An Ultrasensitive Analytical Method Based on Chemiluminescence Sensing Electrochemical Parallel Catalytic Reaction Event

An ultrasensitive electrochemiluminescence (ECL) method on the combination of electrochemical parallel catalytic reaction and chemiluminesence signal sensing was proposed for improving ECL analytical characteristics using vanadate(V) as a representative. Vanadate(V) could be electrochemically reduced to generate vanadate(II) which could be chemically oxidized by potassium periodate to regenerate vanadate(V) and give parallel catalytic wave effect. Then, the reduced product of potassium periodate could react with butyl‐rhodamine B to emit a sensitive chemiluminescence signal. The chemiluminescence intensity was correlative with vanadate(V) concentration. The investigation on the electrochemical reaction rate constant (k⁰) confirmed that the speed of electrochemical reaction was faster than that of the subsequent chemiluminescence reaction. The possibility of the combination of electrochemical parallel catalytic reaction with chemiluminescence signal sensing was proved. The similar ECL behaviors could be observed at zirconia nanowires‐Nafion modified electrode. Because of the separation and enrichment effect of the modified electrode on vanadate(V), the selectivity and sensitivity was further improved greatly. Based on these findings, a new concept on the combination of electrochemical parallel catalytic reaction and chemiluminesence signal sensing was proposed and an ultrasensitive ECL method for the determination of vanadate(V) was developed at zirconia nanowires‐Nafion modified electrode. Under the optimum experimental conditions, the ECL intensity was linear with the concentration of vanadate(V) in the range of 2.0×10^?12 mol/L–2.0×10^?10 mol/L. The detection limit was 8.0×10^?13 mol/L, which was more than 6 orders of magnitude lower than that observed by electrochemical current transduction for electrochemical parallel catalytic reaction at zirconia nanowires‐Nafion modified electrode.     

A novel electrogenerated chemiluminescence sensor for pyrogallol with core-shell luminol-doped silica nanoparticles modified electrode by the self-assembled technique

The core-shell luminol-doped SiO₂ nanoparticles were synthesized and immobilized on the surface of chitosan film coating graphite electrode by the self-assembled technique. Then, a novel electrogenerated chemiluminescence (ECL) sensor for pyrogallol was developed based on its ECL enhancing effect for the core-shell luminol-doped silica nanoparticles. The ECL analytical performances and the sensing mechanism of this ECL sensor for pyrogallol were investigated in detail. The corresponding results showed that: compared with the conventional ECL reaction procedures by luminol ECL reaction system, the electrochemical (EC) reaction of pyrogallol and its subsequent chemiluminescence (CL) reaction occurred in the different spatial region whilst offering a high efficiency to couple the EC with the CL reaction to form the ECL procedures. In this case, this new sensing scheme offered more potential to improve the analytical performances of the ECL reaction. Under the optimum experimental conditions, this ECL sensor showed less than 5% decrease in continuums over 100 times ECL measurements, the detection limit was 1.0 × 1.0⁻⁹ mol/L for pyrogallol. The linear range extended from 3.0 × 10⁻⁹ mol/L to 2.0 × 10⁻⁵ mol/L for pyrogallol.     

Highly selective electrogenerated chemiluminescence (ECL) for sulfide ion determination at multi-wall carbon nanotubes-modified graphite electrode

In the present work, a novel method for immobilization of carbon nanotubes (CNTs) on the surface of graphite electrode was proposed. We further found that superoxide ion was electrogenerated on this CNTs-modified electrode, which can react with sulfide ion combing with a weak but fast electrogenerated chemiluminescence (ECL) emission, and this weak ECL signal could be enhanced by the oxidative products of rhodamine B. In addition, the rate constant of this electrochemical reaction k⁰ was investigated and confirmed that the speed of electrogenerating superoxide ion was in accordance with the subsequent fast CL reaction. Thus, the fast CL reaction of superoxide ion with target brought in the possibility of high selectivity based on time-resolved, relative to other interferences. Based on these findings, an excellently selective and highly sensitive ECL method for sulfide ion was developed. Under the optimum conditions, the enhancing ECL signals were linear with the sulfide ion concentration in the range from 6.0 × 10⁻¹⁰ to 1.0 × 10⁻⁸ mol L⁻¹, and a 2.0 × 10⁻¹⁰ mol L⁻¹ detection limits (3σ) was achieved. In addition, the proposed method was successfully used to detect sulfide ion in environmental water samples.     

