The Sensitized Solid‐Phase Electrochemiluminescence of Electrodeposited Poly‐Luminol/Aniline on AuAg/TiO2 Nanohybrid Functionalized Electrode for Flow Injection Analysis

In this study, a copolymer of luminol with aniline is electrochemically deposited onto the AuAg/TiO₂ nanohybrid functionalized indium tin oxide coated glass. It is used as a reagentless electrochemiluminescent (ECL) electrode for flow‐injection‐analysis (FIA). The properties of this solid phase ECL electrode are characterized by cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy etc. It has stronger ECL emission, sensitive response for target analytes and excellent stability. The so‐prepared ECL electrode shows sensitive response to reactive oxygen species thereafter to be applied for determination of hydrogen peroxide with FIA mode. Under optimized conditions, a mass detection limit of 0.822 pg of hydrogen peroxide was obtained. Thus the hydrogen peroxide residues in samples were detected with satisfactory result.     

Intensification of electrochemiluminescence of luminol on TiO2 supported Au atomic cluster nano-hybrid modified electrode

With TiO(2) nanoparticles as carrier, a supported nano-material of Au atomic cluster/TiO(2) nano-hybrid was synthesized. It was then modified onto the surface of indium tin oxide (ITO) by Nafion to act as a working electrode for exciting the electrochemiluminescence (ECL) of luminol. The properties of the nano-hybrid and the modified electrode were characterized by XRD, XPS, electronic microscopy, electrochemistry and spectroscopy. The experimental results demonstrated that the modification of this nano-hybrid onto the ITO electrode efficiently intensified the ECL of luminol. It was also revealed that the ECL intensity of luminol on this modified electrode showed very sensitive responses to oxygen and hydrogen peroxide. The detection limits for dissolved oxygen and hydrogen peroxide were 2 μg L(-1) and 5.5 × 10(-12) M, respectively. Besides the discussion of the intensifying mechanism of this nano-hybrid for ECL of luminol, the developed method was also applied for monitoring dissolved oxygen and evaluating the scavenging efficiency of reactive oxygen species of the Ganoderma lucidum spore.     

Role of molecular oxygen and its active forms in generation of electrochemiluminescence

A short review is dedicated to the role of molecular oxygen and its active forms in generation of electrochemiluminescence (ECL). It is shown at the example of such widely used luminogens as luminol, lucigenin, acridine esters, acridane, and indoles that the role of O₂ and its active forms, such as hydrogen peroxide, superoxide and hydroperoxide radicals in generation of ECL by organic compounds is largely reduced to oxidation of the initial luminogen or intermediates of its partial electrochemical preoxidation/prereduction. Such intermediates are most often particles in the doublet state (radical-cation, radical-anion, or free radicals) that form unstable emitter precursors of peroxide (dioxetanone) type under interaction with O₂, hydrogen peroxide, or other active oxygen forms. It is also shown that the product of secondary transformations of active oxygen forms is singlet oxygen that may also be a radiation source as a result of cooperative transitions.     

Electrochemiluminescence detection of dichlorvos pesticide in luminol-CTAB medium

A simple, novel electrochemiluminescence (ECL) method for the detection of dichlorvos pesticide (DDVP) with high sensitivity was discovered. Detection was carried out in a static ECL system, in which a glassy carbon electrode was selected as the working electrode. ECL parameters, including the concentrations of cetyrltrimethylammonium bromide and luminol, the solution pH, and the scan rate of the applied potential, were optimized. Under these optimal conditions, the linear response of ECL-emission versus DDVP concentration was valid in the range 5-8000 ng/L (r(2)=0.9982) with a relative standard deviation of 4.3% at 2000 ng/L (n=10), yielding a detection limit (S/N=3) of 0.42 ng/L. The ECL emission was caused by a radical reaction process, in which the dissolved oxygen in the luminol solution reacted with the DDVP and generated free radicals. The free radicals reacted with the luminol anion and yielded the luminol radical. The approach presented was successfully applied to the determination of DDVP residues in vegetable samples.     

Single-Atom Iron Boosts Electrochemiluminescence

The traditional luminol–H₂O₂ electrochemiluminescence (ECL) sensing platform suffers from self-decomposition of H₂O₂ at room temperature, hampering its application for quantitative analysis. In this work, for the first time we employ iron single-atom catalysts (Fe-N-C SACs) as an advanced co-reactant accelerator to directly reduce the dissolved oxygen (O₂) to reactive oxygen species (ROS). Owing to the unique electronic structure and catalytic activity of Fe-N-C SACs, large amounts of ROS are efficiently produced, which then react with the luminol anion radical and significantly amplify the luminol ECL emission. Under the optimum conditions, a Fe-N-C SACs–luminol ECL sensor for antioxidant capacity measurement was developed with a good linear range from 0.8 μm to 1.0 mm of Trolox.     

