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1.
Yulong Gao  Tao Wang  Fengyu Liu 《中国化学》2016,34(12):1297-1303
The electrochemiluminescence (ECL) of the Ru(phen)32+/thymine (T) system at bare and graphene oxide (GO)‐modified glassy carbon (GC) electrodes was utilized to determine Hg2+ in tap water. The ECL intensity of Ru(phen)32+ was considerably enhanced by the addition of thymine because of the occurrence of ECL reaction between them. Subsequently, the ECL intensity of Ru(phen)32+/T system rapidly decreased with the addition of Hg2+ because of the formation of a T‐Hg2+‐T complex. A linear response (R2=0.9914) was obtained over a Hg2+ concentration range of 1.0×10?9 mol/L to 1.0×10?5 mol/L with a detection limit of 3.4×10?10 mol/L at a bare GC electrode in 0.1 mol/L phosphate buffer (pH=8.0). The detection limit can be further reduced to 4.2×10?12 mol/L after modification of the GC electrode by GO. To verify its applicability, the proposed method was utilized to determine Hg2+ in tap water and simulated wastewater. The method exhibited good reproducibility and stability and thus reveals the possibility of developing a novel ECL detection method for Hg2+.  相似文献   

2.
A sensitive electrochemiluminescence (ECL) biosensor for the specific DNA sequence of hepatitis C virus (HCV) was developed based on the efficient quenching effect of the ferrocene cluster functionalized gold nanoparticles (Fc@AuNPs) on the ECL of electrodeposited silica@Ru(bpy)32+-chitosan-graphene oxide nanocomposite (SiO2@Ru−CS−GO). Graphene oxide (GO) can accelerate electron transfer rate, thus improving the ECL of Ru(bpy)32+ on electrode surface. The molecular beacons (MB) was fixed to SiO2@Ru−CS−GO by glutaraldehyde (GA) using the Schiff reaction between amino groups of chitosan (CS) and MB. The ECL of SiO2@Ru−CS−GO was depressed greatly by the Fc@AuNPs labelled at the end of MB, then, a stronger ECL was observed when the distance between Fc@AuNPs and SiO2@Ru−CS−GO increased after the hybridization of target DNA with MB. Under optimum conditions, the restored ECL intensity increased linearly with the target DNA concentration in the range of 1.0×10−16∼1.0×10−10 mol ⋅ L−1, and the limit of detection (LOD) is 1.4×10−17 mol ⋅ L−1. The proposed method exhibits acceptable stability and reproducibility. In general, the constructed HCV biosensor can be used for the sensitive detection of HCV in human serum, suggesting potential application prospects in bioanalysis.  相似文献   

3.
《Electroanalysis》2004,16(17):1401-1405
The immobilization of tris(2,2′‐bipyridyl)ruthenium(II), Ru(bpy)32+, at a glassy carbon electrode was achieved by entrapping the Ru(bpy)32+ in a vapor deposited titania sol‐gel membrane. The electrogenerated chemiluminescence (ECL) of the immobilized Ru(bpy)32+ was studied. The Ru(bpy)32+ modified electrode showed a fast ECL response to both oxalate and proline. The ECL intensity was linearly related to concentrations of oxalate and proline over the ranges from 20 to 700 μmol L?1 and 20 to 600 μmol L?1, respectively. The detection limits for oxalate and proline at 3σ were 5.0 μmol L?1 and 4.0 μmol L?1, respectively. This electrode possessed good precision and stability for oxalate and proline determinations. The electrogenerated chemiluminescence mechanism of proline system was discussed. This work provided a new way for the immobilization of Ru(bpy)32+ and the application of titania sol‐gel membrane in electrogenerated chemiluminescence.  相似文献   

