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1.
An electrochemiluminescence (ECL) approach for methamphetamine determination was developed based on a glassy carbon electrode modified with a Ru(bpy)32+‐doped silica nanoparticles/Nafion composite film. The monodispersed nanoparticles, which were about 50 nm in size, were synthesized using the water‐in‐oil microemulsion method. The ECL results revealed that Ru(bpy)32+ doped in silica nanoparticles retained its original photo‐ and electrochemical properties. The ECL intensity was found to be proportional to methamphetamine concentration over the range from 1.0 × 10?7 to 1.0 × 10?5 mol L?1, and the detection limit was found to be 2.6 × 10?8 mol L?1. The proposed ECL approach was used to analyze the methamphetamine content in drugs. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

2.
In this study, electrochemiluminescence (ECL) of Ru(bpy)32+ (bpy = 2,2′‐bipyridyl) using ascorbic acid (H2A) as co‐reactant was investigated in an aqueous solution. When H2A was co‐existent in a Ru(bpy)32+‐containing buffer solution, ECL peaks were observed at a potential corresponding to the oxidation of Ru(bpy)32+, and the intensity was proportional to H2A concentration at lower concentration levels. The formation of the excited state *Ru(bpy)32+ was confirmed to result from the co‐reaction between Ru(bpy)33+and the intermediate of ascorbate anion radical (A•), which showed the maximum ECL at pH = 8.8. It is our first finding that the ECL intensity would be quenched significantly when the concentration of H2A was relatively higher, or upon ultrasonic irradiation. In most instances, quenching is observed with four‐fold excess of H2A over Ru(bpy)32+. The diffusional self‐quenching scheme as well as the possible reaction pathways involved in the Ru(bpy)32+–H2A ECL system are discussed in this study. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

3.
A novel “off-On” electrogenerated chemiluminescence (ECL) biosensor has been developed for the detection of mercury(II) based on molecular recognition technology. The ECL mercury(II) biosensor comprises two main parts: an ECL substrate and an ECL intensity switch. The ECL substrate was made by modifying the complex of Ruthenium(II) tris-(bipyridine)(Ru(bpy)32+)/Cyclodextrins-Au nanoparticles(CD-AuNps)/Nafion on the surface of glass carbon electrode (GCE), and the ECL intensity switch is the single hairpin DNA probe designed according to the “molecular recognition” strategy which was functionalized with ferrocene tag at one end and attached to Cyclodextrins (CD) on modified GCE through supramolecular noncovalent interaction. We demonstrated that, in the absence of Hg(II) ion, the probe keeps single hairpin structure and resulted in a quenching of ECL of Ru(bpy)32+. Whereas, in the presence of Hg(II) ion, the probe prefers to form the T-Hg(II)-T complex and lead to an obvious recovery of ECL of Ru(bpy)32+, which provided a sensing platform for the detection of Hg(II) ion. Using this sensing platform, a simple, rapid and selective “off-On” ECL biosensor for the detection of mercury(II) with a detection limit of 0.1 nM has been developed.  相似文献   

4.
Although the clinical use of immunoassays based on the oxidative‐reduction electrochemiluminescence (ECL) of tris(2,2′‐bipyridine)ruthenium (II)/tri‐n‐propylamine has been a great success, elucidation of the ECL generation mechanism still remains unsatisfactory. We report here our experimental observations of long‐lived luminescence that remains detectable for several seconds after termination of electrochemical heterogeneous oxidation. Long‐lived luminescence was observed in both a surfactant‐free buffer and a surfactant‐containing broadly used commercial buffer under different conditions. The slow decay of emission seems to have been unnoticed in previous ECL mechanistic studies. Within the frame of the reaction schemes so far proposed, its origin is inconclusively ascribed to the reductive‐oxidation process of ruthenium (II) complex, that is Ru(bpy)32+ → Ru(bpy)31+ → Ru(bpy)32+* → Ru(bpy)32+ with the involvement of the tri‐n‐propylamine‐derived radical cation. It is anticipated that long‐lived ECL will suggest a research approach to separate some homogeneous reactions from the complicated reaction system and therefore help to resolve the mechanistic mystery.  相似文献   

