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1.
In this work, a stable electrogenerated chemiluminescence (ECL) detector was developed. The detector was prepared by packing cation-exchanged resin particles in a glass tube, followed by inserting Pt wires (working electrode) in this tube and sealing. The leakage of Ru(bpy)32+ can be compensated by adding a small amount of Ru(bpy)32+ into solution phase. Coupled with high-performance liquid chromatography separation, the detector has been used for determination of itopride hydrochloride in human serum. Under the optimal conditions, the ECL intensity has a linear relationship with the concentration of itopride hydrochloride in the range of 1.0 × 10−8 g mL−1 to 1.0 × 10−6 g mL−1 and the detection limit was 3 × 10−9 g mL−1 (S/N = 3). The as-prepared ECL detector displayed good sensitivity and stability.  相似文献   

2.
An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)32+ immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.  相似文献   

3.
Electrochemical behavior and electrogenerated chemiluminescence (ECL) of tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) immobilized in poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)-poly(vinyl alcohol) (PEDOT/PSS-PVA) composite films via ion-exchange have been investigated with tripropylamine (TPA) as the co-reactant at a glassy carbon electrode. The immobilized Ru(bpy)32+ performed a surface-controlled electrode reaction. The Ru(bpy)32+ modified electrode showed a fast ECL response to TPA, and was used for the ECL detection of TPA with high sensitivity. The ECL intensity was linearly related to concentrations of TPA over the range from 0.50 μmol L−1 to 0.80 mmol L−1, and the detection limit was 0.10 μmol L−1 (S/N = 3). The as-prepared electrode exhibited good precision and long-term stability for TPA determination.  相似文献   

4.
A novel method for immobilization of tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)3Cl2) on electrode surfaces based on the vapor-surface sol-gel deposition strategy is first demonstrated in this paper. Ru(bpy)3Cl2 immobilized sol-gel (Ru(bpy)3Cl2/sol-gel) films were characterized by UV-vis spectroscopy and field-emitted scanning electron microscopy (FE-SEM). These results showed that Ru(bpy)3Cl2 was successfully incorporated into the silica sol-gel film. It was found that many irregular Ru(bpy)3Cl2/sol-gel clusters were formed on surfaces through one deposition and thick sol-gel films were observed after further deposition. Electrochemical properties and electrochemiluminescence (ECL) behaviors of Ru(bpy)3Cl2/sol-gel films could be easily adjusted by deposition numbers and time. At last, the Ru(bpy)3Cl2/sol-gel film modified electrode was used for solid-state ECL detection of tripropylamine. The linear range was from 5.8 × 10−8 to 2.4 × 10−4 M with the detection limit of 5 nM, which was three orders of magnitude lower than that from pure Nafion-modified electrodes. The ECL sensor also exhibited high stability, and still remained 92% response after being stored in air for 35 days. This method for immobilization of Ru(bpy)3Cl2 is simple, convenient and low-cost relative to others, so it shows promising applications in solid-state ECL detection.  相似文献   

5.
In this paper the strong electrochemiluminescence (ECL) nanoparticles have been prepared based on the anionic polyelectrolyte sodium polyacrylate (PAA)-ECL enhancement for Ru(bpy)32+, which were loaded by the carrier of SiO2 nanoparticle. There were two kinds of Ru(bpy)32+ for the as-prepared nanoparticles, the doped one and the exchanged one. The former was loaded inside the ECL nanoparticles by doping, in a form of ion-pair macromolecules PAA–Ru(bpy)32+. The corresponding ECL was enhanced about 2 times owing to the doping increase of Ru(bpy)32+. The latter was loaded on the PAA-doped Nafion membrane by ion exchange. The corresponding ECL was enhanced about 3 times owing to the ion-exchanging increase of Ru(bpy)32+. At the same time, ECL intensity of the doped-inside Ru(bpy)32+ was further enhanced 13 times because polyelectrolyte PAA in the doped membrane could obviously enhance electron transfer between the doped Ru(bpy)32+ and the working electrode. Furthermore, based on hydrophobic regions of the doped membrane antibody labeling could be easily realized by the as-prepared nanoparticles and then a high sensitive ECL immunoassay for HBsAg was developed. The linear range was between 1.0 and 100 pg mL−1 (R2 = 0.9912). The detection limit could be as low as 0.11 pg mL−1 (signal-to-noise ratio = 3).  相似文献   

