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1.
A sensitive voltammetric technique has been developed for the determination of Fludarabine using amine‐functionalized multi walled carbon nanotubes modified glassy carbon electrode (NH2‐MWCNTs/GCE). Molecular dynamics simulations, an in silico technique, were employed to examine the properties including chemical differences of Fludarabine‐ functionalized MWCNT complexes. The redox behavior of Fludarabine was examined by cyclic, differential pulse and square wave voltammetry in a wide pH range. Cyclic voltammetric investigations emphasized that Fludarabine is irreversibly oxidized at the NH2‐MWCNTs/GCE. The electrochemical behavior of Fludarabine was also studied by cyclic voltammetry to evaluate both the kinetic (ks and Ea) and thermodynamic (ΔH, ΔG and ΔS) parameters on NH2‐MWCNTs/GCE at several temperatures. The mixed diffusion‐adsorption controlled electrochemical oxidation of Fludarabine revealed by studies at different scan rates. The experimental parameters, such as pulse amplitude, frequency, deposition potential optimized for square‐wave voltammetry. Under optimum conditions in phosphate buffer (pH 2.0), a linear calibration curve was obtained in the range of 2×10?7 M–4×10?6 M solution using adsorptive stripping square wave voltammetry. The limit of detection and limit of quantification were calculated 2.9×10?8 M and 9.68×10?8 M, respectively. The developed method was applied to the simple and rapid determination of Fludarabine from pharmaceutical formulations.  相似文献   

2.
The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M1) and polypyrrole (herein called as modifier M2) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L?1 and 0.05–100 mg L?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M1)‐GCE respectively. The MWCNT(M2)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L?1, 0.9 μg L?1 and 0.1 μg L?1 for CYP, DEL and FEN respectively on MWCNT(M2)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.  相似文献   

3.
A sensitive electrochemical method was developed for the determination of bisphenol A (BPA) at a glassy carbon electrode (GCE) modified with a multiwalled carbon nanotubes (MWCNTs)‐gold nanoparticles (GNPs) hybrid film, which was prepared based on the electrostatic interaction between positively charged cetyltrimethylammonium bromide (CTAB) and negatively charged MWCNTs and GNPs. The MWCNT‐GNPs/GCE exhibited an enhanced electroactivity for BPA oxidation versus unmodified GCE and MWCNTs/GCE. The experimental parameters, including the amounts of modified MWCNTs and GNPs, the pH of the supporting electrolyte, scan rate and accumulation time, were examined and optimized. Under the optimal conditions, the differential pulse voltammetric anodic peak current of BPA was linear with the BPA concentration from 2.0×10?8 to 2×10?5 mol L?1, with a limit of detection of 7.5 nmol L?1. The proposed procedure was applied to determine BPA leached from real plastic samples with satisfactory results.  相似文献   

4.
Hybrid membranes containing multi‐walled carbon nanotubes (MWCNTs) were initially prepared to separate benzene/cyclohexane mixtures. Subsequently, MWCNT surfaces were chemically modified using two methods to change the surface polarity of the MWCNTs and improve the distribution thereof in Poly(methylmethacrylate) (PMMA). This change consequently enhanced the separation performance of hybrid membranes with MWCNTs. Raman spectroscopy was used to characterize the structure of the pristine MWCNTs and the modified MWCNTs. The morphology and distribution of the MWCNTs in PMMA were investigated by transmission electron microscopy. The results showed that the addition of MWCNTs clearly improved the separation performance of the hybrid membranes. Surface modification introduced polar groups onto the MWCNT surface, which significantly improved the distribution of MWCNTs in the PMMA membranes and the performance of hybrid membranes. MWCNTs with higher surface polarity also increased the amount of MWCNTs distributed homogeneously in PMMA. Aminated MWCNTs (MWCNT‐NH2) showed the highest surface polarity. Thus, the content of MWCNT‐NH2 well distributed in PMMA was the highest among the three types of MWCNTs. The highest separation factor for the hybrid membranes with 1.0 wt% MWCNT‐NH2 was about seven times that of membranes containing pristine MWCNTs. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