5.
Quenching effects of bergenin, based on the electrochemiluminescence (ECL) of the tris(2,2′‐bipyridyl)‐ruthenium(II) (Ru(bpy)32+)/tri‐n‐propylamine (TPrA) system in aqueous solution, is been described. The quenching behavior can be observed with a 100‐fold excess of bergenin over Ru(bpy)32+. In the presence of 0.1 m TPrA, the Stern–Volmer constant (KSV) of the ECL quenching is as high as 1.16 × 104 M?1 for bergenin. The logarithmic plot of the inhibited ECL versus logarithmic plot of the concentration of bergenin was linear over the range 3.0 × 10?6–1.0 × 10?4 mol/L. The corresponding limit of detection was 6.0 × 10?7 mol/L for bergenin (S/N = 3). In the mechanism of quenching it is believed that the competition of the active free radicals between Ru(bpy)32+/TPrA and bergenin was the key factor for the ECL inhibition of the system. Photoluminescence, cyclic voltammetry, coupled with bulk electrolysis, supports the supposition mechanism of the Ru(bpy)32+/TPrA–bergenin system. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

6.
Electrochemiluminescence (ECL) of tris(2,2’‐bipyridyl)ruthenium(II) [Ru(bpy)32+] is an active research area and includes the synthesis of ECL‐active materials, mechanistic studies and broad applications. Extensive research has been focused on this area, due to its scientific and practical importance. In this mini‐review we focus on the bio‐related applications of ECL. After a brief introduction to Ru(bpy)32+ ECL and its mechanisms, its application in constructing an effective bioassay is discussed in detail. Three types of ECL assay are covered: DNA, immunoassay and functional nucleic acid sensors. Finally, future directions for these assays are discussed. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

7.
《Luminescence》2002,17(2):117-122
The electrogenerated chemiluminescence of Ru(bpy)32+/C2O42? system on a pre‐polarized Au electrode was studied using a potential‐resolved electrochemiluminescence (PRECL) method. Two anodic ECL peaks were observed at 1.22 V (vs. SCE) (EP1), 1.41 V (vs. SCE) (EP2), respectively. The effects of the concentration of oxalate and Ru(bpy)32+, adsorbed sulphur, CO2, O2, pH of the solution and pretreatment of the Au electrode on the two PRECL peaks were examined. The surface state of the pre‐oxidized gold electrode was also studied using the X‐ray photoelectron spectroscopy (XPS) technique. Moreover, comparative studies on i–E and I–E curves were carried out and a possible mechanism involving both the catalytic and the direct electro‐oxidation pathways was proposed for the ECL of Ru(bpy)32+/C2O42? system. EP1 is attributed to the Ru(bpy)32/3+ reaction catalysed by C2O42? to generate Ru(bpy)32+*. EP2 is likely because C2O42? was oxidized at the electrode to form CO2, followed by reaction with Ru(bpy)33+ to generate Ru(bpy)32+*. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

8.
A simple and sensitive electrochemiluminescence (ECL) method for the determination of etamsylate has been developed by coupling an electrochemical flow‐through cell with a tris(2,2'‐bipyridyl)ruthenium(II) (Ru(bpy)32+)–Nafion‐modified carbon electrode. It is based on the oxidized Ru(bpy)32+ on the electrode surface reacting with etamsylate and producing an excellent ECL signal. Under optimized experimental conditions, the proposed method allows the measurement of etamsylate over the range of 8–1000 ng/mL with a correlation coefficient of r = 0.9997 (n = 7) and a limit of detection of 1.57 ng/mL (3σ), the relative standard deviation (RSD) for 1000 ng/mL etamsylate (n = 7) is 0.96%. The immobilized Ru(bpy)32+ carbon paste electrode shows good electrochemical and photochemical stability. This method is rapid, simple, sensitive and has good reproducibility. It has been successfully applied to the determination of the studied etamsylate in pharmaceutical preparations with satisfactory results. The possible ECL reaction mechanism has also been discussed. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

9.
The electrochemiluminescence (ECL) of tris(2,2‐bipyridyl)ruthenium [Ru(bpy)3]2+ has received much attention. By immobilizing [Ru(bpy)3]2+ on an electrode surface, solid‐state ECL has several advantages over solution‐phase ECL, such as reduced amounts of costly reagent and a simplified experimental design. Herein, different types of solid‐state ECL sensors were fabricated and the performances of paraffin oil and two ionic liquids (ILs) as the binders were compared for the construction of solid‐state ECL. Scanning electron microscopy (SEM), CCD camera, UV–vis, fluorescence spectroscopy, electrochemistry and ECL were applied to characterize and evaluate the performance of the solid‐state composites. According to the obtained results, Ru–graphite/IL octyl pyridinium hexaflurophosphate (OPPF6) was introduced as a new solid‐state ECL with excellent properties such as simple preparation, low background current, fast electron‐transfer rate and good reproducibility and stability. Moreover, for a study of the effect of carbon structure on the performance of the electrode, graphite was replaced by multi‐walled carbon nanotubes (MWCNTs) and Ru–MWCNT/OPPF6 was constructed and its efficiency was compared with Ru–graphite/OPPF6 composite electrode. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

