碳纳米管/聚二烯丙基二甲基氯化铵/磷钼酸复合膜的组装及其在溴酸盐检测中的应用

通过静电层层组装技术在玻碳(GC)电极表面制备{多壁碳纳米管(MWCNT)/聚二烯丙基二甲基氯化铵(PDDA)}n多层膜,并采用循环伏安法在多层膜的表面电化学修饰一层磷钼酸(PMo12)膜,构筑GC/{MWCNT/PDDA}n-PMo12复合膜修饰电极.利用SEM对比观察{MWCNT/PDDA}n和{PDDA/MWCNT}n-PMo12的微观结构,并研究该复合膜修饰电极的电化学及其对溴酸盐(BrO3-)电催化还原性质.在此基础上研发一种基于GC/{MWCNT/PDDA}n-PMo12复合膜修饰电极的电流型BrO3-传感器,该传感器表现出明显增大的响应电流.在最优的实验条件下,采用电流时间曲线(i-t)法考察该复合膜修饰电极对BrO3-的安培响应.实验结果表明,该传感器在BrO3-浓度为50～400nmol/L的范围内具有良好的线性关系,相关系数R2为0.9950,响应时间为1.53s,检出限为20nmol/L,灵敏度为13.81mA(mmol/L)-1cm-2.     

Direct Electrochemistry of Glucose Oxidase at Carbon Nanotube‐gold Colloid Modified Electrode with Poly(diallyldimethylammonium chloride) Coating

Glucose oxidase showed direct electrochemical transfer at glassy carbon electrodes immobilized with carbon nanotube‐gold colloid (CNT‐Au) composites with poly(diallydimethylammonium chloride) (PDDA) coatings. The modified electrode (GC/CNT/Au/PDDA‐GOD) was employed for the amperometric determination of glucose. Under optimal conditions, the biosensor displayed linear response to glucose from 0.5 to 5 mM with a sensitivity of 2.50 mA M^?1 at an applied potential of ?0.3 V (vs. Ag|AgCl reference).     

Evaluation of a novel composite based on functionalized multi-walled carbon nanotube and iron phthalocyanine for electroanalytical determination of isoniazid

A novel platform for electroanalysis of isoniazid based on graphene-functionalized multi-walled carbon nanotube as support for iron phthalocyanine (FePc/f-MWCNT) has been developed. The FePc/f-MWCNT composite has been dropped on glassy carbon forming FePc/f-MWCNT/GC electrode, which is sensible for isoniazid, decreasing substantially its oxidation potential to +200 mV vs Ag/AgCl. Electrochemical and electroanalytical properties of the FePc/f-MWCNT/GC-modified electrode were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, scanning electrochemical microscopy, and amperometry. The sensor presents better performance in 0.1 mol L^?1 phosphate buffer at pH 7.4. Under optimized conditions, a linear response range from 5 to 476 μmol L^?1 was obtained with a limit of detection and sensitivity of 0.56 μmol L^?1 and 0.023 μA L μmol^?1, respectively. The relative standard deviation for 10 determinations of 100 μmol L^?1 isoniazid was 2.5%. The sensor was successfully applied for isoniazid selective determination in simulated body fluids.     

Fabrication of Nickel Tetrasulfonated Phthalocyanine Functionalized Multiwalled Carbon Nanotubes on Activated Glassy Carbon Electrode for the Detection of Dopamine

The nickel tetrasulfonated phthalocyanine (NiTsPc) functionalized multiwalled carbon nanotube (MWCNT) nanocomposite was prepared by a simple sonochemical method. Here, NiTsPc served as a dispersing agent for MWCNT via π? π interaction between MWCNT and NiTsPc. The activated glassy carbon electrode (AGCE) modified with MWCNT‐NiTsPc composite exhibited a good electrocatalytic ability toward dopamine and displayed a good linear dependence in the concentration range of 20 nM–1.384 mM with a sensitivity of 0.17 µA µM^?1 cm^?2. The detection limit is 1 nM based on the signal‐to‐noise ratio of 3.     