4.
When the concentration of dodecyl benzene sulfonic acid sodium salt (SDBS) is 0.7 mmol·L?1, the electrochemical and electrochemiluminescence (ECL) intensity of Ru(bpy)32+‐chlorpheniramine maleate (CPM) system at the Au electrode were studied. The results showed that compared with the absence of SDBS, enhancement of the ECL intensity was 14‐fold at Au electrode. Base on this, an ECL method was established for efficient and simple determination of CPM at Au electrode. Under the optimum experimental condition, the enhanced ECL intensities had good linear relationship with the concentration of CPM in the range of 1.0×10?4–1.0×10?7 mol·L?1, and a linear regression equation was obtained as follows: I (counts)=48.805×106c+394.03 (r=0.9975), the detection limit for CPM was 1.4×10?8 mol·L?1. The RSD for 5 times determinations of 1.0×10?5 mol·L?1 CPM was 3.2%. The results of recovery test were between 96.3%–102.5%, and the RSD of recovery test (n=5) was 2.7%. In addition, eleven kinds of tertiary amines‐Ru(bpy)32+ systems were investigated in the absence and presence of SDBS. The results showed that the enhancement of SDBS on ECL intensity of tertiary amines‐Ru(bpy)32+ systems was universal.  相似文献   

5.
A bud-like poly-L-tyrosine/Bi modified glassy carbon electrode (p-Tyr/Bi/GC) was prepared by CV and in situ Bi plating, whose conductivity and membrane morphology were characterized by CV, EIS and SEM, respectively. The p-Tyr membrane can effectively promote the enrichment of Cd2+. The optimal Tyr concentration and scanning number for p-Tyr/GC preparation were 2.0 mmol ⋅ L−1 and 35, while the optimal Bi3+ concentration, pH and Cd2+ accumulation potential in test medium were 3.0 μmol ⋅ L−1, 6.5 and −1.3 V, respectively. The linear equation of p-Tyr/Bi/GC's response to Cd2+ (1.0 nmol ⋅ L−1 to 2.0 μmol ⋅ L−1) was ip (μA) = −0.6809 + 100.2c (μmol ⋅ L−1) (R2 = 0.9985) with a detection limit of 0.11 nmol ⋅ L−1 (3S/N). The elimination of interference caused by Cu2+ in sample was studied by electrodeposition. The p-Tyr/Bi/GC electrode was successfully used for detecting Cd in rice samples with good reliability and accuracy. The developed Cd2+ sensor exhibits high sensitivity, wide linear range and low detection limit, especially the designed method of eliminating Cu2+ interference has the characteristics of high selectivity, simple operation and wide application range.  相似文献   

6.
Metal organic frameworks (MOFs) have attracted extensive attention in electrochemical research fields due to their high surface area and controlled porosity. Current study is design to investigate the ECL performance of the chemically modified electrode (CME) based on the bio-MOF-1, a porous zinc-adenine framework, which loaded ruthenium complex and employed for the detection of dopamine (DA). The composite material [Ru(bpy)3]2+@bio-MOF-1 (Ru-bMOF) modified carbon glassy electrode (Ru-bMOF/GCE) exhibited an excellent ECL performance having a linear co-efficient response (R2=0.9968) for 2-(dibutyl amino) ethanol (DBAE), a classical ECL co-reactant was obtained over a concentration range of 1.0×10−9 M to 1.0×10−4 M in 0.10 M pH=6.0 phosphate buffer solution (PBS). Furthermore, DA was detected based on its inhibition effect on [Ru(bpy)3]2+/DBAE system. Compared to traditional analytical methods, this method has various advantages such as simple electrode preparation, quick response, high reproducibility (RSD<2.0 %), low limit of detection (LOD=1.0×10−10 mol/L). This chemical investigated modified electrode had exploited potential for detection of DA.  相似文献   

