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1.
A metallodendrimer-based electrochemical DNA biosensor was constructed by a layer-by-layer assembly of cobalt(II) salicylaldiimine metallodendrimer (SDD-Co(II)) and a 21 bases oligonucleotide NH2-5′-GAGGAGTTGGGGGAGCACATT-3′ (pDNA) on a gold electrode. The complementary oligonucleotide was 5′-AATGTGCTCCCCCAACTCCTC-3′ (tDNA). UV-visible spectra of SDD-Co(II) in 1:1 (v/v) acetone-ethanol solution showed absorption bands at 325 nm and 365-420 nm related to π-π* intra-dendrimer transitions and d-π* metal-dendrimer charge transfer transitions, respectively. Square-wave voltammetry (SWV) characterisation of the Au|SDD-Co(II)|pDNA biosensor system in phosphate buffer saline solution of pH 7.4, indicated a reversible one-electron electrochemical process with a formal potential, E°′, value of +210 mV. Electrochemical impedance spectroscopy (EIS) data confirmed that the hybridisation of the biosensor's pDNA with the tDNA to form double-stranded DNA (dsDNA) resulted in an increase of the impedimetric charge transfer resistance, Rct, value from 6.52 to 12.85 kΩ. The limit of detection (LOD), calculated as 3σ of the background noise, and sensitivity of the sensor were 1.29 kΩ/nmol L−1 and 0.34 pmol L−1, respectively.  相似文献   

2.
The interactions of promethazine hydrochloride (PZH) with thiolated single-stranded DNA (HS-ssDNA) and double-stranded DNA (HS-dsDNA) self-assembled on gold electrodes have been studied electrochemically. The binding of PZH with ssDNA shows a mechanism containing an electrostatic interaction, while the mode of PZH interaction with dsDNA contains both electrostatic and intercalative bindings. The redox system belongs to the category of diffusion control approved by cyclic voltammetry (CV). The diffusion coefficients of PZH at the bare, HS-dsDNA and HS-ssDNA modified gold electrodes decrease regularly as 1.34 × 10−3 cm2 s−1, 1.04 × 10−3 cm2 s−1, 7.47 × 10−4 cm2 s−1, respectively. The electron transfer standard rate constant ks of PZH at bare gold, HS-ssDNA and HS-dsDNA modified electrodes are 0.419 s−1, 0.131 s−1, and 0.154 s−1, respectively. The presence of adsorbed dsDNA results in a great increase in the peak currents of PZH in comparison with those obtained at a bare or ssDNA adsorbed gold electrode. The difference between interactions of PZH with HS-ssDNA and HS-dsDNA has been used for hybridization recognition of 14-mer DNA oligonucleotide. The peak current (ipa) of PZH is linearly proportional to the logarithmic concentration of complementary target DNA in the range from 2.0 × 10−9 mol L−1 to 5.0 × 10−7 mol L−1 with the detection limit of 3.8 × 10−10 mol L−1.  相似文献   

3.
A highly selective electrochemical biosensor for the detection of Hg2+ in aqueous solution has been developed. This sensor is based on the strong and specific binding of Hg2+ by two DNA thymine bases (T–Hg2+–T). The hemin worked as a redox indicator to generate a readable electrochemical signal. Short oligonucleotide strands containing 5 thymine (T5) were used as probe. Thiolated T5 strands were self-assembled through Au–S bonding on gold electrode. In the presence of Hg2+, the specific coordination between Hg2+ and thymine bases resulted in more stable and porous arrangement of oligonucleotide strands, so hemin could be adsorbed on the surface of gold electrode and produced an electrochemical signal, which was monitored by differential pulse voltammetry (DPV). The DPV showed a linear correlation between the signal and the concentration of Hg2+ over the range 0–2 μM (R2 = 0.9983) with a detection limit of 50 nM. The length of probe DNA had no significant impact on the sensor performance. This electrochemical biosensor could be widely used for selective detection of Hg2+.  相似文献   