5.
We report the advantages of the adsorption and electrooxidation of oligonucleotides and calf‐thymus double stranded DNA (dsDNA) at glassy carbon electrodes (GCE) modified with a dispersion of multiwalled carbon nanotubes (MWCNT) in poly‐L ‐lysine (Plys) (GCE/MWCNT‐Plys). Important enhancement in the guanine oxidation signal was obtained by adsorptive stripping voltammetry (AdSV) due to a most favorable interaction between the negatively charged DNAs and the positively charged Plys that support the MWCNT. The layer of oligo(dG)11 immobilized at GCE/MWCNT‐Plys was successfully used for the selective detection of the hybridization event using oligo(dG)11/oligo(dC)11 as model.  相似文献   

6.
《Electroanalysis》2005,17(20):1854-1860
A novel type of sol‐gel inorganic‐organic hybrid material coated on glassy carbon electrode used for immobilization of double‐stranded DNA (dsDNA) and study of dsDNA with redox‐active molecules was developed. The hybrid material coating was produced by sol‐gel method with nano hydroxyapatite (HAp)‐polyvinyl alcohol (PVA). The optimum composition of the hybrid material was first examined, and the morphology of the nano HAp‐PVA coatings was investigated with the help of Scanning Electron Microscope (SEM). DsDNA was immobilized in/on the nano HAp‐PVA hybrid coatings by adsorption and the characteristics of the dsDNA/HAp‐PVA/GCE were studied by cyclic voltammetry (CV) using the probes of Co(phen) and Fe(CN) . The results indicate that the dsDNA can be immobilized on the nano porous HAp‐PVA coating effectively and its stability can satisfy the necessity of study on the interactions of dsDNA with redox‐active molecules on the electrode surface. Co(bpy) and Co(phen) were used as the model molecule to study the interactions of dsDNA with redox‐active molecules. Information such as ratio (KOx/KRed) of the binding constant for the oxidized and reduced forms of a bound species, interaction mode, including change in the mode of interaction, and “limiting” ratio K /K at zero ionic strength (μ) can be obtained using dsDNA/HAp‐PVA/GCE with about 2 μg of DNA samples.  相似文献   

7.
Ni(OH)2 nanoflowers were synthesized by a simple and energy‐efficient wet chemistry method. The product was characterized by scanning electron microscopy (SEM) and X‐ray powder diffraction (XRD). Then Ni(OH)2 nanoflowers attached multi‐walled carbon nanotubes (MWCNTs) modified glassy carbon electrodes (GCE) were proposed (MWCNTs/Ni(OH)2/GCE) to use as electrochemical sensor to detect hydrogen peroxide. The results showed that the synergistic effect was obtained on the MWCNTs/Ni(OH)2/GCE whose sensitivity was better than that of Ni(OH)2/GCE. The linear range is from 0.2 to 22 mmol/L, the detection limit is 0.066 mmol/L, and the response time is <5 s. Satisfyingly, the MWCNTs/Ni(OH)2/GCE was not only successfully employed to eliminate the interferences from uric acid (UA), acid ascorbic (AA), dopamine (DA), glucose (GO) but also NO2? during the detection. The MWCNTs/Ni(OH)2/GCE allows highly sensitive, excellently selective and fast amperometric sensing of hydrogen peroxide and thus is promising for the future development of hydrogen peroxide sensors.  相似文献   

8.
The electrochemical behavior of aquabis(1,10‐phenanthroline)copper(II) perchlorate [Cu(H2O)(phen)2]·2ClO4, where phen=1,10‐phenanthroline, on binding to DNA at a glassy carbon electrode (GCE) and in solution, was described. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) results showed that [Cu(H2O)(phen)2]2+ had excellent electrochemical activity on the GCE with a couple of quasi‐reversible redox peaks. The interaction mode between [Cu(H2O)(phen)2]2+ and double‐strand DNA (dsDNA) was identified to be intercalative binding. An electrochemical DNA biosensor was developed with covalent immobilization of human immunodeficiency virus (HIV) probe for single‐strand DNA (ssDNA) on the modified GCE. Numerous factors affecting the probe immobilization, target hybridization, and indicator binding reactions were optimized to maximize the sensitivity and speed of the assay. With this approach, a sequence of the HIV could be quantified over the range from 7.8×10?9 to 3.1×10?7 mol·L?1 with a linear correlation of γ=0.9987 and a detection limit of 1.3×10?9 mol·L?1.  相似文献   

