Electrochemical biosensor based on multi-walled carbon nanotubes and Au nanoparticles synthesized in chitosan

A new biosensor is prepared by cross-linking glucose oxidase (GOD) with glutaradehyde at the electrode combining Au nanoparticles (AuNP) with multi-walled carbon nanotubes (MWCNTs). Au nanoparticles-doped chitosan (CS) solution (AuNP-CS) is prepared by treating the CS solution followed by chemical reduction of Au (III) with NaBH4. MWCNTs are then dispersed in AuNP-CS solution. TEM, FT-IR, and UV-Vis show that the AuNP-CS solution is highly dispersed and stable. The synergistic effect between AuNP and CNTs of the AuNP-CNTs-CS material has been investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and amperometric methods. The modified glassy carbon electrode (GCE) allows low-potential detection of H2O2 with high sensitivity and fast response time. With the immobilization of GOD, a biosensor has been constructed. In phosphate buffer solutions (PBS, pH 7.0), nearly free interference determination of glucose has been realized at 0.4 V(vs. Ag/AgCl/3.0 M KCI) with a wide linear range from 2.0 x 10(-5) to 1.5 x 10(-2) M and a fast response time within 5s. The biosensor has been used to determine glucose in human serum samples and the results are satisfactory.     

Determination of pentachlorophenol at carbon nanotubes modified electrode incorporated with beta-cyclodextrin

A facile and reliable electrochemical technique at beta-cyclodextrin incorporated carbon nanotubes modified glassy carbon electrode (beta-CD/CNTs/GCE) was proposed for determination of pentachlorophenol (PCP). The electrochemical behavior of PCP at the beta-CD/CNTs/GCE was investigated by cyclic voltammetry and linear sweep voltammetry. The beta-CD/CNTs/GCE showed good analytical performance characteristics in electrocatalytic oxidation of PCP, compared with the simple carbon nanotube modified electrode (CNTs/GCE) and bare glassy carbon electrode (GCE). After accumulation for 5 min on beta-CD/CNTs/GCE, the peak current increased linearly with the concentration of PCP in the range from 8.0 x 10(-7) to 1.04 x 10(-5) mol/L. The detection limit was 4.0 x 10(-8) mol/L at 3 sigma level. The proposed electrode presented good repeatability for the determination of PCP in artificial wastewater, and the recovery was 97%-103%. This modified electrode combined the advantages of carbon nanotubes and supramolecular cyclodextrin, leading to new capabilities for electrochemical detection of PCP.     

Simultaneous determination of serotonin and dopamine at the PEDOP/MWCNTs-Pd nanoparticle modified glassy carbon electrode

Electrochemical determination of dopamine (DA) and serotonin (5-HT) have been studied at a modified glassy carbon electrode (GCE) in 0.1 M phosphate buffer solution (PBS) using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) at pH 7.4, all over the interfering biomolecule ascorbic acid (AA). The GCE was modified by palladium-functionalized, multi-walled carbon nanotubes (MWCNTs-Pd) with electrochemical deposition of poly 3,4-ethylenedioxy pyrrole (PEDOP), denoted as PEDOP/MWCNTs-Pd/GCE, and investigated by SEM and EIS experiments. The highly electrocatalytic activity of the modified electrode toward 5-HT and DA was demonstrated from the sensitive and well-separated voltammetric experiment. The oxidation peaks found were 0.165 and 0.355 mV for DA and 5-HT, respectively. The composite film shows a significant accumulation effects on two species, as well as the mutual interference among the analytes. This biosensor was best in response compared to other modified electrodes made in the same lab. The lowest detection limits were found to be 5.0 x 10(-9) and 1.0 x 10(-8) for 5-HT and DA, respectively. The respective linear ranges were determined as 1.0 x 10(-7) to 2.0 x 10(-4) and 1.0 x 10(-7) to 2.0 x 10(-4) for 5-HT and DA.     