Voltammetric Determination of Hydroquinone using β‐Cyclodextrin/Poly(N‐Acetylaniline)/Carbon Nanotube Composite Modified Glassy Carbon Electrode

Abstract

An electrochemical sensor for hydroquinone (HQ) using β‐cyclodextrin/poly(N‐acetylaniline)/carbon nanotube composite (β‐CD/PAA/MWNTs) modified glassy carbon electrode has been successfully developed. Based on the synergistic effect of MWNTs and conducting PAA polymer and the accumulation effect of β‐CD, the analytical response of the β‐CD/PAA/MWNTs film to the electrochemical behavior of HQ was better than that of a β‐CD/PAA film, a PAA/MWNTs film, a PAA film, or a bare glassy carbon (GC) electrode. Under the conditions chosen, the anodic currents increased linearly with HQ concentration from 1×10^?6 to 5×10^?3 mol l^?1 and the detection limit was 8×10^?7 mol l^?1. This electrochemical sensor showed excellent reproducibility, stability and recovery for the determination of HQ.     

Glucose Biosensor Based on Multi‐Walled Carbon Nanotube Modified Glassy Carbon Electrode

An amperometric glucose biosensor based on multi‐walled carbon nanotube (MWCNT) modified glassy carbon electrode has been developed. MWCNT‐modified glassy carbon electrode was obtained by casting the electrode surface with multi‐walled carbon nanotube materials. Glucose oxidase was co‐immobilized on the MWCNT‐modified glassy carbon surface by electrochemical deposition of poly(o‐phenylenediamine) film. Enhanced catalytic electroreduction behavior of oxygen at MWCNT‐modified electrode surface was observed at a potential of ?0.40 V (vs. Ag|AgCl) in neutral medium. The steady‐state amperometric response to glucose was determined at a selected potential of ?0.30 V by means of the reduction of dissolved oxygen consumed by the enzymatic reaction. Common interferents such as ascorbic acid, 4‐acetamidophenol, and uric acid did not interfere in the glucose determination. The linear range for glucose determination extended to 2.0 mM and the detection limit was estimated to be about 0.03 mM.     

Preparation and Electrochemical Characterization of an Enzyme Electrode Based on Catalase Immobilized onto a Multiwall Carbon Nanotube‐Thionine Film

The present study was aimed at investigating the use of a mixture multiwall carbon nanotube (MWCNT) and thionine (Th) dye in designing of a thionine‐based electrochemical biosensor containing catalase (Ct) enzyme (MWCNT‐Nafion‐Th/Ct) onto a glassy carbon electrode (GCE). The effects of pH, MWCNT concentration and thionine concentration on electrochemical response were explored for optimum analytical performance. The modified electrode exhibited a pair of well‐defined, quasi‐reversible peaks at formal potential (E^o′) = ‐0.218 ± 0.017 V vs. Ag/AgCl corresponding to the Th_ox/Th_red redox couples in the presence of MWCNT, Nafion, and Ct. The electrochemical parameters, including charge‐transfer coefficient (0.36), and apparent heterogeneous electron transfer rate constant (4.28 ± 0.26 s^?1) were determined. Using differential pulse voltammetry, the prepared enzyme electrode exhibited a linear response to hydrogen peroxide (H₂O₂) in the range of 10.0‐100.0 μM with a detection limit 8.7 μM and a sensitivity of 6051.0 μA mM^?1 cm^?2.     

Low potential detection of nicotine at multiwalled carbon nanotube–alumina-coated silica nanocomposite

Electrocatalytic oxidation of nicotine at multiwalled carbon nanotube (MWCNT)–alumina-coated silica (ACS) nanocomposite modified glassy carbon electrode are described. The sensing performance of the MWCNT–ACS nanocomposite modified glassy carbon electrode for the electrooxidation of nicotine was investigated using cyclic voltammetry and amperometry in 0.1 M phosphate buffer solution (pH 8). The MWCNT–ACS nanocomposite modified glassy carbon electrode exhibited the abilities to decrease the electrooxidation potential, to prevent the electrode surface fouling, and to raise the current responses. The MWCNT–ACS nanocomposite responded rapidly to nicotine with a sensitivity of 1.786 A M^?1 cm^?2 and a detection limit of 1.42 μM (according to 3σ criterion). A signal almost 180 times more sensitive was obtained at MWCNT–ACS nanocomposite modified glassy carbon electrodes as compared to bare glassy carbon electrode. The nicotine oxidation potential obtained in this study is much lower than that at boron-doped diamond electrodes.     