Determination of cytochrome c based on its enhancing effect on the electrogenerated chemiluminescence of carbon quantum dots

Microchimica Acta - Carbon dots (C-dots) display strong cathodic electrogenerated chemiluminescence (ECL) in neutral aqueous solution in the presence of potassium persulfate. ECL intensities...     

Lab-on-paper-based devices using chemiluminescence and electrogenerated chemiluminescence detection

As an analytical support, paper, being low cost, highly abundant, of high porosity, disposable or biodegradable, and easy to use, store, transport, and print, has excellent chemical compatibility with many applications. Since the first microfluidic paper-based analytical device (μ-PAD or lab-on-paper) was proposed, the paper-based assay has never attracted as much attention as it does now. There has recently been rapidly increasing interest in using sensitive luminescence methods, for example chemiluminescence (CL) and electrogenerated chemiluminescence (ECL), as the detection strategy for lab-on-paper devices. Because of their intrinsic characteristics, CL and ECL provide outstanding performance while retaining the simplicity, low cost, multifunctionality, versatility, flexibility, and disposability of μ-PADs. The objective of this review is to cover the development of lab-on-paper-based devices using CL and ECL detection, including fabrication of paper devices, construction of sensing interfaces, signal amplification strategies, external instruments used, and applications. We believe that lab-on-paper devices with CL and ECL detection methods will meet the diverse requirements of point-of-care diagnosis.     

Advances in bipolar electrochemiluminescence for the detection of biorelevant molecular targets

Bipolar electrochemistry (BPE) contrasts very much with conventional electrochemistry because it is based on the control of the solution potential instead of the working electrode potential. In a typical setup, a piece of conducting materials is immersed in an electrolyte and submitted to an electric field. Such conditions split the interfacial nature of the materials into cathodic and anodic domains where electrochemical reactions can readily take place. BPE has many potential applications, and the present contribution aims to focus on recent analytical applications that involve electrogenerated chemiluminescence (ECL) detection. ECL is a special case of luminescence where the excited state of the luminophore is populated after a sequence of reaction that is triggered by an initial electron transfer step occurring at the electrode surface. The coupling between BPE and ECL is a powerful approach because it provides a unique opportunity to combine the intrinsic advantages of both techniques. BPE enables the spatial separation of sensing and reporting poles, whereas ECL provides a simple and sensitive visual readout. This opinion article will describe the experimental possibilities and the most recent applications of BPE/ECL coupling for the detection of biorelevant molecular targets.     

A Novel Electrogenerated Chemiluminescence Reaction Scheme Using Core-Shell LuminoI-Based SiO2 Nanoparticles as a Regulator and Its Analytical Application

A novel core-shell luminol-based SiO2 nanoparticle While these nanoparticles were used as electrogenerated was synthesized by two step micro-emulsion method. chemiluminescence （ECL） reagent, the electrochemical （EC） reaction as well as the subsequent chemiluminescence （CL） reaction not only could be separated spatially, but also presented high efficiency for analytical purpose. In this case, the core-shell luminol-based SiO2 nanoparticles offered more potential to avoid the contradiction between the EC and the CL reaction conditions. A new ECL method based on the nanoparticle was developed, and isoniazid was selected as a model analyte to illustrate the characteristics of this new ECL method. Under the selected conditions, the proposed ECL response to isoniazid concentration was linear in the range of 1.0 ×10^-10 to 1.0 × 10^-6 g/mL with 2 × 10^-11g/mL detection limit.     