10.
This study describes the quenching effects of p‐aminobenzenesulfonic acid (p‐ABSA) based on electrochemiluminescence (ECL) of the tris (2,2‐bipyridyl)‐ruthenium(II)(Ru(bpy)32+)/tri‐n‐propylamine (TPrA) system in aqueous solution. Quenching behaviours were observed with a 200‐fold excess of p‐ABSA over Ru(bpy)32+. In the presence of 0.1 M TPrA, the Stern‐Volmer constant (KSV) of ECL quenching was as high as 1.39 × 104 M‐1 for p‐ABSA. The logarithmic plot of inhibited ECL versus concentration of p‐ABSA was linear over the range of 6.0 × 10‐6 ‐3.0 × 10‐4 mol/L. The corresponding limit of detection was 1.2 × 10‐6 mol/L for p‐ABSA (S/N = 3). The mechanism of quenching is believed to involve an energy transfer from the excited‐state luminophore to a dimer of p‐ABSA and the adsorption of free radicals of p‐ABSA at the electrode surface that impeded the oxidation of the Ru(bpy)32+/TPrA system. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

11.
Based on the strong electrochemiluminescence (ECL) reaction between thiamazole and tris(2,2′‐bipyridine)ruthenium(II) (Ru(bpy)32+), a sensitive, simple and rapid flow injection analysis method for the determination of thiamazole was developed. When a Pt working electrode was maintained at a potential of +1.50 V (vs Ag/AgCl) in pH 12.0 H3PO4–NaOH solution containing thiamazole and Ru(bpy)32+ at a flow rate of 1.0 mL/min, a linear range of 2.0 × 10−7–1.0 × 10−4 mol/L with a detection limit of 5.0 × 10−8 mol/L was obtained for the detection of thiamazole. The method showed good reproducibility with a relative standard deviation (RSD) of 0.75%. The method has been successfully applied to the determination of thiamazole in spiked animal feeds. In addition, a co‐reactant ECL mechanism was proposed for the thiamazole–Ru(bpy)32+ system. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

12.
《Luminescence》2003,18(4):199-202
Two cathodic electrochemiluminescence (ECL) peaks have been obtained at ?0.99 and ?1.80 V (vs. SCE), respectively, from Ru(bpy)/Na?on coated onto a graphite oxide electrode in purely aqueous solution under cyclic voltammetric (CV) conditions, without addition of any reducing or oxidative reagents. These two ECL peaks were found to correlate to initial scan direction, pH, and reversal potential. Na?on played an important role in the generation of these two ECL peaks because no cathodic emission was observed in the system without Na?on. It seems that a part of Ru(bpy) electrogenerated at positive potential can remain in the Na?on, even at negative potentials. It was con?rmed that Ru(bpy)+ was formed at ?1.80 V by addition of S2O. The ECL peak at ?0.99 V is attributed to the reaction of Ru(bpy)3+ and OH?. The ECL peak at ?1.80 V is probably due to the annihilation reaction of Ru(bpy)3+ and Ru(bpy)+. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

13.
Amplification and detection of target DNA sequences are made possible in a polymerase chain reaction (PCR) by using a mixture of biotinylated and ruthenium(II) trisbipyridal (Ru(bpy)32+)-end-labelled primers. In this way, biotin for capture and Ru(bpy)32+ for detection are directly incorporated into the PCR product obviating subsequent probe hybridization. PCR of a bacterial DNA template from Alteromonas species strain JD6.5 using a cocktail of biotin- and Ru(bpy)32+-labelled primers amplified a 1 kilobase region. Serial dilution of PCR product followed by magnetic separation with Streptavidin (SA)-coated magnetic beads and an electrochemiluminescence (ECL) assay using the semi-automated QPCR System 5000 demonstrated sensitive (pg range) DNA detection. ECL assay of probe hybridization to a human immunodeficiency virus (HIV) sequence also produced pg level sensitivity. Quantitative DNA determination by ECL assay correlated well with visual detection of DNA in electrophoretic gels. However, DNA detection by ECL assay was 10 to 100 times more sensitive than conventional ethidium bromide staining. The combination of DNA-based magnetic separation with ECL assay provides a very sensitive and rapid method of quantitating DNA which, owing to its rapid and facile nature, may have many applications in the research, environmental monitoring, industrial and clinical fields.  相似文献   