Electrochemical oxidation of salicylic acid at well-aligned multiwalled carbon nanotube electrode and its detection

In this paper, an electrochemical sensor for sensitive and convenient determination of salicylic acid (SA) was constructed using well-aligned multiwalled carbon nanotubes as electrode material. Compared to the glassy carbon electrode, the electro-oxidation of SA significantly enhanced at the multiwalled carbon nanotube (MWCNT) electrode. The MWCNT electrode shows a sensitivity of 59.25 μA mM⁻¹, a low detection limit of 0.8 × 10⁻⁶ M and a good response linear range with SA concentration from 2.0 × 10⁻⁶ to 3.0 × 10⁻³ M. In addition, acetylsalicylic acid was determined indirectly after hydrolysis to SA and acetic acid, which simplified the detection process. The mechanism of electrochemical oxidation of SA at the MWCNT electrode is also discussed.     

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.     

毛细管电泳-修饰电极电化学检测法测定饮用水中溴酸盐

通过静电组装技术在碳圆盘电极（PGE）表面制备{聚二烯丙基二甲基氯化铵（PDDA）/多壁碳纳米管（MWCNT）}n/PDDA多膜,并采用循环伏安法在多膜表面电化学修饰一磷钼酸（PMo12）膜,构筑PGE/{PDDA/MWNTs}5/PDDA/PMo12复合膜修饰电极,研究该复合膜修饰电极电化学及其对溴酸盐（BrO3-）电催化还原性质.在此基础上建立毛细管电泳-PGE/{PDDA/MWNTs}5/PDDA/PMo12修饰电极电化学检法定饮用水中溴酸盐分析新方法.在优化实验条件下,电泳峰面积与溴酸根浓度在5.0×10-8～5.0×10-5mol/L范围内呈良好性关系（r=0.9954）,检出为2.0×10-8mol/L（S/N=3）.     

Preparation of an Electrode That Immobilizes NAD‐Dependent Alcohol Dehydrogenase by Using a Redox Polymer Containing 1,10‐Phenanthroline‐5,6‐dione

A redox polymer (PAHA‐Ru), modified electrode exhibited excellent catalytic activity for the electrochemical oxidation of β‐nicotinamide adenine dinucleotide (NADH). PAHA‐Ru was composed of carboxyl groups and ruthenium complexes containing 1,10‐phenanthroline‐5,6‐dione (phen‐dione). The stability of the PAHA‐Ru film was increased by incorporating poly(diallyldimethylammonium chloride) (PDDA) owing to the formation of a polyelectrolyte complex between the PAHA‐Ru and PDDA. The catalytic efficiency of the oxidation of NADH using the PAHA‐Ru/PDDA‐modified electrode was also greater than that using a PAHA‐Ru‐modified electrode. NAD‐dependent alcohol dehydrogenase (ADH) was entrapped in the PAHA‐Ru/PDDA film on the surface of the glassy carbon electrode. Electrochemical oxidation of ethanol using the ADH‐entrapped electrode was also observed.     