7.
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   

8.
A novel [Ru(bpy)2(dcbpy)NHS] labeling/aptamer‐based biosensor combined with gold nanoparticle amplification for the determination of lysozyme with an electrochemiluminescence (ECL) method is presented. In this work, an aptamer, an ECL probe, gold nanoparticle amplification, and competition assay are the main protocols employed in ECL detection. With all the protocols used, an original biosensor coupled with an aptamer and [Ru(bpy)2(dcbpy)NHS] has been prepared. Its high selectivity and sensitivity are the main advantages over other traditional [Ru(bpy)3]2+ biosensors. The electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM) characterization illustrate that this biosensor is fabricated successfully. Finally, the biosensor was applied to a displacement assay in different concentrations of lysozyme solution, and an ultrasensitive ECL signal was obtained. The ECL intensity decreased proportionally to the lysozyme concentration over the range 1.0×10?13–1.0×10?8 mol L?1 with a detection limit of 1.0×10?13 mol L?1. This strategy for the aptasensor opens a rapid, selective, and sensitive route for the detection of lysozyme and potentially other proteins.  相似文献   

9.
本文应用核酸适配体构建了一种新型的电致化学发光检测蛋白体系。两个核酸适配体结合凝血酶的两个不同位点,利用这两核酸适配体与凝血酶的高亲和力构建三明治传感体系检测凝血酶。一个核酸适配体固定在金电极上用来捕获凝血酶,另一个标记有包裹电致化学发光活性物Ru(bpy)32+的二氧化硅纳米颗粒,用来检测电致化学发光信号。此核酸适配体传感器对凝血酶具有特异识别性,电致化学发光信号与凝血酶的浓度直接相关,非特异性识别的牛血红蛋白、牛血清白蛋白不干扰测定。由于在检测的核酸适配体上标记的纳米颗粒包裹有多个发光活性物,因此大大提高了发光效率和灵敏度,此法对凝血酶的线性响应范围为2.0 fmol•L-1~2.0 pmol•L-1,检测限可达1.0 fmol•L-1。  相似文献   

10.
The novel method of amoxicillin (AM) determination has been developed using single-sweep polarography. The proposed method is based on the obtaining of yellow coloured azo compound due to azo coupling reaction of previous diazotized sulphanilamide (SA) (in the medium of 0.6 M hydrochloric acid) with amoxicillin at pH=9.0 with the further reduction of the formed analytical form on a dropping mercury electrode. Voltammetric determination of amoxicillin is carried out due to the reduction peak of azo group of the obtained azo compound in the presence of 0.05 mol ⋅ L−1 Na2B4O7 as a background electrolyte at the potential Ecp2=−0.55 V and potential sweep rate of 2.5 V ⋅ s−1. The developed voltammetric method has two linear ranges of the determined concentrations (0.05–2.0) ⋅ 10−5 mol ⋅ L−1 and (0.2–1.0) ⋅ 10−4 mol ⋅ L−1 and the high sensitivity: LOD without the removing of unreacted sodium nitrite is 1.1 ⋅ 10−6 mol ⋅ L−1, and 7.2 ⋅ 10−7 mol ⋅ L−1, when NaNO2 excess is removed using urea. The developed voltammetric technique of AM determination has been approved during the analyses of tablets and oral suspension.  相似文献   

11.
An ultrasensitive electrogenerated chemiluminescence (ECL) immunoassay was proposed by using magnetic nanobeads (MNBs) as the carrier of ECL labels for ECL emission amplification. Carcinoembryonic antigen (CEA) and MNBs were initially immobilized on a platform in 1 : 1 molar ratio via sandwich immunoreaction. Subsequently, the MNBs were released from the platform and labeled with Ru(bpy)32+ species. After the MNBs with Ru(bpy)32+ were immobilized on an Au electrode, ECL of the Ru(bpy)32+ was measured for CEA determination. A linear relation between the ECL intensity and CEA concentration was obtained in a range of 1×10?14 to 3×10?13 mol/L (2.0 to 60 pg/mL) with a limit of detection of 8.0×10?15 mol/L (1.6 pg/mL).  相似文献   