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).     

Single‐Atom Iron Boosts Electrochemiluminescence

The traditional luminol–H₂O₂ electrochemiluminescence (ECL) sensing platform suffers from self‐decomposition of H₂O₂ at room temperature, hampering its application for quantitative analysis. In this work, for the first time we employ iron single‐atom catalysts (Fe‐N‐C SACs) as an advanced co‐reactant accelerator to directly reduce the dissolved oxygen (O₂) to reactive oxygen species (ROS). Owing to the unique electronic structure and catalytic activity of Fe‐N‐C SACs, large amounts of ROS are efficiently produced, which then react with the luminol anion radical and significantly amplify the luminol ECL emission. Under the optimum conditions, a Fe‐N‐C SACs–luminol ECL sensor for antioxidant capacity measurement was developed with a good linear range from 0.8 μm to 1.0 mm of Trolox.     

PCB-based integration of electrochemiluminescence detection for microfluidic systems

This communication presents an instrumental development based on the printed circuit board (PCB) technology to integrate electrochemiluminescence (ECL) analysis in microfluidic systems. PCB gold macro- (10 mm2) and micro- (0.09 mm2) electrodes and two ECL microfluidic devices are designed, fabricated and tested via luminol ECL detection. Potential modulation is performed between 0.7 and 0 V vs. Ag/AgCl for luminol oxidation, thus giving rise to on/off ECL responses in the presence of hydrogen peroxide. Synchronous detection is adopted to allow weak ECL signal recovery at a very low signal-to-noise ratio (SNR). The detection limit obtained with the two ECL microfluidic devices is 50 nM and 100 nM H2O2 for macroelectrodes and microelectrodes, respectively.     

Enhancement in Chemiluminescence by Carbonate for Cobalt(II)‐catalyzed Oxidation of Luminol with Hydrogen Peroxide

Chemiluminescence (CL) from the cobalt(II)‐catalyzed oxidation of luminol with hydrogen peroxide was dramatically enhanced by the presence of carbonate. The CL signal increases by several orders of magnitude over a wide range of concentrations of Co(II), luminol, or hydrogen peroxide. A limit of detection of 10^?12 M for Co(II) and luminol and 10^?8 M for hydrogen peroxide can be achieved. The CL emission spectrum exhibits a maximum at 425 nm, indicating that the excited 3‐aminophthalate is the emitting species. ESR spin‐trapping experiments revealed a large increase in the production of hydroxyl and carbonate radicals by the presence of carbonate, which is responsible for the enormous CL enhancement. Uric acid, ascorbic acid, acetaminophen, and p‐hydroxyphenyl acetic acid are capable of scavenging the radicals, thereby inhibiting the CL emission. The inhibition of CL intensity can be used to determine these substances at the sub‐micromolar level.     

电化学发光淬灭法测定SOD

在硼酸缓冲溶液（pH6．7）中性介质中,O2和H2O2均对鲁米诺的电化学发光（ECL）有敏化作用,而超氧化物歧化酶（SOD）对此敏化的电化学发光具有淬灭作用,SOD的浓度与两种发光体系的ECL光强成线性关系,可用于SOD的测定,为SOD的测定提供了一种灵敏、可靠的测定方法。     

基于CoFe(Ⅲ)PBA/GO过氧化物模拟酶化学发光法检测H2O2和抗坏血酸

制备了一种具有过氧化物酶活性的类普鲁士蓝/氧化石墨烯复合纳米材料(CoFe(Ⅲ)PBA/GO)。将具有过氧化物酶活性的CoFe(Ⅲ)PBA/GO和化学发光法相结合,构建了一种用于检测H₂O₂和抗坏血酸(AA)的化学发光分析法。CoFe(Ⅲ)PBA/GO催化H₂O₂产生的O₂·^-,·OH,1O₂自由基氧化Luminol会产生很强的化学发光信号,通过检测化学发光强度可以实现对H₂O₂的检测。该方法检测H₂O₂的线性范围为0~0.8μmol/L,检测限为11 nmol/L。利用AA作为活性氧消除剂可以抑制化学发光反应的特点,实现了AA的检测。该方法测定AA的线性范围为0.02~0.8μmol/L,检测限为20 nmol/L。方法已应用于H₂O₂消毒水中H₂O₂和维生素C片中抗坏血酸的检测。     