4.
An electrochemical DNA biosensor (EDB) was prepared using an oligonucleotide of 21 bases with sequence NH2-5′-GAGGAGTTGGGGGAGCACATT-3′ (probe DNA) immobilized on a novel multinuclear nickel(II) salicylaldimine metallodendrimer on glassy carbon electrode (GCE). The metallodendrimer was synthesized from amino functionalized polypropylene imine dendrimer, DAB-(NH2)8. The EDB was prepared by depositing probe DNA on a dendrimer-modified GCE surface and left to immobilize for 1 h. Voltammetric and electrochemical impedance spectroscopic (EIS) studies were carried out to characterize the novel metallodendrimer, the EDB and its hybridization response in PBS using [Fe(CN)6]3−/4− as a redox probe at pH 7.2. The metallodendrimer was electroactive in PBS with two reversible redox couples at E°′ = +200 mV and E°′ = +434 mV; catalytic by reducing the Epa of [Fe(CN)6]3−/4− by 22 mV; conducting and has diffusion coefficient of 8.597 × 10−8 cm2 s−1. From the EIS circuit fitting results, the EDB responded to 5 nM target DNA by exhibiting a decrease in charge transfer resistance (Rct) in PBS and increase in Rct in [Fe(CN)6]3−/4− redox probe; while in voltammetry, increase in peak anodic current was observed in PBS after hybridization, thus giving the EDB a dual probe advantage.  相似文献   

5.
The interactions of nile blue (NB) with calf-thymus double-stranded DNA (dsDNA) in solution, single-stranded DNA (ssDNA) and dsDNA adsorbed on gold electrodes were studied electrochemically. The binding of NB with dsDNA showed a mechanism containing an electrostatic interaction with the binding constant of (5.9 ± 0.2) × 104 M−1 in 0.01 M pH 7.4 Tris-HCl. The presence of adsorbed dsDNA resulted in a great increase in the peak currents of NB in comparison with those obtained at a bare or ssDNA adsorbed gold electrode. The electron transfer rate constants of nile blue adsorbed on bare gold and bound to ss- and dsDNA/Au electrodes were 1.4 ± 0.1, 1.2 ± 0.02 and 2.9 ± 0.2 s−1, respectively. Nile blue showed an electrostatic action with adsorbed ssDNA and an action with adsorbed dsDNA by the mechanism containing both electrostatic and intercalative bindings. The Langmuir adsorption constants of NB at ssDNA/Au and dsDNA/Au electrodes were (1.6 ± 0.2) × 105 and (4.2 ± 0.6) × 105 M−1, respectively. The difference between interactions of NB with adsorbed ss- and dsDNA has been used for hybridization recognition of hepatitis B virus DNA fragment. The interactions between NB and covalently immobilized hepatitis B virus ssDNA fragment and its hybridization product showed the mechanisms similar to those of adsorbed calf-thymus DNA.  相似文献   

6.
A. Bonanni 《Electrochimica acta》2008,53(11):4022-4029
Streptavidin-coated gold nanoparticles (strept-AuNPs) were used in this work to amplify the impedimetric signal generated in a biosensor detecting the DNA hybridization event. Probe oligomer was adsorbed onto a graphite epoxy composite (GEC) electrode surface and the impedance measurement was performed in a solution containing the redox marker ferrocyanide/ferricyanide. The biotinylated complementary oligomer was used as target. The change of interfacial charge transfer resistance (Rct), experimented by the redox marker, was recorded to confirm the hybrid formation. The addition of strept-AuNPs, binding to the target due to the strong streptavidin-biotin interaction, led to a further increment of Rct thus obtaining significant signal amplification. Strept-AuNPs on the electrode surface were observed by scanning electron microscopy (SEM) after silver enhancement treatment. A competitive binding assay was also performed using unlabelled DNA target to demonstrate its applicability to real sample analysis.  相似文献   