Determination of serotonin on a glassy carbon electrode modified by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin and single walled carbon nanotubes

A chemically modified electrode [poly(TAPP)-SWNT/GCE] was prepared by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin (TAPP)-single walled carbon nanotubes (SWNT) on the surface of a glassy carbon electrode (GCE). This modified electrode was employed as an electrochemical biosensor for the determination of serotonin concentration and exhibited a typical enhance effect on the current response of serotonin and lower oxidation overpotential. The biosensor was very effective to determined 5-HT in a mixture. The linear response was in the range 2.0 x 10(-7) to 1.0 x 10(-5) M, with a correlation coefficient of 0.999 [i(p)(microA) = 3.406 C (microM)+0.132] on the anodic current, with a detection limit of 1 x 10(-9) M. Due to the relatively low currents and different potentials in the electrochemical responses to ascorbic acid and dopamine, the modified electrode is a useful and effective sensing device for the selective and sensitive serotonin determination in the presence of ascorbic acid and dopamine.     

纳米TiO2/还原石墨烯复合修饰电极用于食品中 柠檬黄的检测

为了检测食品中柠檬黄的含量,利用滴涂法和电化学还原法制备纳米TiO_2/还原石墨烯复合修饰玻碳电极(TiO_2-Er GO/GCE)。采用透射电子显微镜和X射线粉末衍射仪对TiO_2和TiO_2-GO两种修饰电极材料进行表征;通过循环伏安法观察了柠檬黄在不同电极上的电化学行为,并对检测条件如p H值、富集电位、富集时间进行了优化。实验结果表明:TiO_2-Er GO/GCE增大了电极的电化学活性面积,提高了柠檬黄的电化学氧化响应;最优的检测条件为p H值为3.7、富集电位为-0.20 V、富集时间为180 s;在最优的检测条件下,采用线性扫描伏安法检测柠檬黄的线性范围为2.0×10-8~2.0×10-5 mol/L,检测限为8.0×10-9 mol/L(信噪比为3)。     

Simultaneous determination of 3,4-dihydroxyphenylacetic acid, uric acid and ascorbic acid by poly(L-arginine)/multi-walled carbon nanotubes composite film

The poly(L-Arginine)(PArg)-multiwalled carbon nanotubes (MWCNTs) composite film was used to modify glassy carbon electrode (GCE) to fabricate PArg/MWCNTs/GCE through electropolymerization of L-Arginine on MWCNTs/GCE. The PArg/MWCNTs/GCE exhibited high electro-catalytic activities towards the oxidation of 3,4-dihydroxyphenylacetic acid (DOPAC), uric acid (UA), and ascorbic acid (AA), and could be sensitively used for simultaneous determination of DOPAC, AA, and UA in pH 7.4 phosphate-buffered solution (PBS).The linear ranges were 7 microM to 2.7 mM for DOPAC, 3 microM to 1.2 mM for UA, and 70 microM to 1.4 mM for AA. The detection limits were 1.3 microM for DOPAC, 0.7 microM for UA and 20 microM for AA.     

Facile deposition of polyvinylpyrrolidone-grafted multi-walled carbon nanotube on glassy carbon electrode and its application in the sensing of biomolecules

Polyvinylpyrrolidone-grafted multi-walled carbon nanotube (PVP/MWCNT) was deposited on carboxylated glassy carbon electrode (GCE) from acidic water via the electrostatic force between the positively charged PVP/MWCNTs and negatively charged GCE. It was found out that PVP/MWCNT-modified GCE (PVP/MWCNT/GCE) exhibited great catalytic capability for the oxidation of dopamine (DA), uric acid (UA), tyrosine (Tyr) and nitrite) by enhancing their oxidation currents and lowering their overpotentials. For PVP/MWCNT/GCE, the linear calibration plots for DA, UA, Tyr and nitrite were obtained over the range of 0.1–50 μM, 1–500 μM, 1–200 μM and 1–500 μM with detection limits of 0.04 μM, 0.17 μM, 0.26 μM and 0.30 μM, respectively. In addition, satisfactory results were obtained by applying PVP/MWCNT/GCE in the determination of DA, UA, Tyr and nitrite in human serum samples with standard addition method.     