9.
Graphene/mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin multilayer films composed of graphene sheet (GS) and mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (NH2β‐CD) were fabricated easily by two steps. First, negatively charged graphene oxide (GO) and positively charged mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (NH2β‐CD) were layer‐by‐layer (LBL) self‐assembled on glassy carbon electrode (GCE) modified with a layer of poly(diallyldimethylammonium chloride) (PDDA). Then graphene/mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (GS/NH2β‐CD) multilayer films were built up by electrochemical reduction of graphene oxide/mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (GO/NH2β‐CD). Combining the high surface area of GS and the active recognition sites on β‐cyclodextrin (β‐CD), the GS/NH2β‐CD multilayer films show excellent electrochemical sensing performance for the detection of DA with an extraordinary broad linear range from 2.53 to 980.05 µmol·L?1. This study offers a simple route to the controllable formation of graphene‐based electrochemical sensor for the detection of DA.  相似文献   

10.
A good route for the fabrication of CeO2 nanoparticles (nano‐CeO2)/multi‐walled carbon nanotubes (MWCNTs) modified glassy carbon electrodes (GCE) was proposed. MWCNTs are used to immobilize nano‐CeO2. What′s more, with the addition of the MWCNTs, the agglomeration level of CeO2 nanoparticles can be reduced, the extremely large surface area can be obtained and the electron transfer rate can be increased. The morphological characterization of nano‐CeO2/MWCNTs was examined by scanning electron microscopy (SEM). The performances of the nano‐CeO2/MWCNTs/GCE were characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and typical amperometric response (it). The potential utility of the constructed electrodes was demonstrated by applying them to the analytical determination of puerarin concentration. The catalytic oxidation of puerarin has a better result on nano‐CeO2/MWCNTs/GCE because of the synergistic effect of nano‐CeO2 and MWCNTs. An optimized limit of detection of 8.0×10?9 mol/L was obtained at a signal‐to‐noise ratio of 3 and with a fast response time (within 3 s). Additionally, the nano‐CeO2/MWCNTs/GCE exhibited a wide linear range from 0.04 to 6.0 μmol/L and high sensitivity.  相似文献   

11.
The interactions of furazolidone (Fu) with double‐stranded calf thymus DNA (dsDNA) on the multi‐walled carbon nanotubes‐ionic liquid‐modified carbon paste electrode (MWCNT‐IL‐CPE) have been studied by cyclic voltammetry. In the presence of DNA, the cathodic peak current of Fu decreased and the peak potential shifted to a positive potential, indicating the intercalative interaction of Fu with DNA. The binding constant of Fu with DNA and stoichiometric coefficient has been determined according to the Hill's model. This electrochemical method was further applied to the determination of DNA. Two linear calibration curves were obtained for DNA detection in the concentration ranges of 0.03–0.10 and 0.10–4.0 μg l?1 with a detection limit of 0.027 μg l?1. The method was successfully applied to analyze Fu in serum samples.  相似文献   

12.
Amino‐functionalized Fe3O4@carbon microspheres (NH2?Fe3O4@C) were prepared and the electrochemical sensor was constructed using NH2?Fe3O4@C modified glassy carbon electrodes (GCE) to determine toxic heavy metals in aqueous solution. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the structure and phase of NH2?Fe3O4@C. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results indicate that NH2?Fe3O4@C modified GCE possesses large active area and excellent electron transfer. Under optimized electrochemical condition, Cd(II), Pb(II) and Cu(II) were determined using NH2?Fe3O4@C modified GCE. The electrode through amino functionalization exhibits higher sensitivity and lower detection limit toward Cd(II) and Cu(II) due to the acid‐base pairing interaction between the electron‐rich ?NH2 ligand and the electron‐deficient heavy metal ions. Compared with other similar results reported in the literature, the NH2?Fe3O4@C modified electrode exhibits wider linear response range while with comparable lower detection limit. It also exhibits excellent stability, reproducibility and anti‐interference ability.  相似文献   

13.
We report an innovative supramolecular architecture for bienzymatic glucose biosensing based on the non‐covalently functionalization of multi‐walled carbon nanotubes (MWCNTs) with two proteins, glucose oxidase (GOx) (to recognize glucose) and avidin (to allow the specific anchoring of biotinylated horseradish peroxidase (b‐HRP)). The optimum functionalization was obtained by sonicating for 10 min 0.50 mg mL?1 MWCNTs in a solution of 2.00 mg mL?1 GOx+1.00 mg mL?1avidin prepared in 50 : 50 v/v ethanol/water. The sensitivity to glucose for glassy carbon electrodes (GCE) modified with MWCNTs‐GOx‐avidin dispersion and b‐HRP (GCE/MWCNTs‐GOx‐avidin/b‐HRP), obtained from amperometric experiments performed at ?0.100 V in the presence of 5.0×10?4 M hydroquinone, was (4.8±0.3) μA mM?1 (r2=0.9986) and the detection limit was 1.2 μM. The reproducibility for 5 electrodes using the same MWCNTs/GOx‐avidin dispersion was 4.0 %, while the reproducibility for 3 different dispersions and 9 electrodes was 6.0 %. The GCE/MWCNT‐GOx‐avidin/b‐HRP was successfully used for the quantification of glucose in a pharmaceutical product and milk.  相似文献   