6.
Zhou M  Ma YJ  Ren XN  Zhou XY  Li L  Chen H 《Analytica chimica acta》2007,587(1):104-109
A Ru(bpy)32+-based electrochemiluminescence (ECL) detection coupled with capillary electrophoresis (CE) has been established for the determination of sinomenine for the first time. Optimum separation was achieved with a fused-silica capillary column (50 cm × 25 μm i.d.) and a background electrolyte of 50 mM sodium phosphate (pH 5.0) at a separation voltage of 15 kV. The content of sinomenine was detected by ECL at the detection voltage of 1.15 V (versus Ag/AgCl) with 5 mM Ru(bpy)32+ in 75 mM phosphate solution (pH 8.0) when a chemically modified platinum electrode by europium(III)-doped prussian blue analogue (Eu-PB) was used as a working electrode. Under the optimized conditions, the ECL intensity was in proportion to sinomenine concentration in the range from 0.01 to 1.0 μg mL−1 with a detection limit of 2.0 ng mL−1 (3σ). The relative standard derivations of migration time and ECL intensity were 0.93 and 1.11%, respectively. The level of sinomenine in Sinomenium acutum Rehd. et Wils was easily determined with recoveries between 98.6 and 102.7%.  相似文献   

7.
An electrochemiluminescence (ECL) sensor based on Ru(bpy)32+-graphene-Nafion composite film was developed. The graphene sheet was produced by chemical conversion of graphite, and was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and Raman spectroscopy. The introduction of conductive graphene into Nafion not only greatly facilitates the electron transfer of Ru(bpy)32+, but also dramatically improves the long-term stability of the sensor by inhibiting the migration of Ru(bpy)32+ into the electrochemically inactive hydrophobic region of Nafion. The ECL sensor gives a good linear range over 1 × 10−7 to 1 × 10−4 M with a detection limit of 50 nM towards the determination of tripropylamine (TPA), comparable to that obtained by Nafion-CNT. The ECL sensor keeps over 80% and 85% activity towards 0.1 mM TPA after being stored in air and in 0.1 M pH 7.5 phosphate buffer solution (PBS) for a month, respectively. The long-term stability of the modified electrode is better than electrodes modified with Nafion, Nafion-silica, Nafion-titania, or sol-gel films containing Ru(bpy)32+. Furthermore, the ECL sensor was successfully applied to the selective and sensitive determination of oxalate in urine samples.  相似文献   

8.
A new electrogenerated chemiluminescence biosensor was fabricated by immobilizing ECL reagent Ru(bpy)32+ and alcohol dehydrogenase in sol-gel/chitosan/poly(sodium 4-styrene sulfonate) (PSS) organically modified composite material. The component PSS was used to immobilize ECL reagent Ru(bpy)32+ by ion-exchange, while the addition of chitosan was to prevent the cracking of conventional sol-gel-derived glasses and provide biocompatible microenvironment for alcohol dehydrogenase. Such biosensor combined enzymatic selectivity with the sensitivity of ECL detection for quantification of enzyme substrate and it was much simpler than previous double-layer design. The detection limit was 9.3 × 10−6 M for alcohol (S/N = 3) with a linear range from 2.79 × 10−5 to 5.78 × 10−2 M. With ECL detection, the biosensor exhibited wide linear range, high sensitivity and good stability.  相似文献   

9.
Adrenaline was found to inhibit strongly the electrochemiluminescence (ECL) from the Ru(bpy)32+/tripropylamine system when a working Pt electrode was maintained at 1.05 V (versus Ag/AgCl) in pH 8.0 phosphate buffer. On this basis, a flow injection (FI) procedure with inhibited electrochemiluminescence detection has been developed for determination of adrenaline. The method exhibited a good reproducibility, sensitivity, and stability with a detection limit (signal-to-noise ratio = 3) of 7.0×10−9 mol l−1 and dynamic concentration range of 2×10−8 to 1×10−4 mol l−1. The relative standard deviation was 2.2% for 1.0×10−6 mol l−1 adrenaline (n=11). The method was successfully applied to the determination of adrenaline in pharmaceutical samples. Moreover, ECL emission spectra, UV-Vis absorption spectra and cyclic voltammograms of Ru(bpy)32+/tripropylamine/adrenaline were studied. The inhibition mechanism has been proposed as the interaction of electrogenerated Ru(bpy)32+* and the o-benzoquinone derivatives, adrenochrome and adrenalinequinone, at the electrode surface.  相似文献   