7.
A simple and sensitive DNA impedance sensor was prepared for the detection of chronic lymphocytic leukemia. The DNA electrochemical biosensor is worked based on the electrochemical impedance spectroscopic (EIS) detection of the sequence-specific DNA related to chronic lymphocytic leukemia. The ssDNA probe was immobilized on the surface of the gold nanoparticles. Compared to the bare gold electrode, the gold nanoparticles-modified electrode could improve the density of the probe DNA attachment and hence the sensitivity of the DNA sensor greatly. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy were performed in a solution containing 1.0 mmol L−1 K3[Fe(CN)6]/K4[Fe(CN)6] and 50 mmol L−1 phosphate buffer saline pH 6.87 plus 50 mmol L−1 KCl. In the CV studied, the potential was cycled from 0.0 to +0.65 V with a scan rate of 50 mV s−1. Using EIS, the difference of the electron transfer resistance (ΔRet) was linear with the logarithm of the complementary oligonucleotides sequence concentrations in the range of 7.0 × 10−12–2.0 × 10−7 mol L−1, with a detection limit of 1.0 × 10−12 mol L−1. In addition, the DNA sensor showed a good reproducibility and stability during repeated regeneration and hybridization cycles.  相似文献   

8.
The complex of rutin-Cu (C81H86Cu2O48, abbreviated by Cu2R3, R = rutin) was synthesized and characterized by elemental analysis and IR spectra. Cyclic voltammetry (CV) and fluorescence spectroscopy were used to investigate the interaction of Cu2R3 with salmon sperm DNA. It was revealed that Cu2R3 could interact with double-stranded DNA (dsDNA) by a major intercalation role. Using Cu2R3 as a novel electroactive indicator, an electrochemical DNA biosensor for the detection of specific DNA fragment was developed and its selectivity for the recognition with different target DNA was assessed by differential pulse voltammetry (DPV). The target DNA related to coliform virus gene could be quantified ranged from 1.62 × 10−8 mol L−1 to 8.10 × 10−7 mol L−1 with a good linearity (r = 0.9989) and a detection limit of 2.3 × 10−9 mol L−1 (3σ, n = 7) was achieved by the constructed electrochemical DNA biosensor.  相似文献   

9.
This report describes the applications of cobalt tetracarboxylic acid phthalocyanine (CoTCAPc) self-assembled monolayer (SAM) immobilized onto a preformed 2-mercaptoethanol (Au-ME) SAM on gold surface (Au-ME-CoTCAPc SAM) as a potential amperometric sensor for the detection of hydrogen peroxide (H2O2) at neutral pH conditions. The Au-ME-CoTCAPc SAM sensor showed a very fast amperometric response time of approximately 1 s, good linearity at the studied concentration range of up to 5 μM with a coefficient R2 = 0.993 and a detection limit of 0.4 μM oxidatively. Also reductively, the sensor exhibited a very fast amperometric response time (∼1 s), linearity up to 5 μM with a coefficient R2 = 0.986 and a detection limit of 0.2 μM. The cobalt tetracarboxylic acid phthalocyanine self-assembled monolayer was then evaluated as a mediator for glucose oxidase (GOx)-based biosensor. The GOx (enzyme) was immobilized covalently onto Au-ME-CoTCAPc SAM using coupling agents: N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS), and the results demonstrated a good catalytic behavior. Kinetic parameters associated with the enzymatic and mediator reactions were estimated using electrochemical versions of Lineweaver-Burk and Hanes equation, and the stability of the sensor was tested. The biosensor (Au-ME-CoTCAPc-GOx SAM) electrode showed good sensitivity (7.5 nA/mM) with a good detection limit of 8.4 μM at 3σ, smaller Michaelis-Menten constant (4.8 mM from Hanes plot) and very fast response time of approximately 5 s.  相似文献   