14.
A new composite electrode has been fabricated based on coating multi‐walled carbon nanotubes (MWCNTs) and n‐octylpyridinum hexafluorophosphate (OPPF6) ionic liquid composite on a glassy carbon (GC) electrode (OPPF6‐MWCNTs/GCE). This electrode shows very attractive electrochemical performances for electrooxidation of risperidone (RIS) compared to conventional electrodes using carbon and mineral oil, notably improved sensitivity and stability. The oxidation peak potentials in cyclic voltammogram of RIS on the OPPF6‐MWCNTs/GCE was occurred around 230 mV vs. SCE at Britton–Robinson (B–R) buffer (pH 4.0) at scan rate of 100 mV s?1. The electrochemical parameters such as diffusion coefficient (D), charge transfer coefficient (α) and the electron transfer rate constant (k/s) were determined using cyclic voltammetry. Under the optimized conditions, the peak current was linear to risperidone concentration over the concentration range of 10–200 nM with sensitivity of 0.016 μA/nM?1 using differential pulse voltammetry. The detection limit was 6.54 nM (S/N = 3). The electrode also displayed good selectivity and repeatability. In the presence of clozapine (CLZ) the response of RIS kept almost unchanged. Thus this electrode could find application in the determination of RIS in some real samples. The analytical performance of the OPPF6‐MWCNTs/GCE was demonstrated for the determination of RIS in human serum and pharmaceutical samples.  相似文献   

15.
A new biomimetic functional system having an impure multiwalled carbon nanotube (MWCNT‐Fe)–chitosan biopolymer (H2N–CHIT) chemically modified glassy carbon electrode (GCE/[MWCNT‐Fe:H2N‐CHIT]) has been developed and demonstrated efficient hydrogen peroxide electrocatalytic and electrochemical sensing applications in pH 7 phosphate buffer solution (PBS). The hybrid system showed a stable and well‐defined surface confined redox peak at an apparent electrode potential, E°′=?0.22 V versus Ag/AgCl with surface excess value 13.63 nmol cm?2. Physicochemical characterizations of the hybrid by using FESEM, TEM, Raman spectroscopy, FTIR, and various control electrochemical experiments revealed that the iron impurity in the MWCNT interacted with the amino functional group of the chitosan polymer and thereby formed an unique complex‐like structure ([MWCNT‐FeIII/II:NH2‐CHIT]), similar to heme peroxidase with a central FeIII/II‐redox‐active site. The biomimetic system followed Michaelis–Menten‐type reaction kinetics for the H2O2 reduction reaction with a KM value of 0.23 mM . At pH 7, amperometric it sensing and flow‐injection analysis of H2O2 on the biomimetic system showed calibration plots in windows 5–500 and 50–2500 μM , with detection‐limit values of 2.3 and 9.7 μM , respectively. Unlike most of the previously reported systems that undergo serious interferences in physiological pH, the biomimetic system displayed a remarkable tolerance to other co‐existing interferants (such as cysteine, ascorbic acid, uric acid, nitrate, and nitrite), at a H2O2 detection potential similar to the peroxidase enzyme. The ability of the biosensor system to perform routine analyses was demonstrated by the detection of H2O2 present in simulated milk and clinical and cosmetic samples with appreciable recovery values.  相似文献   

16.
A glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes (MWCNTs) and a hydrophobic ionic liquid (IL), was used for the simultaneous voltammetric determination of theophylline (TP) and guaifenesin (GF). The results showed that the oxidations of TP and GF were facilitated at modified electrode and peak‐to‐peak separation at MWCNT? IL/GCE (252 mV) was larger than that observed at unmodified GCE (165 mV). Voltammetric signals for TP and GF exhibited linear ranges of 0.5 to 98.0 µM (R2>0.99) and 1.5 to 480.0 µM (R2>0.99), respectively. The method was used to estimate TP and GF contents in some real samples.  相似文献   

