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1.
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   

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.
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   

4.
Mesoporous films of platinized carbon nanotube–zirconia–Nafion composite have been used for the immobilization of tris(2,2′‐bipyridyl)ruthenium (II) (Ru(bpy)32+) on an electrode surface to yield a solid‐state electrogenerated chemiluminescence (ECL) sensor. The composite films of Pt–CNT–zirconia–Nafion exhibit much larger pore diameter (3.55 nm) than that of Nafion (2.82 nm) and thus leading to much larger ECL response for tripropylamine (TPA) because of the fast diffusion of the analyte within the films. Due to the conducting and electrocatalytic features of CNTs and Pt nanoparticles, their incorporation into the zirconia–Nafion composite films resulted in the decreased electron transfer resistance within the films. The present ECL sensor based on the Pt–CNT–zirconia–Nafion gave a linear response (R2=0.999) for TPA concentration from 3.0 nM to 1.0 mM with a remarkable detection limit (S/N=3) of 1.0 nM, which is much lower compared to those obtained with the ECL sensors based on other types of sol‐gel ceramic–Nafion composite films such as silica–Nafion and titania–Nafion.  相似文献   

5.
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   

6.
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   

7.
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   

8.
《Electroanalysis》2006,18(3):275-281
Mesoporous V2O5/Nafion composite films have been used for the immobilization of tris(2,2′‐bipyridyl)ruthenium (II) (Ru(bpy) ) on an electrode surface to yield a solid‐state electrogenerated chemiluminescence (ECL) sensor. The electrochemical and ECL behavior of Ru(bpy) ion‐exchanged into the composite films has been characterized as a function of the amount of Nafion incorporated into the V2O5/Nafion composite. The composite film with 80% Nafion content has the largest pore diameter (4.19 nm) and yields the maximum ECL response for tripropylamine (TPA) because of the fast diffusion of analyte into the film with large pores. Due to the enlarged pore size and enhanced conductivity of the V2O5/Nafion composite, the present ECL sensor based on the composite films exhibited around 2 orders of magnitude higher ECL response and one order of magnitude lower detection limit for TPA (10 nM) compared to those obtained with the ECL sensors based on other types of sol–gel ceramic/Nafion composite films such as SiO2/Nafion and TiO2/Nafion.  相似文献   

9.
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   

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.
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   

12.
Lei Qian  Xiurong Yang 《Talanta》2007,73(1):189-193
In this paper, we demonstrate an electrochemiluminescence (ECL) enhancement of tris(2,2-bipyridyl)ruthenium(II) (Ru(bpy)32+) by the addition of silver(I) ions. The maximum enhancement factor of about 5 was obtained on a glassy carbon electrode in the absence of co-reactant. The enhancement of ECL intensity was possibly attributed to the unique catalytic activity of Ag+ for reactions between Ru(bpy)33+ with OH. The higher enhancement was observed in phosphate buffer solutions compared with that from borate buffer solutions. This resulted from the fact that formation of nanoparticles with large surface area in the phosphate buffer solution exhibited high catalytic activity. The amount of Ag+, solution pH and working electrode materials played important roles for the ECL enhancement. We also studied the effects of Ag+ on Ru(bpy)32+/tripropylamine and Ru(bpy)32+/C2O42− ECL systems.  相似文献   

13.
In this paper, we describe the electrochemiluminescent (ECL) behavior of Ru(bpy)33+-incorporated clay colloids. Experimental results based on the electrochemical-quartz-crystal-microbalance (EQCM) techniques showed that Ru(bpy)33+ could be adsorbed by the clay colloids (montmorillonite K10, denoted K10). The resulting clay particles could emit light (λem 610 nm) when they were fabricated as thin films sandwiched by two conductive ITO electrodes with opposite biases. These Ru(bpy)33+-incorporated clay-modified electrodes could also emit light in aqueous oxalate solutions (pH 10) when potentials more positive than 0.9 V vs. SCE were applied. EDTA was an effective promoter for the Ru(bpy)3 (clay)3+-oxalate ECL reaction. The resulting ECL showed a remarkable sensitivity to oxygen. A glucose optrode was thus fabricated based on the Ru(bpy)33+-incorporated K10 colloids and glucose oxidase (GOx). The ECL signals behaved as a function of [glucose], covering a range from 0.1 to 10 mM at pH 10. The detection limits reached a level of 0.1 mM at this pH.  相似文献   

14.
A new method for uric acid (UA) determination based on the quenching of the cathodic ECL of the tris(2,2-bipyridine)ruthenium(II)–uricase system is described. The biosensor is based on a double-layer design containing first tris(2,2-bipyridine)ruthenium(II) (Ru(bpy)32+) electrochemically immobilized on graphite screen-printed cells and uricase in chitosan as a second layer. The uric acid biosensing is based on the ECL quenching produced by uric acid over the cathodic ECL caused by immobilized Ru(bpy)32+ in the presence of uricase. The use of a −1.1 V pulse for 1 s with a dwelling time of 10 s makes it possible to estimate the initial enzymatic rate, which is used as the analytical signal. The Stern–Volmer type calibration function shows a dynamic range from 1.0 × 10−5 to 1.0 × 10−3 M with a limit of detection of 3.1 × 10−6 M and an accuracy of 13.6% (1.0 × 10−4 M, n = 5) as relative standard deviation. Satisfactory results were obtained for urine samples, creating an affordable alternative for uric acid determination.  相似文献   

