyrrole on a gold foil. Subsequently, the ERGO/PPy composite modified gold electrode was annealed at high temperature. Thus 3DNG modified electrode was obtained. Scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to characterize the structure and morphology of the electrode. The electrode exhibits excellent electroanalytical performance for the reduction of hydrogen peroxide (H₂O₂). By linear sweep voltammetric measurement, the cathodic peak current was linearly proportional to H₂O₂ concentration in the range from 0.6 μM to 2.1 mM with a sensitivity of 1.0 μA μM⁻¹ cm⁻². The detection limit was ascertained to be 0.3 μM. The anti‐interference ability, reproducibility and stability of the electrode were carried out and the electrode was applied to the detection of H₂O₂ in serum sample with recoveries from 98.4 % to 103.2 %.     

An Electrochemical Sensor Based on Nitrogen‐doped Carbon Nanofiber for Bisphenol A Determination

In this paper, bisphenol A was determined by electrochemical method at a nitrogen‐doped carbon nanofiber modified carbon paste electrode (NCNF/CPE) with high sensitivity and good selectivity. NCNF was obtained by a simple electrospinning followed by carbonization procedure, in which polyacrylonitrile (PAN) as precursor and nitrogen doping was realized by re‐utilizing the tail gas that produced in the thermal pretreatment process. Good reproducibility and high stability were obtained for BPA detection at NCNF modified CPE. Current response plotted with BPA concentration was linear in the range of 0.1–60 μM with LOD of 0.05 μM. The proposed electrochemical sensor was employed for BPA determination with satisfactory recoveries for real water samples, indicating the practical applicability of NCNF/CPE.     

Electrochemical Detection of Thioether‐Based Fluorosurfactants in Aqueous Film‐Forming Foam (AFFF)

Using cyclic voltammetry (CV) and impedance (IMP), we report a simple approach to detect new fluorosurfactant ingredient formulated in aqueous film‐forming foam (AFFF), specifically the thioether‐based one. First, we employ ion chromatography (IC) to identify all possible elements with the help of chemical oxidation and infrared spectrum (IR) to identify all possible functional groups. We thus propose a possible thioether‐based molecular structure of fluorosurfactant formulated in AFFF. By studying the self‐assembled monolayer (SAM) formed on gold (Au) surface via thio‐Au bond, we establish a relationship between the SAM density and the amount of the thioether‐based fluorosurfactant for the AFFF detection. Solid phase extraction (SPE) and nanoporous Au electrode are employed to enhance the sensitivity. Consequently, a detection limit of 10 ppb (v/v) has been achieved for AFFF‐spiked tap water sample.     

Electrochemical Characterization of Screen‐Printed Carbon Electrodes by Modification with Chitosan Oligomers

The kinetics on the current amplification of the disposable screen‐printed carbon electrodes (SPCEs) by modification with chitosan oligomers (COs), coupled with the Fe(CN) redox system, were characterized with the variation of electron‐transfer rate constant (k°) and the electroactive area (A_ea) at electrode surface. The nonlinear response characteristics of peak currents with increase in Fe(CN) bulk concentrations complicated the estimation of A_ea in cyclic voltammetric analysis. Upon the modification with COs, the rate constant of SPCEs was not much influenced and the current amplification was characterized with the increase of a better estimated A_ea, obtained from electrochemical impedance measurements and verified with the reciprocal of electron‐transfer resistances linearly proportional to the Fe(CN) bulk concentrations. It is hereby provided for an evaluation of the carbon based electrodes with modification.