17.
Direct‐methanol fuel cells are proton‐exchange fuel cell in which methanol is used as the fuel. The important advantage of these fuel cells is the simplicity of transport and storage of methanol. In this study, methanol fuel cell electrocatalysts including graphene quantum dots (GQDs), functionalized multi‐walled carbon nanotubes (f‐MWCNTs) and GQDs/f‐MWCNTs composite were synthesized. The structures of synthesized electrocatalysts were highlighted by scanning electron microscope (SEM), raman spectroscopy, UV–vis spectroscopy, fourier transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS) and x‐ray diffraction (XRD) method. After that, the effective surface areas (ESA) of GQDs, f‐MWCNTs and GQDs/f‐MWCNTs were calculated. Finally, GQDs/f‐MWCNTs composite modified glassy carbon electrode (GQDs/f‐MWCNTs/GCE) showed highest current signals for methanol oxidation than those of comparable GQDs/GCE and f‐MWCNTs/GCE.  相似文献   

18.
《Electroanalysis》2017,29(7):1674-1682
Human cytochrome CYP1A2 is one of the major hepatic cytochrome P450s involved in many drugs metabolism, and chemical carcinogens activation. The CYP1A2‐dsDNA interaction in situ evaluation using a DNA‐electrochemical biosensor and differential pulse voltammetry was investigated. A dsDNA‐electrochemical biosensor showed that CYP1A2 interacted with dsDNA causing conformational changes in the double helix chain and DNA oxidative damage. A preferential interaction between the dsDNA guanosine residues and CYP1A2 was found, as free guanine and 8‐oxoguanine, a DNA oxidative damage biomarker, oxidation peaks were detected. This was confirmed using guanine and adenine homopolynucleotides‐electrochemical biosensors. The CYP1A2‐dsDNA interaction and dsDNA conformation changes was also confirmed by UV‐Vis spectrophotometry.  相似文献   

19.
Core–shell carboxyl‐functionalized multiwall carbon nanotube (c‐MWCNT)/poly(m‐aminophenol) (PmAP) nanocomposite were prepared through in‐situ polymerization of m‐aminophenol (m‐AP) in the presence of MWCNTs, and explicated as a dielectric material for electronic applications. The formation of thin PmAP layer on individual c‐MWCNT with excellent molecular level interactions at interfaces was confirmed by morphological and spectroscopic analyses. Here we conducted a comparative study of the dielectric performances of PmAP based nanocomposite films with pristine MWCNTs and c‐MWCNTs as fillers. Compared to PmAP/MWCNT nanocomposites, the PmAP/c‐MWCNT nanocomposites exhibited higher dielectric permittivity and lower dielectric loss. The well dispersed c‐MWCNTs in PmAP/c‐MWCNT nanocomposite produce huge interfacial area together with numerous active polarized centers (crystallographic defects), which in turn intensified the Maxwell‐Wagner‐Sillars (MWS) effect based on excellent molecular level interactions and thus, produce large dielectric permittivity (8810 at 1 kHz). The percolation threshold of PmAP/c‐MWCNT nanocomposites is found lower than that of the PmAP/MWCNT nanocomposites, which could be attributed to homogeneous distribution of c‐MWCNTs and strong c‐MWCNT//PmAP interfacial interactions in the nanocomposites. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

20.
In the present investigation, the preparation, characterization, and surface morphology of poly(amide‐imide) (PAI)/multi‐walled carbon nanotubes (MWCNTs) bionanocomposites (BNCs) were the main goals of the study. At first, an optically active PAI based on S‐valine as a biodegradable segment was synthesized. Then, carboxyl‐modified MWCNTs were functionalized with glucose (f‐MWCNT) as a biological active molecule in a green method to achieve a fine dispersion of f‐MWCNT bundles in the PAI matrix. The existence of S‐valine in the PAI matrix and functionalized MWCNT with glucose resulted in a series of potentially biodegradable nanocomposites. The obtained BNCs were characterized by various techniques. Field emission scanning and transmission electron microscopy micrographs of the composites showed a fine dispersion of f‐MWCNTs in the polymer matrix because of hydrogen bonding and π–π stacking interaction between f‐MWCNTs and polymer functional groups and aromatic moieties. Adding f‐MWCNTs into polymer matrix significantly improved the thermal stability of BNCs because of the increased interfacial interaction between the PAI matrix and f‐MWCNTs and also good dispersion of f‐MWCNT in the polymer matrix. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

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