10.
Tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) has been successfully immobilized onto electrode through the electrodeposition of Ru(bpy)32+/AuNPs/chitosan composite film. In the experiments, chitosan solution was first mixed with Au nanoparticles (AuNPs) and Ru(bpy)32+. Then, during chronopotentiometry experiments in this mixed solution, a porous 3D network structured film containing Ru(bpy)32+, AuNPs and chitosan has been electrodeposited onto cathode due to the deposition of chitosan when pH value is over its pKa (6.3). The applied current density is crucial to the film thickness and the amount of the entrapped Ru(bpy)32+. Additionally, these doping Ru(bpy)32+ in the composite film maintained their intrinsic electrochemical and electrochemiluminescence activities. Consequently, this Ru(bpy)32+/AuNPs/chitosan modified electrode has been used in ECL to detect tripropylamine, and the detection limit was 5 × 10−10 M.  相似文献   

11.
Li Mao  Ruo Yuan  Yaqin Chai  Xia Yang 《Talanta》2010,80(5):1692-4551
An effective method for immobilization of Ru(bpy)32+ on glassy carbon electrode surface (GCE) is developed for the preparation of a novel electrochemiluminescence sensor. First of all, the positively charged Ru(bpy)32+ is modified on the surface of negatively charged gold nanoparticles (nano-Au) via the electrostatic interactions to obtain the Ru(bpy)32+/nano-Au nano-sphere (abbreviate as Ru-AuNPs). Subsequently, the large amount of Ru-AuNPs are immobilized on the multi-wall carbon nanotubes (MWCNTs)-Nafion homogeneous composite coated GCE by dual interaction: firstly, the Nafion, a kind of typical cation-exchange membrane, can absorb the Ru-AuNPs as the enrichment of cation Ru(bpy)32+ on the Ru-AuNPs surface; secondly, the employment of carboxylic MWCNTs in the Nafion film can also chemosorb the Ru(bpy)32+ cation on the Ru-AuNPs surface to increase the carrier content. At the same time, the experiment confirms that the enhancement of the ECL intensity on the sensor is attributed to following reasons. One hand, the employment of MWCNTs in the Nafion film enlarged the electro-active surface areas to benefit the contact between the signal probe on the composite film and coreactant used as reinforcing agent. On the other hand, the nano-materials of MWCNTs and nano-Au also improve the conductivity of the assembled film to increase the quantity of excited state of Ru(bpy)32+ in the unit time under the electrochemical condition and finally cause better properties in luminescence. In the experiment, the influence of the coreactant tripropylamine (TPA) on proposed ECL sensor is investigated. The logarithm of ECL intensity is proportional to the logarithm of TPA concentration on the range of 4 × 10−10 M to 2.8 × 10−6 M and 2.8 × 10−6 M to 0.71 × 10−3 M. After optimizing these conditions, the ECL sensor with TPA as coreactant is employed to detect a kind of alkaloid medicine, Matrine, for evaluating the practical application in the medicine analysis. The present sensor with TPA as coreactant shows the good response to the medicine concentration of the Matrine from 2.0 × 10−6 M to 6.0 × 10−3 M, which is used to detect the Matrine concentration in the Matrine injection.  相似文献   

12.
Here, we describe a new approach for electrochemiluminescence (ECL) assay with Ru(bpy)32+-encapsulated silica nanoparticle (SiO2@Ru) as labels. A water-in-oil (W/O) microemulsion method was employed for one-pot synthesis of SiO2@Ru nanoparticles. The as-synthesized SiO2@Ru nanoparticles have a narrow size distribution, which allows reproducible loading of Ru(bpy)32+ inside the silica shell and of α-fetoprotein antibody (anti-AFP), a model antibody, on the silica surface with glutaraldehyde as linkage. The silica shell effectively prevents leakage of Ru(bpy)32+ into the aqueous solution due to strong electrostatic interaction between the positively charged Ru(bpy)32+ and the negatively charged surface of silica. The porous structure of silica shell allowed the ion to move easily through the pore to exchange energy/electrons with the entrapped Ru(bpy)32+. The as-synthesized SiO2@Ru can be used as a label for ultrasensitive detection of biomarkers through a sandwiched immunoassay process. The calibration range of AFP concentration was 0.05-30 ng mL−1 with linear relation from 0.05 to 20 ng mL−1 and a detection limit of 0.035 ng mL−1 at 3σ. The resulting immunosensors possess high sensitivity and good analytical performance.  相似文献   