Characterization of an EDTA bonded conducting polymer modified electrode: its application for the simultaneous determination of heavy metal ions

An EDTA bonded conducting polymer modified electrode (EDTA-CPME) was fabricated by polymerization of 3',4'-diamino-2,2';5',2'-terthiophene monomer on a GCE, followed by the reaction with EDTA in the presence of catalyst. The surface of the resulting modified electrode was characterized with EQCM, ESCA, SEM, Auger electron spectroscopy, scanning Auger microscopy, and electrochemical methods. The amounts of polymer and EDTA attached on the polymer film were determined. Simple immersing of the EDTA-CPME into a sample solution led to the chemical deposition through the complexation with Pb2+, Cu2+, and Hg2+ ions, simultaniously. Various experimental parameters that affect the simultaneous analysis of the metal ions, e.g., EDTA amount, pH, deposition time, and deposition temperature, were optimized. Calibration plots for the EDTA-CPME with square wave voltammetry were obtained in the concentration range between 5.0 x 10(-10) and 1.0 x 10(-7) M for Cu(II) and between 7.5 x 10(-10) and 1.0 x 10(-7) M for Pb(II) and Hg(II). The detection limits for Pb(II), Cu(II), and Hg(II) ions were determined to be about 6.0 x 10(-10), 2.0 x 10(-10), and 5.0 x 10(-10) M, respectively. Interference effects from other metal ions were studied at various pHs and it was found that there was little or no effect on the simultaneous determination. The stability of the EDTA-CPME was remarkably improved by coating the surface with the Nafion film, and the electrode can be used for more than one month. Analytical availability of the EDTA-CPME was demonstrated by the application for the certified standard urine reference material and tap water.     

Voltammetric determination of tryptophan at a single-wall carbon nanotubes modified electrode

A single-wall carbon nanotubes (SWNT)-film coated glassy carbon electrode (GCE) was described for the determination of tryptophan. In pH 2.5 Na2HPO4-citric acid buffer, tryptophan yields a well-defined and very sensitive oxidation peak at about 1.08 V at the SWNT-film coated GCE. The oxidation peak current increases greatly and the peak potential shifts toward more negative direction at the SWNT-modified GCE in contrast to that at the bare GCE. Under optimized conditions, the oxidation peak current is proportional to the concentration of tryptophan over the range from 4 x 10(-8) to 1 x 10(-5) mol/L. The detection limit is 1 x 10(-8) mol/L at 3 min of accumulation. Using the proposed method, tryptophan in the human's blood serum samples was determined.     

Development of an amperometric l-lactate biosensor based on l-lactate oxidase immobilized through silica sol–gel film on multi-walled carbon nanotubes/platinum nanoparticle modified glassy carbon electrode

Platinum nanoparticles (Ptnano) were used in combination with multi-walled carbon nanotubes (MWCNTs) for fabricating sensitivity-enhanced electrochemical l-lactate biosensor. The composite film of MWCNTs and Ptnano was dispersed on the surface of the glassy carbon electrode (GCE). l-lactate oxidase (LOD) was immobilized on MWCNTs/Ptnano/GCE surface by adsorption. The resulting LOD/MWCNTs/Ptnano electrode was covered by a thin layer of sol–gel to avoid the loss of LOD in determination and to improve the anti-interferent ability. Moreover, the sol–gel microenviroment contributes to both intensified stability and permselectivity. The cyclic voltammetry results indicated that MWCNTs/Ptnano catalyst displayed a higher performance than MWCNTs. Under the optimized conditions of applied potential 0.5 V, pH 6.4, room temperature, the proposed biosensor showed a large determination range (0.2–2.0 mM), a short response time (within 5 s), a high sensitivity (6.36 μA mM^{− 1}) and good stability (90% remains after 4 weeks). The fabricated biosensor had practically good selectivity against interferences. The results for whole blood samples measured by the present biosensor showed a good agreement with those measured by spectrophotometric method.     