Electrochemiluminescence from successive electro- and chemo-oxidation of rifampicin and its application to the determination of rifampicin in pharmaceutical preparations and human urine

A novel electrochemiluminescence (ECL) type was proposed based on successive electro- and chemo-oxidation of oxidable analyte, which was different from both annihilation and coreactant ECL types in mechanism. Rifampicin was used as a model compound. No any chemiluminescence (CL) was produced by either electrochemical oxidation or chemical oxidation of rifampicin in KH(2)PO(4)--Na(2)B(4)O(7) (pH 6.6) buffer-dodecyl trimethyl ammonium chloride (DTAC) solution. However, an ECL was observed by electrochemical oxidization of rifampicin in the same solution in the presence of oxidant such as dissolved oxygen, activated oxygen and potassium peroxydisulfate (K(2)S(2)O(8)). The ECL was attributed to electrochemical oxidation of rifampicin to form semiquinone free radical, and then subsequently chemical oxidation of the formed radical by oxidant to form excited state rifampicin quinone. The proposed ECL type introduced additional advantages such as high selectivity, simple and convenient operation, and effective avoidance of side reaction that often took place in homogenous CL reaction, and will open a novel application field. In addition, with the ECL in the presence of K(2)S(2)O(8) as oxidant, a flow injection ECL method for the determination of rifampicin was proposed. The ECL intensity was linear with rifampicin concentration in the range of 1.0 x 10(-7) to 4.0 x 10(-5) mol l(-1) and the limit of detection (s/n=3) was 3.9 x 10(-8) mol l(-1). The proposed method was applied to the determination of rifampicin in pharmaceutical preparations and human urine.     

The enhanced electrochemiluminescence of luminol on the nickel phthalocyanine modified electrode

A glassy carbon electrode (GCE) modified with nickel(II) tetrasulfophthalocyanine (NiTSPc) and Nafion was used for the investigation of the catalytic oxidation of luminol. The modified electrode was found to much more effectively improve the emission of electrochemiluminescence(ECL) of luminol in a solution containing hydrogen peroxide. The enhanced ECL signal corresponded to the catalytic oxidation of both luminol and H(2)O(2) by NiTSPc. Attached Ni(II) on GCE was oxidised to Ni(III) and then used as the catalyst for the chemiluminescence of luminol. The enhanced stability of the ECL signal with Nafion would mainly result from the prevention of the dissolution of NiTSPc and the adsorption of the oxidation product of luminol on the electrode surface. The proposed method enables a detection limit for luminal of 6.0 x 10(-8) mol L(-1) to be achieved in the presence of H(2)O(2) in the neutral solution. The enhanced ECL intensity had a linear relationship with the concentration of luminol in the range of 1.0 x 10(-7)-8.0 x 10(-6) mol L(-1).     

Sensitive determination of heroin based on electrogenerated chemiluminescence of tris(2,2'-bipyridyl)ruthenium(II) immobilized in zeolite Y modified carbon paste electrode

A novel method for rapid, inexpensive, sensitive and selective determination of heroin was proposed by flow injection electrogenerated chemiluminescence (ECL). Zeolite Y sieves were used for the preparation of a ECL sensor by immobilizing tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+)) in their supercages, which was achieved through the ion exchange properties of the sieves. The electrochemical and ECL behaviors of Ru(bpy)3(2+) immobilized in zeolite Y modified carbon paste electrode was investigated. The immobilized Ru(bpy)3(2+) displayed a pair of surface-controlled redox peaks with an electron transfer rate constant of 1.2 +/- 0.1 s(-1) in 0.1 mol dm(-3) pH 6.3 phosphate buffer. The modified electrode showed an electrocatalytic response to the oxidation of heroin, producing a sensitized ECL signal. The ECL sensor showed a linear response to flow injection of heroin in the range of 2.0-80 micromol dm(-3) with a detection limit of 1.1 micromol dm(-3). This method for heroin determination possessed good sensitivity and reproducibility with a coefficient of variation of 1.99% (n = 15) at 50.0 micromol dm(-3). The ECL sensor showed good selectivity and long-term stability. Its surface could be renewed quickly and reproducibly by a simple polish step.     

Flow-injection electrogenerated chemiluminescence detection of hydrazine based on its in-situ electrochemical modification at a pre-anodized platinum electrode

In this paper. it was found that the enhancing effect of hydrazine on the weak electrogenerated chemiluminescence (ECL) signal of the electrooxidation of luminol at a pre-anodized platinum electrode was stronger than that of hydrazine at a bare platinum electrode. Based on this finding and the combination of this finding with a flow-injection technique, a novel, sensitive and selective ECL method for hydrazine was developed. Under the optimum experimental conditions, the relative ECL intensity was linear with hydrazine concentration over the range 2.0 x 10(-8) - 5.0 x 10(-5) mol L(-1), with a detection limit of 6.0 x 10(-9) mol L(-1).     