12.
Hot electron induced cathodic electrochemiluminescence (ECL) was observed at screen printed carbon electrodes (SPCEs) during pulse polarization. The thin insulating film resulted from the printing inks was found to be suitable for generating hot electrons, which can further be converted to hydrated electrons and induce the subsequent luminescence. Compared with disposable Al/Al2O3 electrode, SPCEs show more stable and reproducible ECL in a wider pH range without background emission. A sensitive ECL method for determination of quercetin is proposed. The detection limit is 8.0×10?10 mol L?1(S/N=3), which is two magnitudes lower than that of common ECL method.  相似文献   

13.
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   

14.
A sensitive electrochemiluminescence (ECL) sensor for melamine analysis was fabricated based on Ru(bpy)32+-doped silica (Ru(bpy)32+@SiO2) nanoparticles and graphene composite. Spherical Ru(bpy)32+@SiO2 nanoparticles with uniform size about 55 nm were prepared by the reverse microemulsion method. Since per Ru(bpy)32+@SiO2 nanoparticle encapsulated a great deal of Ru(bpy)32+, the ECL intensity has been greatly enhanced, which resulted in high sensitivity. Due to its extraordinary electric conductivity, graphene improved the conductivity and accelerated the electron transfer rate. In addition, graphene could work as electronic channel improving the efficient luminophor amount participating in the ECL reaction, which further enhanced the ECL signal. This proposed sensor was used to melamine analysis and the ECL intensity was proportional to logarithmic melamine concentration range from 1 × 10−13 M to 1 × 10−8 M with the detect limit as low as 1 × 10−13 M. In application to detect melamine in milk, satisfactory recoveries could be obtained, which indicated this sensor having potential application in melamine analysis in real samples.  相似文献   

15.
陈晓彤  董彬  崔孟超  王科志  金林培 《化学学报》2007,65(12):1181-1184
比较研究了以C2O42-为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)2L1]2+, [Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+, [Ru(phen)2L1]2+和[Ru(phen)2L2]2+(其中bpy=2,2′-联吡啶, phen=1,10-邻菲啰啉, L1=4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L2=3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L3=3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+和[Ru(phen)2L2]2+的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)3]2+相差不大.  相似文献   

16.
Different effects of divalent metal ions on electrochemiluminescence (ECL) sensor with Ru(bpy)32+ immobilized in Eastman‐AQ membrane were investigated. Mg2+, Ca2+ and Fe2+ can elevate the ECL of Ru(bpy)32+/proline; while metal ions that underwent redox reactions on the electrode such as Mn2+ and Co2+ presented intensive quenching effects on Ru(bpy)32+ ECL. Also, the quenching effect of Mn2+ on the ECL sensor with Ru(bpy)32+ immobilized in Eastman‐AQ membrane enhanced to about 30‐folds compared with the case that Ru(bpy)32+ was dissolved in phosphate buffer, and the enhanced quenching effects of Mn2+ were studied.  相似文献   

17.
In this study, a novel electrochemiluminescence (ECL) sensor for highly sensitive and selective detection of Pb(II) was developed based on Ru(bpy)32+ encapsulated UiO66 metal‐organic‐framework (Ru(bpy)32+?UiO66 MOF) and ?NH2 group functionalized silica (NH2?SiO2). The NH2?SiO2 with large surface area provided an excellent platform for the ECL sensor. As numerous exposed carboxyl groups were present on UiO66 backbone, the Ru(bpy)32+?UiO66 could be steadily immobilized to NH2?SiO2 by forming amide bonds. Meanwhile, the introduced UiO66 MOF which used for the encapsulation of Ru(bpy)32+, significantly enhanced the ECL efficiency of the proposed sensor, as it possessed a large specific surface area and porosity for the loading of Ru(bpy)32+. Moreover, a high quenching effect on ECL intensity was obtained in the presence of Pb(II) in the electrolyte. Under the optimal conditions, the quenched ECL intensity showed a good linear relationship within Pb(II) concentration in the range from 1.0×10?6 to 1.0×102 μM, with a detection limit of 1.0×10?7 μM (S/N=3). The proposed sensor for Pb(II) detection was simple in operation, rapid in testing, stable in signal, and showed a good anti‐interference ability to some other metal ions. Besides, its application for detecting Pb(II) in a real sample was also investigated here. This work provides a potential platform for metal ions detection in environmental monitoring field.  相似文献   