A reduced graphene oxide based electrochemical biosensor for tyrosine detection

In this paper, a 'green' and safe hydrothermal method has been used to reduce graphene oxide and produce hemin modified graphene nanosheet (HGN) based electrochemical biosensors for the determination of l-tyrosine levels. The as-fabricated HGN biosensors were characterized by UV-visible absorption spectra, fluorescence spectra, Fourier transform infrared spectroscopy (FTIR) spectra and thermogravimetric analysis (TGA). The experimental results indicated that hemin was successfully immobilized on the reduced graphene oxide nanosheet (rGO) through π-π interaction. TEM images and EDX results further confirmed the attachment of hemin on the rGO nanosheet. Cyclic voltammetry tests were carried out for the bare glass carbon electrode (GCE), the rGO electrode (rGO/GCE), and the hemin-rGO electrode (HGN/GCE). The HGN/GCE based biosensor exhibits a tyrosine detection linear range from 5?×?10(-7)?M to 2?×?10(-5)?M with a detection limitation of 7.5?×?10(-8)?M at a signal-to-noise ratio of 3. The sensitivity of this biosensor is 133 times higher than that of the bare GCE. In comparison with other works, electroactive biosensors are easily fabricated, easily controlled and cost-effective. Moreover, the hemin-rGO based biosensors demonstrate higher stability, a broader detection linear range and better detection sensitivity. Study of the oxidation scheme reveals that the rGO enhances the electron transfer between the electrode and the hemin, and the existence of hemin groups effectively electrocatalyzes the oxidation of tyrosine. This study contributes to a widespread clinical application of nanomaterial based biosensor devices with a broader detection linear range, improved stability, enhanced sensitivity and reduced costs.     

Amperometric determination of hydrogen peroxide by functionalized carbon nanotubes through EDC/NHS coupling chemistry

The electrochemistry of the redox mediator Toluidine blue (TB) which was covalently linked to the carboxyl group of the multiwalled carbon nanotubes (MWNTs) by coupling reactions, in which N-hydroxysuccinimide was used to assist 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride catalyzed amidation reaction is described. The results from cyclic voltammetry (CV) and amperometry suggested that the redox mediator is linked to the surface of the MWNTs and the nanotubes showed an obvious promotion for the direct electron-transfer between the redox mediator and the electrode. A couple of well-defined redox peak of TB was observed in a phosphate buffer solution (pH 7.0). The redox mediator immobilized to MWNTs exhibits remarkable electrocatalytic activity for the reduction of hydrogen peroxide (H2O2). The analytical applicability of the modified electrode for the determination of hydrogen peroxide was examined. A linear response in the concentration range of 6.8 x 10(-7)-3.4 x 10(-2) M (r = 0.9958) was obtained with detection limit of 3.4 x 10(-7) M for the determination of hydrogen peroxide. The modified electrode has advantages of being highly stable, sensitive, ease of construction and use.     

MnO2纳米棒-还原石墨烯复合修饰玻碳电极用于苋菜红的检测

利用电化学还原法制备MnO₂纳米棒-还原石墨烯复合修饰电极（MnO₂ NRs-ErGO/GCE）用于苋菜红的检测。采用SEM和XRD分别对修饰电极材料进行微观形貌和成分结构表征。通过循环伏安法考察了苋菜红在裸电极、ErGO/GCE和MnO₂ NRs-ErGO/GCE上的电化学行为,并对测定条件如pH值、富集电位、富集时间进行了优化。结果表明,MnO₂ NRs-ErGO增大了GCE电化学活性面积,提高了苋菜红的电化学氧化响应。在最优的检测条件下,MnO₂ NRs-ErGO/GCE线性扫描伏安法检测苋菜红线性范围为2.0×10^-8~1.0×10^-5 mol/L和1.0×10^-5~4.0×10^-4 mol/L,检测限为1.0×10^-8 mol/L。MnO₂ NRs-ErGO/GCE用于真实饮料样品检测,获得满意结果。     

Electrochemical biosensor for detection of BCR/ABL fusion gene using locked nucleic acids on 4-aminobenzenesulfonic acid-modified glassy carbon electrode