A Novel Sensor Based on Manganese azo‐Macrocycle/Carbon Nanotubes to Perform the Oxidation and Reduction Processes of Two Diphenol Isomers

The present work describes the development of a selective and sensitive voltammetric sensor for simultaneous determination of catechol (CC) and hydroquinone (HQ), based on a glassy carbon (GC) electrode modified with manganese phthalocyanine azo‐macrocycle (MnPc) adsorbed on multiwalled carbon nanotubes (MWCNT). Scanning electron microscopy and scanning electrochemical microscopy were used to characterize the composite material (MnPc/MWCNT) on the glassy carbon electrode surface. The modified electrode showed excellent electrochemical activity towards the simultaneous oxidation and reduction of CC and HQ. On the MnPc/MWCNT/GC electrode, both CC and HQ can generate a pair of quasi‐reversible and well‐defined redox peaks. Under optimized experimental and operational conditions, the cathodic peak currents were linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.095 and 0.041 µmol L^?1, respectively. The anodic peak currents were also linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.096 and 0.048 µmol L^?1, respectively. The proposed method was effectively applied for the simultaneous detection of hydroquinone and catechol in water samples and the results were in agreement with those obtained by a comparative method described in the literature.     

Preparation,Characterization, and Bioelectrocatalytic Properties of Hemoglobin Incorporated Multiwalled Carbon Nanotubes‐Poly‐L‐lysine Composite Film Modified Electrodes Towards Bromate

The present work describes preparation of hemoglobin‐incorporated multiwalled carbon nanotubes‐poly‐L ‐lysine (MWCNT‐PLL)/Hb) composite modified electrode film modified glassy carbon electrode (GCE) and its electrocatalytic behavior towards reduction of bromate ( ) in 0.1 M acetate buffer (pH 5.6). The modified electrode has been successfully fabricated by immobilizing hemoglobin on MWCNT dispersed in poly‐L ‐lysine. The surface morphologies of MWCNT, PLL and Hb were characterized using atomic force microscopy (AFM). The voltammetric features suggested that the charge transport through the film was fast and the electrochemical behavior resembles that of surface‐confined redox species. Cyclic voltammetry was used to investigate the electrocatalytic behavior of the modified electrode towards bromate and was compared with that of the CNT‐modified as well as bare electrode. The analytical determination of bromate has been carried out in stirred solution at an optimized potential with a sensitivity of 7.56 μA mM^?1 and the calibration curve was linear between 1.5×0^?5 to 6.0×0^?3 M.     

Electrochemical Sensor Based on Multi‐walled Carbon Nanotube/Gold Nanoparticle Modified Glassy Carbon Electrode for Detection of Estradiol in Environmental Samples

We report a rapid and simple method for sensing estradiol by electro‐oxidation on a multi‐walled carbon nanotube (MWCNT) and gold nanoparticle (AuNP) modified glassy carbon electrode (GCE). Compared with a bare GCE, AuNP/GCE and MWCNT/GCE, the composite modified GCE shows an enhanced response to estradiol in 0.1 M phosphate buffer solution. Experimental parameters, including pH and accumulation time for estradiol determination were optimised at AuNP/MWCNT/GCE. A pH of 7.0 was found to be optimum pH with an accumulation time of 5 minutes. Estradiol was determined by linear sweep voltammetry over a dynamic range up to 20 %mol L^?1 and the limit of detection was estimated to be 7.0×10^?8 mol L^?1. The sensor was successfully applied to estradiol determination in tap water and waste water.     

聚甲苯胺蓝-(多壁碳纳米管/PDDA)_n杂化膜修饰印刷电极的制备及其对NADH的测定

利用静电层层组装的方式在印刷电极表面制备了(多壁碳纳米管/邻苯二甲酸二乙二醇二丙烯酸酯(PDDA))n多层膜,采用电位扫描电聚合法在修饰有多层膜的印刷电极表面聚合甲苯胺蓝,制备了聚甲苯胺蓝-(多壁碳纳米管/PDDA)n杂化膜修饰电极。扫描电镜实验表明,多壁碳纳米管均匀分布在杂化膜中,且多壁碳纳米管的掺杂使杂化膜表现出明显的多孔性。电化学实验表明,杂化膜具有良好的导电性且多壁碳纳米管的掺杂显著增加了聚甲苯胺蓝在电极表面的担载量,提高了检测灵敏度。在pH7.4的磷酸盐缓冲液中,杂化膜修饰电极对β-烟酰胺腺嘌呤二核苷酸(NADH)的氧化具有良好的催化作用,与裸电极相比氧化电位降低了560 mV,灵敏度明显提高。在8.7×10-8~1.3×10-4mol/L范围内,NADH的浓度与氧化电流呈线性关系,检出限为2.8×10-8mol/L,该修饰电极可用于NADH的测定。     