10.
This work presents a method of enhancing the kinetics of the interfacial reaction using 1,3,5-trifluorobenzene (TFB) which is used as an electron acceptor due to its locally biased polarity and as a source of rearranging the layer of the electrolyte around LiCoO2 electrode, not a SEI layer source. The full cells with TFB show a decrease in irreversible capacity loss during the first charge-to-discharge process, regardless of the SEI layer formation, and also show better discharge properties even at high rate conditions. The charge transfer resistance (Rct) of the LiCoO2 half cell with TFB shows the smaller resistance than that of the TFB free half cell, and the activation energy calculated from the Rct was 24.7 kJ/mol for the TFB free half cell and 19.3 kJ/mol for the half cell with TFB. In addition, the film resistance of the half cell with TFB shows higher value when the temperature is below 283 K. Since Rct is related to the transfer resistance of the solvated Li+ ions on the surface of the LiCoO2 electrode, it will help design the electrolyte to improve the transfer velocity of Li+ ions around the cathode electrode for high power Li ion battery.  相似文献   

11.
A novel DNA biosensor was fabricated by modified multilayer of ssDNA, cytochrome c, l-cysteine, metal gold nanoparticles and Chitosan (denoted as ssDNA/Cyt c/l-Cys/GNPs/Chits/GCE). The behavior of the DNA biosensor was then investigated by voltammetry, impedance spectrum and atomic force microscope (AFM), and the morphologic differences among each layer of the DNA biosensor were also observed. Results revealed that two well-defined redox peaks exhibited at 0.120 V and 0.362 V, and the amount of adsorbed DNA was 1.672 × 10−10 mol cm−2. We concluded that the modified electrode could be used to detect DNA with the indicator daunomycin.  相似文献   

12.
Copper oxide (CuO)/copper oxalate (CuOx) modified non-enzymatic electrochemical sensor for the detection of glucose in alkaline medium was fabricated by electrochemical anodisation of copper electrodes in potassium oxalate solution. Morphology of the modified copper electrode was studied by Scanning Electron Microscopy (SEM) and its electrochemical behaviour by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). The formation of CuOx on the copper electrode was confirmed by the Infra-red Reflection Absorption Spectrum (IRRAS). The modified electrodes were found to be microporous and rough. Linear Sweep Voltammetry (LSV) and amperometry were adopted to investigate the direct electrocatalytic oxidation of glucose on CuO/CuOx modified electrode in alkaline medium which showed excellent catalytic activity. The best performance of the sensor was obtained at 0.7 V and in 0.1 M sodium hydroxide (NaOH). At this optimum potential, the sensor was highly selective to glucose in the presence of ascorbic acid (AA) and uric acid (UA) which are common interfering species in biological fluids. The sensitivity was found to be very high (1890 μA mM−1 cm−2) with excellent linearity (R = 0.9999) up to 15 mM having a low detection limit of 0.05 μM (S/N = 3). The modified electrode was tested for glucose level in blood serum. Based on the optimised conditions, a working model of the sensor was made and successfully tested for glucose.  相似文献   

13.
A novel electroanalytical method for the detection of paraquat using DNA modified gold nanoparticles immobilized at a gold electrode is demonstrated. The electrode surface was first modified using the self-assembly of gold nanoparticles (NPs) followed by the simple adsorption of DNA onto the NPs, which was straightforward, fast and cost effective. The DNA-nanoparticle composite sensor was then characterized in terms of electrochemical responses both in the absence and in the presence of paraquat using cyclic voltammetry, differential pulse voltammetry and square wave voltammetry. The DNA-NPs composite electrode proved to work adequately as a biosensor for the quantitative analysis of paraquat concentrations, taking advantage of utilizing both the modified gold nanoparticles and the interaction between DNA with paraquat molecules. In addition, the NPs modified electrode demonstrated good sensitivity and stability towards the first reversible reduction step of the double charged paraquat ion. Good linearity between paraquat concentration and peak current was observed for the concentration range of 5.0 × 10−6 to 1.0 × 10−3 M when using differential pulse voltammetry. The use of modified electrodes improves the performance of the biosensor in the presence of interfering species in particular when square wave voltammetry is used.  相似文献   