14.
A sensitive electrochemiluminescence (ECL) detection of etimicin at Tris(2,2′‐bipyridyl)ruthenium(II) [Ru(bpy)32+]–Nafion modified carbon paste electrodes was developed. The immobilized Ru(bpy)32+ shows good electrochemical and photochemical activities. Electrochemical and electrochemiluminescence characterizations of the modified carbon electrodes were made by means of cyclic voltammetry and electrochemical impendence spectroscopy. The modified electrode showed an electrocatalytic response to the oxidation of etimicin, producing a sensitized ECL signal. The ECL sensor showed a linear response to etimicin in the range of 8.0–160.0 ng mL?1 with a detection limit of 6.7 ng mL?1. This method for etimicin determination possessed good sensitivity and reproducibility with a coefficient of variation of 5.1% (n = 7) at 100 ng mL?1. The ECL sensor showed good selectivity and long‐term stability. Its surface could be renewed quickly and reproducibly by a simple polish step. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

15.
On the basis of an europium (III)‐doped Prussian blue analog film modifying platinum electrode as the working electrode, a Ru(bpy)32+‐based electrochemiluminescence (ECL) assay coupled with capillary electrophoresis has been first established for the determination of ketotifen fumarate (KTF). Analytes were injected onto a separation capillary of 50 cm length (50 μm i.d., 360 μm o.d.) by electrokinetic injection for 10 s at 10 kV. Parameters related to the separation and detection were discussed and optimized. It was proved that 15 mm phosphate buffer at pH 8.0 could achieve the most favorable resolution, and the highest sensitivity of detection was obtained using the detection potential at 1.25 V and 5 mm Ru(bpy)32+ in 100 mm phosphate buffer at pH 8.0 in the detection reservoir. Under the optimized conditions, the ECL intensity was in proportion to KTF concentration over the range from 3.0 × 10?8 to 5.0 × 10?6 g mL?1 with a detection limit of 2.1 × 10?8 g mL?1 (3σ). The relative standard deviations of the ECL intensity and the migration time were 0.95 and 0.26%, respectively. The developed method was successfully applied to determine KTF contents in pharmaceuticals and human urine with recoveries between 99.5 and 107.0%. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

16.
A new metal-organic nanocomposite with synergistic catalysis function was prepared and developed to construct an electrochemiluminescence (ECL) immunosensor for ultrasensitive detection of tumor biomarker CA125. Silver nanoparticles (AgNPs) and nicotinamide adenine dinucleotide hydride (NADH) that can participate and catalyze the ECL reaction of Ru(bpy)(3)(2+) were employed as the metal component and the organic component to synthesize the metal-organic nanocomposite of NADH-AgNPs (NA). The novel ECL immunosensor was assembled via Ru(bpy)(3)(2+)-doped silica nanoparticles (Ru-SiO(2)) modified electrode with the NA as immune labels. First, the chitosan-suspended Ru-SiO(2) nanoparticles were cast on the gold electrode surface to immobilize the ECL probes of Ru(bpy)(3)(2+) and link gold nanoparticles. Then, the primary antibodies were loaded onto the modified electrode via the gold sulfhydryl covalent binding. After immunobinding the analytes of antigen, NA-attached secondary antibodies could be captured as a sandwich type on the electrode. Finally, based on the circularly synergistic catalysis by the silver and NADH for the solid-phase ECL of Ru(bpy)(3)(2+), the proposed immunosensor sensed the concentration of antigen. The synergistic ECL catalysis of metal-organic nanocomposite amplified response signal and pushed the detection limit down to 0.03 U ml(-1), which initiated a new ECL labeling field and has great significance for ECL immunoassays.  相似文献   