利用Cu0/多壁碳纳米管纳米复合物修饰玻碳电极快速非酶法检测葡萄糖和果糖(英文)

A nonenzymatic electrochemical sensor for glucose and fructose was fabricated that contained a glassy carbon electrode modified with a copper oxide (CuO)/multiwalled carbon nanotube (MWCNT) nanocomposite. The electrochemical properties of the CuO/MWCNT‐modified glassy carbon electrode were investigated. Two distinguishable anodic peaks were observed around 0.30 and 0.44 V corresponding to the oxidation of glucose and fructose, respectively, at the surface of the modified electrode. The detection limits for glucose and fructose were both 0.04 mmol/L. The sensor was used to simultaneously determine the concentrations of glucose and fructose in hydrolyzed sucrose samples, and to measure glucose in blood serum samples, demonstrating its potential as a nonenzymatic carbohydrate sensor.     

The NADH Electrochemical Detection Performed at Carbon Nanofibers Modified Glassy Carbon Electrode

In this work, the capability of carbon nanofibers to be used for the design of catalytic electrochemical biosensors is demonstrated. The direct electrochemistry of NADH was studied at a glassy carbon electrode modified using carbon nanofibers. A decrease of the oxidation potential of NADH by more than 300 mV is observed in the case of the assembled carbon nanofiber‐glassy carbon electrode comparing with a bare glassy carbon electrode. The carbon nanofiber‐modified electrode exhibited a wide linear response range of 3×10^?5 to 2.1×10^?3 mol L^?1 with a correlation coefficient of 0.997 for the detection of NADH, a high specific sensitivity of 3637.65 (μA/M cm²), a low detection of limit (LOD=3σ) of 11 μM, and a fast response time (3 s). These results have confirmed the fact that the carbon nanofibers represent a promising material to assemble electrochemical sensors and biosensors.     

Fabrication of Co3O4 particles-modified multi-walled carbon nanotube and poly(phenosafranine) composite electrode for selective and sensitive rutin detection

The preparation and characterisation of a new composite electrode with Co₃O₄ particles-modified multi-walled carbon nanotube (MWCNT) and poly(phenosafranine), as well as its novel application for the voltammetric detection of rutin was described. The resulting composite electrode was characterised using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). In the optimised experimental conditions, the oxidation peak current (I_pa) of rutin showed a linear increase in concentration, between 0.008–0.6 and 0.80–6.0 μmol L⁻¹, with a detection limit of 0.00379 μmol L⁻¹. Due to its good selectivity and stability, the composite electrode was successfully applied in detecting rutin in pharmaceutical formulations.     

Characterization of electrodes modified with nanocomposites of cobalt tetraaminophenoxyphthalocyanine,reduced graphene and multi-walled carbon nanotubes

Abstract

Glassy carbon electrodes or plates were modified with nanocomposites consisting of cobalt tetraaminophenoxyphthalocyanine (CoTAPhPc), reduced graphene oxide nanosheets (rGONs) and multi-walled carbon nanotubes (MWCNTs). The modified electrodes were characterized using cyclic voltammetry, scanning electrochemical microscopy (SECM) and time-of-flight-secondary ion mass spectrometer (TOF-SIMS). The electrocatalytic activity of the modified electrode was tested for detection of L-cysteine. The presence of CoTAPhPc on sequential layers of MWCNT and rGONs resulted in improved detection currents compared to CoTAPhPc alone or when MWCNT/rGONs are mixed in CoTAPhPc–MWCNT/rGONs (mix)–glassy carbon electrode (GCE). CoTAPhPc–MWCNT–GCE (without rGONS) showed higher sensitivity toward l-cysteine as compared to the probes incorporating rGONs with a catalytic rate constant of 4.62?×?10⁴ M^?1s^?1 and a detection limit of 30?nM. The presence of rGONs improved the stability of the electrode.