14.
Zhiyi Jiang 《Electrochimica acta》2009,54(11):3059-3065
Taking Y2O3 stabilized Bi2O3 (YSB) as an example, bismuth oxide-added (La,Sr)MnO3 (LSM) is evaluated as a cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs) with 8 mol% Y2O3 stabilized ZrO2 (YSZ) electrolytes. YSB was added to LSM cathodes using an impregnation method, dramatically improving the electrode performance. The interfacial polarization resistance Rp, at 700 °C for the electrode coated with 50 wt.% of YSB is 0.14 Ω cm2, which is only 0.2% of the value for a pure LSM electrode. The high oxygen ionic conductivity and the catalytic activity of YSB, as well as the favorable electrode microstructure are likely reasons for the dramatic reduction of Rp. The YSB-added LSM cathodes also exhibited lower overpotential and higher exchange current density than the pure LSM cathode. Moreover, these electrodes show much lower Rp than that of parallel-fabricated LSM electrodes with samaria-doped-CeO2 as well as other LSM-based electrodes reported in the literature, demonstrating the superiority of the of YSB as the ionic conduction component in composite LSM electrodes. The superior performance of the single cell further demonstrates that the bismuth oxide-added LSM cathode is an excellent candidate for IT-SOFCs.  相似文献   

15.
Self-assembled monolayers of dodecanethiol (C12SH-SAMs) on polycrystalline gold were prepared under ultrasonic irradiation at 100 W (the actual ultrasonic power intensity is about 0.1 W cm−2 including the heat loss) for different time and investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). CV experiments show that the differential capacitance Cd values of the C12SH-SAM prepared under ultrasonic irradiation at 100 W (0.1 W cm−2) for 15 min are independent of the scan rate, the thickness d value of this monolayer is 17.5 Å, the tilt angle φ value of the molecules in this monolayer from the gold surface normal was calculated to be 30° and the difference value of the current density at −0.2 and 0.5 V (Δip) is only 0.69 μA cm−2. From the EIS experiments, we find that the phase angle value at 1 Hz Φ1 Hz of the C12SH-SAM prepared under ultrasonic irradiation at 100 W (0.1 W cm−2) for 15 min is 89°, the charge transfer resistance Rct value of this monolayer is 1.40 × 106 Ω cm2 and the surface coverage θ value of this monolayer was calculated to be 99.997% from Rct. These results indicate that the C12SH-SAM of almost defect-free structure and very low ionic permeability can be formed under ultrasonic irradiation at 100 W (0.1 W cm−2) in a short time (15 min).  相似文献   

16.
The electrocatalytic activity of various metal hexacyanoferrates (Mhcfs) (i) immobilized on graphite electrodes, and (ii) as components of a composite electrode was investigated with respect to the reduction of hydrogen peroxide. The flow-through working electrode was a thin layer consisting of a composite of Mhcf, graphite, and polymethylmetacrylate (PMMA) as a binder, sandwiched between two Plexiglas plates. Among the pure Mhcfs immobilized on a graphite electrode, iron(III) hexacyanoferrate (Prussian blue) exhibits the highest electrocatalytic effect, whereas in the composite electrodes chromium(III) hexacyanoferrate (Crhcf) shows the highest activity and best performance and reproducibility for the electrochemical reduction of H2O2. The Crhcf electrode provides a linear dependence on H2O2 concentration in the range 2.5 × 10−6 mol L−1 (LOD) to 1 × 10−4 mol L−1 (phosphate buffer, pH 7). The sensor was applied for the detection of H2O2 enzymatically produced by glucose oxidase. The optimal conditions for the peroxide injection were 2 min after the beginning of the reaction and 25 °C with a detection limit of 7.0 × 10−6 mol L−1 for glucose.  相似文献   