13.
Herein, highly efficient solid-state ECL sensor was introduced for the first time onto the screen printed electrodes of the paper-based chips (PCs) based on the composite film of poly(sodium 4-styrenesulfonate) functionalized graphene (PSSG) and Nafion. Attributed to the cooperative characteristics of both PSS and graphene, PSSG ensured both effective Ru(bpy)32+ immobilization and fast electron transfer of Ru(bpy)32+ in the composite film. The ECL behaviors at the developed sensor were investigated using tripropylamine as a representative analyte and low detection limit (S N−1 = 3) of 5.0 nM was obtained. It also exhibited more excellent reproducibility (relative standard deviations of 0.63% for continuous 45 cycles) and long-term stability (∼80% of its initial ECL intensity could be retained over 3 months). More importantly, assisted by the developed ECL sensor, discrimination of 1.0 nM single-nucleotide mismatch in human urine matrix could be realized on the PCs for the first attempt. Thus, the developed sensor was confirmed with the advantages of highly sensitivity, long-term stability, simplicity, low cost, disposability, high efficiency and potential applicability.  相似文献   

14.
Liu H  Yuan R  Chai Y  Mao L  Yang X  Zhuo Y  Yuan Y 《Talanta》2011,84(2):387-392
A new electrochemiluminescence (ECL) detector for capillary electrophoresis (CE) based on tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) immobilized in Nafion/PTC-NH2 (an ammonolysis product of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA)) composite film was presented for the first time. The Nafion/PTC-NH2 composite film could effectively immobilize tris(2,2′-bipyridyl)ruthenium(II) via ion-exchange and electrostatic interaction. Cyclic voltammetric and ECL behavior of Nafion/PTC-NH2/Ru composite film was investigated compared to Nafion/Ru composite. The Nafion/PTC-NH2/Ru composite film exhibited good ECL stability and simple operability. Then the CE with solid-state ECL detector system was successfully used to detect sophora - a quinolizidine type - alkaloids as sophoridine (SR) and matrine (MT). The CE-ECL parameters that affected separation and detection were optimized. Under the optimized conditions, the linear range was from 2.5 × 10−8 to 2 × 10−6 mol/L for SR, 1.0 × 10−8 to 1.0 × 10−6 mol/L for MT. The detection limit (S/N = 3) was estimated to be 5 × 10−9 and 10−9 mol/L for SR and MT, respectively. It was shown that the CE coupling with solid-state ECL detector system exhibited satisfying sensitivity of analysis.  相似文献   

15.
Electrochemiluminescence (ECL) of ruthenium complexes has broad applications and the immobilization of Ru(bpy)32+ has received extensive attention. In comparison with Ru(bpy)32+, Ru(phen)32+ can be immobilized more easily because of its better adsorbability. In this study, immobilization of Ru(phen)32+ for ECL analysis has been demonstrated for the first time by using graphene oxide (GO) as an immobilization matrix. The immobilization of Ru(phen)32+ is achieved easily by mixing Ru(phen)32+ with GO without using any ion exchange polymer or covalent method. The strong binding of Ru(phen)32+ with GO is attributed to both the π–π stacking interaction and the electrostatic interaction. The Ru(phen)32+/GO modified electrode was characterized by using tripropylamine (TPA) as the coreactant. The linear range of TPA is from 3 × 10−7 to 3 × 10−2 mol L−1 with the detection limit of 3 × 10−7 mol L−1. The ECL sensor demonstrates outstanding long-term stability. After the storage in the ambient environment for 90 days, the ECL response remains comparable with its original signal.  相似文献   