17.
Herein, for the first time, the electrochemiluminescent sensor based on Ru(bpy)3 2+-modified electrode using dopamine as an adhesive was successfully developed. After halloysite nanotube slurry was cast on a glassy carbon electrode and dried, an alkaline dopamine solution was added on the electrode surface. Initially, polydopamine belts with dimensions of tens to hundreds of nanometers formed via oxidization of the dopamine by ambient oxygen. As the incubation time increased, the nanobelts became broader and then united with each other to form a polydopamine film. The halloysite nanotubes were embedded within the polydopamine film. The above electrode was soaked in Ru(bpy)3 2+ aqueous solution to adsorb Ru(bpy)3 2+ into the active sites of the halloysite nanotubes via cation-exchange procedure. Through this simple procedure, a Ru(bpy)3 2+-modified electrode was obtained using only 6.25 µg Ru(bpy)3 2+, 15.0 µg dopamine, and 9.0 µg halloysite nanotubes. The electrochemistry and electrochemiluminescence (ECL) of the modified electrode was investigated using tripropylamine (TPA) and nitrilotriacetic acid (NTA) as co-reactants. The different ECL behaviors of the modified electrode using NTA and TPA as well as the contact angle measurements reflected the hydrophilic character of the electrode. The results indicate that halloysite nanotubes have a high loading capacity for Ru(bpy)3 2+ and that dopamine is suitable for the preparation of modified electrodes.  相似文献   

18.
A new method for the analysis of mebeverine hydrochloride (MEB) has been developed using a two‐chip device. The method is highly selective, sensitive, rapid and consumes minute amount of reagents. The developed method is free of interference from the degradation products of MEB and from common ingredients present in pharmaceutical formulations. The limit of detection was 0.043 µg/mL, and the limit of quantification was 0.138 µg/mL. The short analysis time per sample (20 s) allowed a large number of analyses to be performed within a very short time. Various samples were analyzed, including two different pharmaceutical formulations and a uniformity of content analysis for 20 tablets from a known batch and two biological samples at different concentrations. In addition, the method was compared with a validated high‐performance liquid chromatography (HPLC) method and the results clearly indicated the suitability of the developed method for routine analyses. A new mechanism for the tris(2,2'‐bipyridyl)ruthenium(II) (Ru(bpy)32+)‐peroxodisulfate (S2O82?) chemiluminescence (CL) system has also been proposed. The mechanism is based on photoinduced oxidation of Ru(bpy)32+ to Ru(bpy)33+ via the formation of Ru(bpy)32+* upon irradiation with visible light. S2O82? then oxidizes Ru(bpy)32+* to Ru(bpy)33+ and the analyte subsequently reduces the resultant Ru(bpy)33+ to Ru(bpy)32+*, which then produces the CL signal. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

19.
Oxalate is quantitated in both urine and plasma samples using reversed-phase ion-pair high-performance liquid chromatography (HPLC) with tris(2,2′-bipyridyl)ruthenium(II) [Ru(bpy)32+]-electrogenerated chemiluminescent (ECL) detection. Underivatized oxalate was separated on a reversed-phase column (Zorbax ODS) using a mobile phase of 10% methanol in 100 mM phsophate buffer at pH 7.0. The eluted compounds were combined with a stream of 2 mM Ru(bpy)32+ at a mixing tee before the ECL flow-cell. In the flow-cell, Ru(bpy)32+ is oxidized to Ru(bpy)32+ at a platinum electrode, and reacts with oxalate to produce chemiluminescence (CL). Urine samples were filtered and diluted prior to injection. Plasma samples were deproteinized before injection. A 25-μl aliquot of sample was injected for analysis. Possible interferants, including amino acids and indole-based compounds, present in biological samples were investigated. Without the separation, amino acids interfere by increasing the total observed CL intensity; this is expected because they give rise to CL emission on their own in reaction with Ru(bpy)33+. Indole compounds exhibit a unique interference by decreasing the CL signal when present with oxalate. Indoles inhibit their own CL emission at high concentration. By use of the indicated HPLC separation, oxalate was adequately separated from both types of interferants, which thus had no effect on the oxalate signal. Urine samples were assayed by both HPLC and enzymatic tests, the two techniques giving similar results, differing only by 1%. Detection limits were determined to be below 1 μM (1 nmol/ml) or 25 pmol injected. The working curve for oxalate was linear throughout the entire clinical range in both urine and plasma.  相似文献   

20.
Flavones such as morin, rutin, quercitrin, quercetin and wogonin were found to be able to strongly enhance the electrochemiluminescence (ECL) of the Ru(bpy)32+ system. Based on this, a novel ECL method with good stability and reproducibility could be developed for determination of flavones. Under the optimum conditions, the enhanced ECL intensity was linear with the flavones concentration in a wide range. The detection limits (defined as S:N = 3) for morin, rutin, quercitrin, quercetin and wogonin were 3.2 × 10–7 mol/L, 4.3 × 10–7, 1.8 × 10–7, 8.0 × 10–8 and 1.0 × 10–7 mol/L, respectively. In addition, the possible mechanism for the Ru(bpy)32+ ECL system in the presence of flavones is also discussed. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

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