17.
Amperometric detection of tolazoline (TL) was carried out on a gold nanoparticles (AuNPs)/poly-o-aminothiophenol (PoAT)-modified electrode by a molecular imprinting technique and electropolymerization method. The modification procedure was characterized via electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The recognition between the imprinted sensor and target molecule was observed by measuring the variation of amperometric response of the oxidation-reduction probe, K3Fe(CN)6 on electrode. Under the optimal experimental conditions, the peak currents were proportional to the concentrations of tolazoline in two ranges of 0.05-5.0 μg mL−1 and 5.0-240 μg mL−1 with the detection limit of 0.016 μg mL−1. Meanwhile the prepared sensor showed sensitive and selective binding sites for tolazoline. The enhancement of sensitivity was attributed to the presence of AuNPs which decreased the electron-transfer impedance.  相似文献   

18.
The copper complex of 4,5-diazafluorene-9-one (dafone) and bromine ligands ([Cu(dafone)2]Br2) was prepared and its interaction with double-stranded salmon sperm DNA (dsDNA) in pH 8.0 Britton-Robinson (B-R) buffer solution was studied by electrochemical experiments at the glassy carbon electrode (GCE). It was revealed that Cu(dafone)2Br2 could bind with salmon sperm DNA strands mainly by intercalation mode. The binding number of [Cu(dafone)2]Br2 for each salmon sperm dsDNA chain and equilibrium constant of the binding reaction were calculated to be 3 and 2.8 × 1012 L3 mol−3, respectively. The Cu(dafone)2Br2 was further utilized as a new electrochemical DNA indicator for the detection of human hepatitis B virus (HBV) DNA fragment by differential pulse voltammetry (DPV). The difference of its electrochemical responses occurred between hybridized dsDNA duplex and probe DNA was explored to assess the selectivity of the developed electrochemical DNA biosensor. The constructed electrochemical DNA biosensor achieved a detection limit of 3.18 × 10−9 mol L−1 for complementary target DNA and also realized a robust stability and good reusability.  相似文献   

19.
The catalytic mechanism Oad + ne ? Rad, , involving a redox couple (Oad, Rad) attached to the electrode, and soluble species (Csol, Dsol), is a precursor for many contemporary electrocatalytic reaction models. The theory of cyclic voltammetry for this mechanism was presented long ago for planar electrodes. Analogous rigorous theory for spherical electrodes has not been available thus far, despite the fact that the use of spherical microelectrodes for kinetic studies is often advantageous. By adopting the integral equation formalism, combined with the recently developed adaptive Huber method for integral equations, we obtain such a rigorous theory. The theory is applicable for any value of the electrode radius r0, from planar electrodes (r0 → ∞), to ultramicroelectrodes (r0 → 0). With the decreasing electrode radii the current functions increase, gradually approaching steady-state sigmoidal waves. Equations for the dependences of the forward peak potentials on dimensionless model parameters, and equations for steady-state voltammograms, obtained in this work, can be used for model verification and parameter estimation.  相似文献   

20.
A novel nonenzymatic glucose sensor based on flower-shaped (FS) Au@Pd core-shell nanoparticles-ionic liquids (ILs i.e., trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl) imide, [P(C6)3C14][Tf2N]) composite film modified glassy carbon electrodes (GCE) was reported. The Au@Pd nanocatalysts were prepared by seed-mediated growth method, forming the three-dimensional FS nanoparticles, where tens of small Pd nanoparticles (∼3 nm) aggregated on gold seeds (∼20 nm). The FS Au@Pd nanoparticle was a good candidate for the catalytic efficiency of nanometallic surfaces because of its flower-shaped nature, which has greater adsorption capacity. XPS analysis and zeta potential indicated that the surface of Pd atoms is positively charged, profiting the oxidation process of glucose. And ILs acted as bridge connecting Au@Pd one another and bucky gel as platform within the whole nanocomposite. So the modified electrode has higher sensitivity and selectivity owing to intrinsic synergistic effects of this nanocomposite. Amperometric measurements allow observation of the electrochemical oxidation of glucose at 0.0 V (vs. Ag/AgCl), the glucose oxidation current is linear to its concentration in the range of 5 nM-0.5 μM, and the detection limit was found to be 1.0 nM (S/N = 3). The as-prepared nonenzyme glucose sensor exhibited excellent stability, repeatability, and selectivity.  相似文献   

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