18.
Abstract

The emission produced by sulfite after oxidation by potassium permanganate in acidic solution in the presence of Ru(phen)3 2+ is used to determine 1.0 × 10?7 to 2.5 × 10?5 mol/L sulfite. The limit of detection is 4.5 × 10?9 mol/L and the relative standard deviation is 3.1% for a 1 × 10?5 mol/L sulfite solution (n=8). The method was also applied satisfactorily to the determination of sulfur dioxide in air by using triethanolamine (TEA) as absorbent material.  相似文献   

19.
DNA methyltransferase (DNA MTase) can act as biomarker for many diseases and it is important to develop some new methods for sensitive detection of DNA MTase. In this work, a highly efficient electrochemiluminescence (ECL) sensor had been designed for detection of DNA MTase based on Ru(phen)32+ loaded double strand DNA (dsDNA- Ru(phen)32+) as signal tags. Ru(phen)32+ had been efficiently embed in the dsDNA produced through a simple hybridization chain reaction. First, a hairpin probe was designed, which can be specifically recognized by Dam MTase and modified with -SH at one end. It was modified on the surface of gold electrode by -SH as an immobilization probe (IP). This IP will be methylated in the present of Dam MTase and digested by DpnI following. Results in the release of capture probe (CP) which remains on the surface of gold electrode. The CP can hybridize with the single stand part of the dsDNA- Ru(phen)32+ and make the immobilization of ECL tags on the electrode surface, which results in a strong ECL signals detected. However, without the effect of Dam MTase, the hairpin structure of IP remains stable and cannot capture signal tags, and can only detecte weak ECL signals. The biosensor can detect the activity of Dam MTase in the concentration range of 0.01 U/mL to 20 U/mL with the ECL intensity and the logarithm of the concentration have a linear relationship, and the detection limit is calculated to be 7.6 mU/mL. The developed sensor has the ability to specifically detect Dam MTase, which can be differentiated from other types of DNA MTase. In addition, the designed method has good applicability to detect Dam MTase activity in serum samples and been applied to detect its inhibitor with high efficiency.  相似文献   

20.
In this study, we for the first time presented an efficient, accurate, rapid, simple and ultrasensitive detection system for small molecule ochratoxin A (OTA) by using the integration of loop-mediated isothermal amplification (LAMP) technique and subsequently direct readout of LAMP amplicons with a signal-on electrochemiluminescent (ECL) system. Firstly, the dsDNA composed by OTA aptamer and its capture DNA were immobilized on the electrode. After the target recognition, the OTA aptamer bond with target OTA and subsequently left off the electrode, which effectively decreased the immobilization amount of OTA aptamer on electrode. Then, the remaining OTA aptamers on the electrode served as inner primer to initiate the LAMP reaction. Interestingly, the LAMP amplification was detected by monitoring the intercalation of DNA-binding Ru(phen)32+ ECL indictors into newly formed amplicons with a set of integrated electrodes. The ECL indictor Ru(phen)32+ binding to amplicons caused the reduction of the ECL intensity due to the slow diffusion of Ru(phen)32+–amplicons complex to the electrode surface. Therefore, the presence of more OTA was expected to lead to the release of more OTA aptamer, which meant less OTA aptamer remained on electrode for producing LAMP amplicons, resulting in less Ru(phen)32+ interlaced into the formed amplicons within a fixed Ru(phen)32+ amount with an obviously increased ECL signal input. As a result, a detection limit as low as 10 fM for OTA was achieved. The aptasensor also has good reproducibility and stability.  相似文献   

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