In this study, an electrochemical DNA biosensor was developed for detection of the breakpoint cluster region gene and the cellular abl (BCR/ABL) fusion gene in chronic myelogenous leukemia by using 18-mer locked, nucleic acid-modified, single-stranded DNA as the capture probe. The capture probe was covalently attached on the sulfonic-terminated aminobenzenesulfonic acid monolayer-modified glassy carbon electrode through the free amines of DNA bases based on the acyl chloride cross-linking reaction. The covalently immobilized capture probe could selectively hybridize with its target DNA to form double-stranded DNA (dsDNA) on the LNA/4-ABSA/GCE surface. Differential pulse voltammetry was used to monitor the hybridization reaction on the capture probe electrode. The decrease of the peak current of methylene blue, an electroactive indicator, was observed upon hybridization of the probe with the target DNA. The results indicated that, in pH 7.0 Tris-HCl buffer solution, the peak current was linear with the concentration of complementary strand in the range of 1.0 x 10 (-12)1.1 x 10 (-11) M with a detection limit of 9.4 x 10 (-13) M. This new method demonstrates its excellent specificity for single-base mismatch and complementary dsDNA after hybridization, and this probe has been used for assay of PCR real sample with satisfactory results.     

Copper(II) nanosensor based on a gold cysteamine self-assembled monolayer functionalized with salicylaldehyde

Fabrication and electrochemical characterization of a novel nanosensor for determination of Cu2+ in subnanomolar concentrations is described. The sensor is based on gold cysteamine self-assembled monolayer functionalized with salicylaldehyde by means of Schiff's base formation. Cyclic voltammetry, Electrochemical impedance spectroscopy (EIS), and electrochemical quartz crystal microbalance were used to probe the fabrication and characterization of the modified electrode. The sensor was used for quantitative determination of Cu2+ by the EIS in the presence of parabenzoquinone in comparison with stripping Osteryoung square wave voltammetry (OSWV). The attractive ability of the sensor to efficiently preconcentrate trace amounts of Cu2+ allowed a simple and reproducible method for copper determination. A wide range linear calibration curve was observed, 5.0 x 10(-11)-5.0 x 10(-6) and 5.0 x 10(-10)-5.0 x 10(-6) M Cu2+, by using the EIS and OSWV, respectively. Moreover, the sensor presented excellent stability with lower than 10% change in the response, as tested for more than three months daily experiments, and a high repeatability with relative standard deviations of 6.1 and 4.6% obtained for a series of eight successive measurements in 5.0 x 10(-7) M Cu2+ solution, by the EIS and OSWV, respectively.     

Fabrication of nano-porous hydroxyapatite modified electrode and its application for determination of p-chlorophenol

Nano-porous hydroxyapatite (HAp) modified electrode was fabricated by simply electrodepositing HAp onto the glassy carbon electrode (GCE) from the electrolytes solution containing Ca(NO3)2 4H2O and NH4H2PO4, the resulting electrode (nano-HAp/GCE) was characterized with scanning electron microscopy (SEM). The electrochemical behavior of p-chlorophenol (p-CP) at nano-HAp/GCE was studied by cyclic voltammetry. The electrode displayed selective and enhanced electroanalytical response towards p-CP, obviously because p-CP is accumulated at the electrode. For the greater sensitivity, a semi-derivative technique was adopted to obtain the current signal. The results indicated that the nano-HAp/GCE exhibits substantial enhancement in electrochemical sensitivity for p-CP due to its large surface area and particular adsorbability. After accumulation of 4 min for p-CP on nano-HAp/GCE, the peak height was linearly related to the concentration of p-CP in the range of 1.0 x 10(-8) to 1.0 x 10(-7) mol L(-1). The detection limit was 4.0 x 10(-9) mol L-(1) at 3sigma level. Based on this, the modified electrode was successfully applied in water samples with low cost and high sensitivity.     