Peroxidase-catalysed luminol chemiluminescence method for the determination of glutathione

A luminol chemiluminescence (CL) method was developed for the determination of glutathione (GSH). GSH was indirectly determined by measuring the amount of hydrogen peroxide formed during the Cu(II)-catalysed oxidation of GSH with oxygen. The amount of hydrogen peroxide formed was continuously measured using the Arthromyces ramosus peroxidase-catalysed luminol CL reaction. The CL intensities at maximum light emission were linearly correlated with the concentration of GSH over the range 7.5 x 10(-7)-3.0 x 10(-5) M. The detection limit for GSH was about 10 times better than that of the spectrophotometric method using Ellman reagent.     

A novel electrochemiluminescence glucose biosensor based on platinum nanoflowers/graphene oxide/glucose oxidase modified glassy carbon electrode

A novel electrochemiluminescence (ECL) biosensor based on platinum nanoflowers (PtNFs)/graphene oxide (GO)/glucose oxidase (GODx) was discovered for glucose detection. PtNFs/GO was synthesized using a nontoxic, rapid, one-pot and template-free method and characterized by transmission electron microscopy (TEM) and high-resolution TEM techniques. The as-prepared PtNFs/GO with clean surface and multiporous structure was used to assemble GODx to form a glucose biosensor. Based on ECL results, the PtNFs/GO/GODx film-modified electrode displayed a high electrocatalytic activity towards the oxidation of glucose, which generated hydrogen peroxide (H₂O₂) to react with the luminol radicals thus enhanced the luminol ECL. Under the optimized conditions, two linear regions of ECL intensity to glucose concentration were valid in the range from 5 to 80 μmol/L (r?=?0.9957) and 80 to 1,000 μmol/L (r?=?0.9909) with a detection limit (S/N?=?3) of 2.8 μmol/L. In order to verify the reliability, the thus-fabricated biosensor was applied to determine the glucose concentration in glucose injection, glucose functional drink, and blood serum. The results indicated that the proposed biosensor presented good characteristics in terms of high sensitivity and good reproducibility for glucose determination, promising the applicability of this sensor in practical analysis.     

A luminol-based micro-flow-injection electrochemiluminescent system to determine reactive oxygen species

A flow injection analysis (FIA) system with electrochemiluminescent (ECL) detection has been established. Based on a specially designed flow-through ECL cell with a very simple structure, the system possesses rapid response and high sensitivity. With luminol as the ECL reagent, the response of hydrogen peroxide (H₂O₂) was investigated on the developed FIA-ECL system. After optimizing the experimental conditions, such as the electric parameters, the buffer condition and the flow rate, it was demonstrated that the developed FIA-ECL system works well for quantified assays. Compared with reported works, the present results indicate that the developed FIA-ECL system has the lowest limit of detection (S/N = 3) of 3.0 × 10⁻⁹ mol/L for H₂O₂, which is equal to the level of chemiluminescence (CL). The developed system was successfully used to monitor the yield of reactive oxygen species (ROSs) in water vapour during the work of an ultrasonic humidifier with H₂O₂ as index. And the amount of ROSs in some other real samples, including tap water, drinking water and river water was detected with recoveries from 92.0% to 106%.     

Fabrication of a new ECL biosensor for choline by encapsulating choline oxidase into titanate nanotubes and Nafion composite film

A simple strategy for encapsulating choline oxidase (ChOD) into the titanate nanotubes (TNTs) and Nafion composite film for choline sensing was proposed. Hydrogen peroxide, as the product of the redox enzymatic reaction, could enhance the ECL of luminol. Therefore, the substrates of corresponding redox enzymes could be detected indirectly through the determination of hydrogen peroxide in the luminol ECL system. Through this approach, it was found that ChOD could be fixed firmly into the TNTs contained composite film. TNTs would not only offer excellent photocatalytic activity toward luminol-H₂O₂ ECL system, but also provide a shelter for the biomolecules, such as redox enzyme to retain its bioactivity.     