16.
A highly sensitive and stable tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) electrogenerated chemiluminescence (ECL) sensor was developed based on carbon nanotube (CNT) dispersed in mesoporous composite films of sol-gel titania and perfluorosulfonated ionomer (Nafion). Single-wall (SWCNT) and multi-wall carbon nanotubes (MWCNT) can be easily dispersed in the titania-Nafion composite solution. The hydrophobic CNT in the titania-Nafion composite films coated on a glassy carbon electrode certainly increased the amount of Ru(bpy)32+ immobilized in the ECL sensor by adsorption of Ru(bpy)32+ onto CNT surface, the electrocatalytic activity towards the oxidation of hydrophobic analytes, and the electronic conductivity of the composite films. Therefore, the present ECL sensor based on the CNT-titania-Nafion showed improved ECL sensitivity for tripropylamine (TPA) compared to the ECL sensors based on both titania-Nafion composite films without CNT and pure Nafion films. The present Ru(bpy)32+ ECL sensor based on the MWCNT-titania--Nafion composite gave a linear response (R2 = 0.999) for TPA concentration from 50 nM to 1.0 mM with a remarkable detection limit (S/N = 3) of 10 nM while the ECL sensors based on titania-Nafion composite without MWCNT, pure Nafion films, and MWCNT-Nafion composite gave a detection limit of 0.1 μM, 1 μM, and 50 nM, respectively. The present ECL sensor showed outstanding long-term stability (no signal loss for 4 months).  相似文献   

17.
A novel method was developed for the determination of amiodarone and desethylamiodarone by high-performance liquid chromatography (HPLC) coupled with chemiluminescent (CL) detection. The procedure is based on the post-column photolysis of the analytes into photoproducts which are active in the tris(2,2′-bipyridyl)ruthenium(III) [Ru(bpy)33+] CL system. Ru(bpy)33+ was on-line generated by photo-oxidation of the Ru(II) complex in the presence of peroxydisulfate. The separation was carried out on a Mediterranea C18 column with isocratic elution using a mixture of methanol and 0.017 mol L−1 ammonium sulfate buffer of pH 6.8. Under the optimum conditions, analytical curves, based on standard solutions, were linear over the range 0.1-50 μg mL−1 for amiodarone and 0.5-25 μg mL−1 for desethylamiodarone. The detection limits of amiodarone and desethylamiodarone were 0.02 and 0.11 μg mL−1, respectively. Intra- and inter-day precision values of 0.9% relative standard deviation (R.S.D.) (n = 10) and 1.6% R.S.D. (n = 15), respectively, were obtained. The method was applied successfully to the determination of these compounds in serum and pharmaceutical formulations.  相似文献   

18.
A new electrochemiluminescent (ECL) detection system equipped with an electrically controlled heating cylindrical microelectrode (HME) was developed in this paper. The cylindrical microelectrode made of platinum wire (25 μm in diameter, 6 mm in long) was used as the working electrode of the ECL detection system, the temperature of the electrode could be controlled electrically. The Ru(bpy)32+-ECL and Ru(bpy)32+-C2O42−-ECL systems were used to evaluate this ECL detection system. The detection limit for oxalate was found to be 3.0 × 10−4 mol/L when Te (temperature of the HME) was 22 °C, and found to be 3.0 × 10−6 mol/L at 80 °C, which indicates that the detection limit can be improved greatly at higher Te, based on which, it is possible to establish a more sensitive method for measurement of ECL by using a heated microelectrode.  相似文献   

19.
Solid-state electrochemiluminescence of a novel iridium(Ⅲ) complex   总被引:2,自引:0,他引:2  
The solid-state ECL behavior of a water-insoluble bis-cyclometalated (pq)2Ir(N-phMA) complex is presented, in which pq is a 2-phenylquinoline anion and N-phMA is N-phenyl methacrylamide, a monoanionic bidentate ligand. The MWNTs/(pq)2Ir(N-phMA) film, MWNTs/Ru(bpy)3^2+ film and (pq)2Ir(N-phMA) directly modified glassy carbon electrode were fabricated; only the MWNTs/(pq)2Ir(N-phMA) film can produce steady ECL in the presence of tri-n-propylamine as a coreactant.  相似文献   

20.
The electrochemistry and electrochemiluminescence (ECL) of novel three-dimensional nanostructured Ru(bpy)32+/Ni(OH)2 microspheres were investigated for the first time. The negatively charged porous Ni(OH)2 microspheres composed of Ni(OH)2 nanowires were specifically designed to interact with Ru(bpy)32+. The large surface area and porous structure of Ni(OH)2 microspheres enhance loading of Ru(bpy)32+ and mass transport of the model analyte, tripropylamine (TPA). Excellent ECL performance of the presented sensor was achieved including good stability and wide linear range from 7.7 × 10−10 to 3.8 × 10−3 M with the detection limit of 2.6 × 10−10 M to TPA.  相似文献   

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