Polypyrrole/multiwall carbon nanotube nanocomposites electropolymerized on copper substrate

Polypyrrole/multiwall carbon nanotube (PPy/MWCNT) nanocomposites were successfully synthesized by electropolymerization of MWCNT-dispersed pyrrole solution on the surface of copper electrodes. The obtained nanocomposites were characterized with scanning electron microscopy (SEM), linear sweep voltammetry (LSV) and thermal gravimetric analysis (TGA). Polypyrrole structures which embraced the MWCNTs led to the formation of nanocomposite striated parallel walls. MWCNTs acted as appropriate substrates for electrodeposition of polypyrrole particulate structures and high yield synthesis of PPy was observed on them. Smooth PPy/MWCNT nanocomposite films were obtained on Cu electrodes by decreasing the potential scan rate. Thermogravimetric analysis showed that MWCNTs increased the thermal stability of polypyrrole.     

Poly(vinyl) chloride membrane copper-selective electrode based on 1-phenyl-2-(2-hydroxyphenylhydrazo)butane-1,3-dione

1-Phenyl-2-(2-hydroxyphenylhydrazo)butane-1,3-dione (H(2)L) was used as an effective ionophore for copper-selective poly(vinyl) chloride (PVC) membrane electrodes. Optimization of the composition of the membrane and of the conditions of the analysis was performed, and under the optimized conditions the electrode has a detection limit of 6.30×10(-7) M Cu(II) at pH 4.0 with response time 10s and displays a linear EMF versus log[Cu(2+)] response over the concentration range 2.0×10(-6) to 5.0×10(-3) M Cu(II) with a Nernstian slope of 28.80±0.11 mV/decade over the pH range of 3.0-8.0. The sensor is stable for 9 weeks and exhibits good selectivity with respect to alkali, alkali earth and transition metal ions (e.g. Na(+), K(+), Ba(2+), Ca(2+), Zn(2+), Cd(2+), Co(2+), Mn(2+), Ni(2+), Fe(2+), Al(3+)) in the 3.0-8.0 pH range. It was successfully applied for the direct determination of copper(II) in zinc, aluminum and nickel based alloys, in soils polluted by oil, and as an indicator electrode for potentiometric titration of copper ions with EDTA.     

Determination of Pb2+ ions by a modified carbon paste electrode based on multi-walled carbon nanotubes (MWCNTs) and nanosilica

A novel carbon paste ion selective electrode for determination of trace amount of lead was prepared. Multi-walled carbon nanotubes (MWCNTs) and nanosilica were used for improvement of a lead carbon paste sensor response. MWCNTs have a good conductivity which helps the transduction of the signal in carbon paste electrode. The electrode composition of 20 wt% paraffin oil, 57% graphite powder, 15% ionophore (thiram), 5% MWCNTs, and 3% nanosilica showed the stable potential response to Pb²⁺ ions with the Nernstian slope of 29.8 (±0.2) mV decade^?1 over a wide linear concentration range of 10^?7–10^?2 mol L^?1. The electrode has fast response time, and long term stability (more than 2 months). The proposed electrode was used to determine the concentration of lead ions in waste water and black tea samples.     

Conducting polymer‐coated, palladium‐functionalized multi‐walled carbon nanotubes for the electrochemical sensing of hydroxylamine

Electrochemical sensors of hydroxylamine were fabricated on glassy carbon electrodes (GCEs) by the electropolymerization of 3,4‐ethylenedioxypyrrole (EDOP) and 3,4‐ethylenedioxythiophene (EDOT) on palladium (Pd) nanoparticles attached to thiolated multi‐walled carbon nanotubes (MWCNTs), denoted as PEDOP/MWCNT‐Pd/GCE and PEDOT/MWCNT‐Pd/GCE. The sensors were characterized by field emission scanning electron microscopy and electrochemical impedance spectroscopy. They showed strong catalytic activity toward the oxidation of hydroxylamine. Cyclic voltammetry and amperometry were used to characterize the sensors' performances. The detection limits of hydroxylamine by PEDOP/MWCNT‐Pd/GCE and PEDOT/MWCNT‐Pd/GCE were 0.22 and 0.24 μM (S/N = 3), respectively. The sensors' sensitivity, selectivity, and stability were also investigated.