Intracellular Wireless Analysis of Single Cells by Bipolar Electrochemiluminescence Confined in a Nanopipette

The inside walls of a nanopipette tip are decorated by a Pt deposit that is used as an open bipolar electrochemiluminescence (ECL) device to achieve intracellular wireless electroanalysis. The synergetic actions of nanopipette and of bipolar ECL lead to the spatial confinement of the voltage drop at the level of the Pt deposit, which generates ECL emission from luminol. The porous structure of Pt deposit permits the electrochemical transport of intracellular molecules into the nanopipette that is coupled with enzymatic reactions. Thus, the intracellular concentrations of hydrogen peroxide or glucose are measured in vivo as well as the intracellular sphingomyelinase activity. In comparison with the classic bipolar ECL, the remarkably low potential applied in our approach is restricted inside the nanopipette and it minimizes the potential bias of the voltage on the cellular activity. Accordingly, this wireless ECL approach provides a new direction for analysis of single living cells.     

Electrochemiluminescence Based Enzymatic Urea Sensor Using Nanohybrid of Isoluminol‐gold Nanoparticle‐graphene Oxide Nanoribbons

This study evaluates on the possibility of using gold nanoparticles functionalized with the luminol derivative N‐(aminobutyl)‐N‐(ethylisoluminol) (ABEI) and hybridized with graphene oxide nanoribbons on a carbon based screen‐printed electrode (ABEI‐AuNP‐GONR/SPE) as an enzymatic electrochemiluminescence (ECL) urea sensor. The electrocatalytic activity and ECL intensity of ABEI‐AuNP‐GONR/SPE were found to increase proportionally with the concentration of urea in the analyte sample, owing to the rise in pH value. These phenomena are attributed to increased formation of luminol monoanion precursors for further electrochemical oxidation, which in turn produce either luminol radicals or excited 3‐amino‐phthalate molecules. The luminescence is most likely caused by the interaction of luminol radicals with superoxide radicals formed from dissolved oxygen. The sensitivity of our sensor was determined to be 170.58 mM⁻¹ and 16.23 mM⁻¹ for urea concentrations from 2 to 5.82 mM and from 5.82 to 30 mM, respectively, covering the normal urea level in human blood.     

鲁米诺在铂电极上阳极电致化学发光的机理研究

研究了碱性鲁米诺溶液在多晶铂电极上的阳极电致化学发光(ECL)行为,观察到电极的预极化处理和溶解氧跟发光峰强度和峰形有直接关系。结合XPS谱图和Pt,Pt|S~a~d~s修饰电极的循环伏安特性,给出了鲁米诺阳极ECL两个发光通道的可能反应机理:(1)鲁米诺阴离子在表面有新鲜Pt原子的电极上氧化生成鲁米诺自由基,然后迅速与溶液中的氧反应形成0.22V(vs.Ag)处的发光肩峰;(2)电极表面的铂氧化物能加速原子态氧的发生过程,并增大0.60V(vs.Ag)附近ECL主峰的发光强度。     

Determination of Melamine in Dairy Products and Melamine Tableware by Inhibition Electrochemiluminescent Method

An electrochemiluminescent (ECL) method has been developed for the determination of melamine based on the inhibition of luminol ECL. A significant luminol ECL can be found at 1.47 V in the phosphate buffer solution at high pHs and low potential scan rates, this ECL signal can be inhibited obviously by melamine. The decrease of ECL intensity was linearly proportional to the logarithm of melamine concentration in the range of 1–100 ng/mL (R²=0.9911) and with the detection limit of 0.1 ng/mL. The method has been applied successfully to determine melamine in dairy products and melamine tableware, the recoveries were in the range of 98.5%–103.7% and 95.5%–106.0%, respectively. The mechanism of the inhibition effect was also proposed, the active oxygen (O₂^{· −}) generated from the electrooxidation of OH⁻ reacted with luminol anion (L^{· −}) to generate light emission, and the present of melamine can eliminate the active oxygen, which cause the decrease of the ECL intensity.     

Electrochemiluminescence of CdSe Quantum Dots Composited with Nitrogen‐Doped Carbon Nanotubes

A nanocomposite of CdSe quantum dots with nitrogen‐doped carbon nanotubes was prepared for enhancing the electrochemiluminescent (ECL) emission of quantum dots. With hydrogen peroxide as co‐reactant, the nanocomposite modified electrode showed a cathodic ECL emission with a starting potential of ?0.97 V (vs. Ag/AgCl) in phosphate buffer solution, which was five‐times stronger than that from pure CdSe quantum dots and three‐times stronger than that from CdSe quantum dots composited with carbon nanotubes. The latter showed a starting potential of ?1.19 V. This result led to a sensitive ECL sensing of hydrogen peroxide with good stability, acceptable reproducibility and a detection limit down to 2.1×10^?7 mol L^?1. Nitrogen‐doped carbon nanotubes could be used as a good material for the construction of sensitive ECL biosensors for chemical and biochemical analysis.