15.
Due to the high performance of glassy carbon in the aspects of mechanical strength, electrical conductivity and high corrosion resistance, etc., glassy carbon has been widely used in the electrochemistry. A new form of glassy carbon, glassy carbon microsphere, was utilized to couple with ionic liquid in preparing a new electrochemiluminescent platform for Ru(bpy)3Cl2. Room temperature ionic liquid has been proposed to be very interesting and efficient pasting binder to replace the non conductive organic binders for the fabrication of composite paste electrode. Attributed to the special characteristics of glassy carbon microspheres and room temperature ionic liquid [N-octylpyridium tetrafluoroborate (OPFP)], this new electrochemiluminescent sensor exhibited excellent electrochemiluminescent performance in Ru(bpy)32+ solution. We first found that fentanyl citrate could increase the ECL of Ru(bpy)32+, hence an ECL approach was developed for the determination of fentanyl citrate based on this glassy carbon microspheres based electrochemiluminescent platform with high sensitivity. Under the optimized conditions, the enhanced electrochemiluminescent intensity versus fentanyl citrate concentration was linear in the range of 1.0 × 10−8 to 1.0 × 10−4 mol L−1 with a detection limit of 8.5 × 10−9 mol L−1, and the relative standard deviation for 1.0 × 10−6 mol L−1 fentanyl citrate was 1.90% (n = 10). This protocol has extended the application scopes of glassy carbon material and promoted the application of glassy carbon microspheres in electroanalysis.  相似文献   

16.
《Analytical letters》2012,45(13):2077-2088
Abstract

An electrochemiluminescence (ECL) method for reduced nicotinamide adenine dinucleotide (NADH) was proposed by immobilizing tris(2,2′‐bipyridyl) ruthenium(II) (Ru(bpy)3 2+) in multiwall carbon nanotubes (MWCNTs)/Nafion composite membrane that was formed on glassy carbon electrode surface. The electrochemical and ECL behaviors of the immobilized Ru(bpy)3 2+ were investigated. The cyclic votammogram of the modified electrode in pH 7.0 phosphate buffer solution showed a couple of redox peaks at +1190 and +1060 mV at 100 mV/s. The composite film had a more open structure and a large surface area allowing faster diffusion of Ru(bpy)3 2+. The presence of MWCNTs resulted in the improved ECL sensitivity and longer‐term stability of the modified electrode. The modified electrode showed a linear response to NADH in the concentration range of 1.0×10?6 to 1.6×10?5 M with a detection limit of 8.2×10?7 M.  相似文献   

17.
A novel electrogenerated chemiluminescence (ECL) sensor based on Ru(bpy)32+‐doped titania (RuDT) nanoparticles dispersed in a perfluorosulfonated ionomer (Nafion) on a glassy carbon electrode (GCE) was developed in this paper. The electroactive component‐Ru(bpy)32+ was entrapped within the titania nanoparticles by the inverse microemulsion polymerization process that produced spherical sensors in the size region of 38±3 nm. The RuDT nanoparticles were characterized by electrochemical, transmission electron and scanning microscopy technology. The Ru(bpy)32+ encapsulation interior of the titania nanoparticles maintains its ECL efficiency and also reduces Ru(bpy)32+ leaching from the titania matrix when immersed in water due to the electrostatic interaction. This is the first attempt to prepare the RuDT nanoparticles and extend the application of electroactive component‐doped nanoparticles into the field of ECL. Since a large amount of Ru(bpy)32+ was immobilized three‐dimensionally on the electrode, the Ru(bpy)32+ ECL signal could be enhanced greatly, which finally resulted in the increased sensitivity. The ECL analytical performance of this ECL sensor for tripropylamine (TPA) was investigated in detail. This sensor shows a detection limit of 1 nmol/L for TPA. Furthermore, the present ECL sensor displays outstanding long‐term stability.  相似文献   

18.
Wang X  Zhou J  Yun W  Xiao S  Chang Z  He P  Fang Y 《Analytica chimica acta》2007,598(2):242-248
A sensitive and selective aptasensor using tri(2,2′-bipyridyl)ruthenium(II)-doped silica nanoparticles (Ru(bpy)32+-doped SNPs) as DNA tags for detection of thrombin is developed based on the target protein-induced strand displacement of the DNA probe. For the proposed aptasensor, the aptamer was assembled on the surface of the Au electrode through Au-S binding. The hybridization event between the DNA probe labeled by the Ru(bpy)32+-doped SNPs and the aptamer was evaluated by electrogenerated chemiluminescence (ECL) measurements. Then, the DNA probe was displaced by thrombin and the binding event between the thrombin and the aptamer was monitored by ECL measurements again. The difference of ECL intensity (ΔIECL) of the two events could be used to quantify the thrombin. Other proteins, such as bovine serum albumin and bovine hemoglobin, had almost negligible ΔIECL. Under the optimal conditions, the ΔIECL was linearly related to the concentration of the thrombin in the range of 10 fM to 10 pM and the detection limit was down to 1.0 fM since SNPs containing a large number of Ru(bpy)32+ molecules were labeled on the DNA probe.  相似文献   

19.
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   

20.
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   

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