Electrochemical sensing in microfluidic systems using electrogenerated chemiluminescence as a photonic reporter of redox reactions

This paper describes a microfluidics-based sensing system that relies on electrochemical detection and electrogenerated chemiluminescent (ECL) reporting. The important result is that the ECL reporting reaction is chemically decoupled from the electrochemical sensing reaction. That is, the electrochemical sensing reaction does not participate directly in the ECL process, but because electrochemical cells require charge balance, the sensing and ECL reactions are electrically coupled. This provides a convenient and sensitive means for direct photonic readout of electrochemical reactions that do not directly participate in an ECL reaction and thus broadens the spectrum of redox compounds that can be detected by ECL. The approach can be implemented in either a two-electrode or bipolar (single-electrode) configuration. By manipulating the placement and dimensions of the conductors, the photonic response can be enhanced. The system is used to electrochemically detect benzyl viologen present in solution and report its presence via Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) luminescence.     

Determination of Biotin in Pharmaceutical Formulations by Potassium Permanganate-luminol-CdTe Nanoparticles Chemiluminescence System

A sensitive flow-injection chemiluminescence method was developed for the determination of biotin in the pharmaceutical formulations. The affinity between avidin and biotin was used to adsorb biotin on the polystyrene, with subsequent quantification of biotin based on its ability to enhance the chemiluminescence(CL) signal generated by the redox reaction of potassium permanganate-luminol-CdTe nanoparticles CL system. The investigations prove that apart from 3-aminophthalate, the CdTe quantum dots(QDs) play both catalytic and emitter roles. Under optimum conditions, the linear range for the determination of biotin was 0.01-25ng/mL with a detection limit of 7.3?10^-3 ng/mL(S/N=3). The relative standard deviation of 5 ng/L biotin was 2.06%(n=7). The proposed method was used to determine the biotin concentration in the pharmaceutical formulations and the recovery was between 96.4% and 104%. The proposed method is simple, convenient, rapid and sensitive.     

Comparative studies on electrogenerated chemiluminescence of luminol on gold nanoparticle modified electrodes

Comparative studies on the electrogenerated chemiluminescence (ECL) behavior of luminol on various electrodes modified with gold nanoparticles of different size were carried out in neutral solution by conventional cyclic voltammetry (CV). The results demonstrated that the gold nanoparticle modified electrodes could generate strong luminol ECL in neutral pH conditions. The catalytic performance of gold nanoparticle modified electrodes on luminol ECL depended not only on the gold nanoparticles but also on the substrate. Gold electrode and glassy carbon electrode were the most suitable substrates for the self-assembly of gold nanoparticles. Moreover, the gold nanoparticle modified gold and glassy carbon electrode had satisfying stability and reproducibility and did not need tedious pretreatment of electrode surface before each measurement. It was also found that luminol ECL behavior depended on the size of gold nanoparticles. The most intense ECL signals were obtained on a 16-nm-diameter gold nanoparticle modified electrode. The modified electrode prepared by the self-assembly method exhibited much better catalytic effect on luminol ECL than that prepared by the electrically deposited method. The ECL behavior of luminol on a gold nanoparticle self-assembled gold electrode was also investigated by other transient-state electrochemical techniques, such as chronoamperometry, differential pulse voltammetry, normal pulse voltammetry, and square wave voltammetry. The strongest ECL intensity was obtained under square wave voltammetric condition.     

碳点的性质及其在生物传感器领域的应用

碳点(carbon dots,CDs)作为一种具有优良生物相容性、低毒性和表面功能可调的新型碳基纳米材料,在生物传感领域具有极大的应用潜力.本文对碳点的生物效应、发光性质及其发光机理进行了简述,并根据传感机制的不同,将CDs在生物传感领域的应用分为荧光(fluorescence,FL)传感器、电致发光(electroc...     

Electrogenerated chemiluminescence of luminol on a gold-nanorod-modified gold electrode

Electrogenerated chemiluminescence (ECL) of luminol on a gold-nanorod-modified gold electrode was studied, and five ECL peaks were obtained under conventional cyclic voltammetry in both neutral and alkaline solutions. Among them, four ECL peaks (ECL-1-4) were also observed on a gold-nanosphere-modified gold electrode, but the intensities of these ECL peaks were enhanced about 2-10-fold on a gold-nanorod-modified gold electrode in neutral solution. One new strong ECL peak (ECL-5) was obtained at -0.28 V (vs SCE) on a gold-nanorod-modified gold electrode in both neutral and alkaline solutions and enhanced with an increase in pH. In strong alkaline solutions, ECL-1 and ECL-2 on a gold-nanosphere-modified electrode were much stronger than those on a gold-nanorod-modified gold electrode, while ECL-3-5 appeared to only happen on a gold-nanorod-modified gold electrode. The emitter of all the ECL peaks was identified as 3-aminophthalate. The ECL peaks were found to depend on the scan direction, the electrolytes, the pH, and the presence of O(2) and N(2). The reaction pathways for ECL-4 have been further elucidated, and the mechanism of the new ECL peak (ECL-5) has been proposed. The results indicate that a gold-nanorod-modified gold electrode has a catalytic effect on luminol ECL different from that of a gold-nanosphere-modified gold electrode, revealing that the shape of the metal nanoparticles has an important effect on the luminol ECL behavior. The strong ECL of luminol in neutral solution obtained on a gold-nanorod-modified electrode may be used for the sensitive detection of biologically important compounds in physiological conditions.     

Progress on the application of electrochemiluminescence biosensor based on nanomaterials

In this review, we check out the number of published literature in the field of ECL biosensors trends during nearly a decade, and compare the research status of four different types of biosensors; summarize the application forms of nanomaterials in ECL biosensor. We have an overview of the building patterns and application example of the four main types of biosensors in the paper.     

联吡啶钌电化学发光传感器测定海洛因

利用离子液体为粘合剂制作碳糊电极,采用高分子聚合法,合成包埋有Ru(bpy)2(dcbpy)2+的高分子聚合物,将钌聚合物掺杂于离子液体碳糊电极中,制作电化学发光传感器.结果表明,此传感器具有很好的电化学发光特性,与用石蜡油为粘合剂制作的电化学发光传感器相比,离子液体为粘合剂的电化学发光传感器检测三丙胺的检出限降低1个数量级.海洛因对电化学发光传感器的发光信号有很好的增强作用,基于此建立了高灵敏度检测海洛因的电化学发光分析法,海洛因浓度与电化学发光信号在2.0×10-9～2.0×10-5 mol/L范围内呈良好的线性关系,检出限为8×10-10 mol/L (S/N=3).将电化学发光传感器在5.0×10-9 mol/L海洛因溶液中采用线性循环电位连续扫描60圈,相对标准偏差小于2.2%.本方法用于血清中海洛因的检测,其回收率为94%～101%.     

Electrogenerated chemiluminesence method for the determination of riboflavin at an ionic liquid modified gold electrode

A highly sensitive electrogenerated chemiluminescence (ECL) method for the determination of riboflavin was developed based on the enhancement of ECL intensity of lucigenin at room temperature ionic liquids (RTILs) modified gold electrode. RTILs modified gold electrode exhibited excellent electrochemical and ECL property to lucigenin system and the ECL intensity of lucigenin was greatly enhanced by riboflavin. The characterization of the RTILs modified electrode and the attractive performance of the sensitive ECL method for the determination of riboflavin were investigated. Under the optimized conditions, the ECL intensity was directly proportional to the concentration of riboflavin in the range from 5.0×10(-10) g/mL to 1.0×10(-8)g/mL with the detection limit of 1×10(-10) g/mL. The method has been applied to the determination of riboflavin in the pharmaceutical preparations with satisfactory recovery from 96% to 101%. This work demonstrates that the incorporation of ECL method with RTILs modified electrode is a promising strategy for the determination of organic compounds with high sensitivity and good reproducibility.