Recent advances in electrogenerated chemiluminescence biosensing methods for pharmaceuticals

Electrogenerated chemiluminescence(electrochemiluminescence, ECL) generates species at electrode surfaces, which undergoes electron-transfer reactions and forms excited states to emit light. It has become a very powerful analytical technique and has been widely used in such as clinical testing, biowarfare agent detection, and pharmaceutical analysis. This review focuses on the current trends of molecular recognition-based biosensing methods for pharmaceutical analysis since 2010. It introduces a background of ECL and presents the recent ECL developments in ECL immunoassay(ECLIA), immunosensors, enzyme-based biosensors, aptamer-based biosensors, and molecularly imprinted polymers(MIP)-based sensors. At last, the future perspective for these analytical methods is briefly discussed.

Electrogenerated chemiluminescence sensor for the determination of metoclopramide using ordered mesoporous carbon for immobilizing tris(2,2'-bipyridyl)ruthenium

A novel electrogenerated chemiluminescence(ECL)sensor for the determination of metoclopramide was developed by employing ruthenium complex as an ECL signal producer and an ordered mesoporous carbon(OMC)material as modified material.The ECL sensor was fabricated by adsorption ruthenium complex into a mixture of OMC and Nafion,which showed good electrochemical and ECL behaviors.It was found that the ECL intensity of the sensor fabricated was greatly enhanced in the presence of metoclopramide.Based on this finding,a highly sensitive and reproducible ECL method was developed for the determination of metoclopramide.The result showed that the ECL intensity was linear with the concentration of metoclopramide in the range from 1.0×10-10 to 5.0×10-7M and the detection limit was 3×10-11M.The ECL sensor exhibited a long-term stability and a fine reproducibility with relative standard deviation of 1.0 % for 1.0×10-10M metoclopramide in 18 continuous determinations.The developed method has been applied to the determination of metoclopramide in tablet samples with satisfactory results.

Flow Injection Analysis of Histidine with Enhanced Electrogenerated Chemiluminescence of Luminol

A simple and sensitive flow injection method is presented for the determination of histidine based on its enhancement of electrogenerated chemiluminescence (ECL) of luminol. After optimization of the experimental parameters, the working range for histidine was in 1.0 x 10-6 to 1.0 x 10 -3 mol/L with a detection limit (S/N = 3) of 0.56 mmol/L. The relative standard deviation was 1.6% for 11 measurements of 5 x 10 5 mol/L histidine solution. The proposed method has been successfully applied to the determination of histidine in real pharmaceutical preparation.

Chemiluminescence flow Sensor for determination of the Ammonium ion

A novel chemiluminescence (CL) sensor for NH4+ combined with flow injection analysis is presented in this paper. It is based on the inhibition effect of NH4+ on the CL reaction between luminol, immobilized electrostatically on an anion-exchange column, and hypochlorous acid electrogenerated on-line. The sensor responds linearly to NH4+ concentration in 1.0x10(-6)-4.0x10(-9) g/ml range. A complete analysis could be performed in 1 min. The system is stable for 200 determination.

ECL-1型电致化学发光仪与APPLE-Ⅱ微机的联用

本文报道新仪器ECL-1型电致化学发光仪与APPLE-Ⅱ微机的联用,实现了扫描时间、静置时间、电极清洗的微机控制,同时具有数据采集、处理和微弱信号叠加功能,提高了仪器使用的灵活性和分析的灵敏度。应用该仪器对新试剂6-(2-羟基-4-二乙基氨苯偶氮)-2,3-二氢-1,4-酞嗪二酮(简称HDEA)测定的线性范围为1.0×10^(-9)～6.0×10^(-7)mol/L。测定13份浓度为5.0×10^(-9)mol/L HDEA的相对标准偏差为5%。

Investigation of Chemiluminescence with Electrogenerated Reagents and Its Analytical Application

In this paper, studies on chemiluminescence (CL) systems with electrogenerated reagents, including BrO -, ClO -, Br_2, [Cu^(HIO_6)_2] 5- , H_2O_2, Mn 3+ , Co 3+ and Ag 2+ , are described. The analytical applications of the CL system with electrogenerated reagents are reviewed.

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.

Blue Electrogenerated Chemiluminescence from Halide Perovskite Nanocrystals

Electrogenerated chemiluminescence(ECL)has been extensively used in ultrasensitive electroanalysis because it can be generated electrochemically without using expensive optics and light sources.Visible ECL emission can be obtained with a reasonable quantum yield and stability.Blue ECL is rare and often suffers from stability and poor quantum efficiency.Blue ECL emission at 473 nm from organometallic halide perovskite nanocrystals(PNCs),CH_(3)NH_(3)PbCl_(1.08)Br_(1.92),is reported here for the first time using tripropylamine(TPrA)as co-reactant.The blue ECL emission peak resembles its photoluminescence peak position.In addition to this blue emission peak,the ECL spectra of CH_(3)NH_(3)PbCl_(1.08)Br_(1.92) PNCs also showed a broad ECL peak at 745 nm.Generation of the second ECL peak at 745 nm from CH_(3)NH_(3)PbCl_(1.08)Br_(1.92) PNCs was can be explained by the existence of surface trap states on as-synthesized PNC due to incomplete surface passivation.Halide anion tunability of ECL emission from CH3NH3PbX3(X:Cl,Br,I)PNCs is also demonstrated.The fluorescence microscopy image of single PNC and stability of selected single PNCs are presented in this with simultaneous acquisition of fluorescence spectra using 405-nm laser excitation.The photoluminescence(PL)decay was described by PL lifetime(τ)of 1.2 ns.The effect of the addition of surfactants(oleic acid and n-octylamine)on the fluorescence intensity and stability of CH_(3)NH_(3)PbCl_(1.08)Br_(1.92) PNCs is also discussed.

鲁米诺电生化学发光(ECL)系统研究初探

文章描述了一个新的鲁米诺电生化学发光流动系统。通过微铂电极流动池,H_2O_2被还原为OH^-,以维持鲁米诺化学发光所要求的pH条件。文章对鲁米诺化学发光机理进行了初步探讨,并详细研究了ECL的最佳条件。该系统明显降低了反应噪声,优于混合反应系统,可作为液相色谱间接测定检测器。

Towards Determining Kinetics of Annihilation Electrogenerated Chemiluminescence by Concentration-Dependent Luminescent Intensity

In ion-annihilation electrochemiluminescence(ECL),luminophore ions are generated by oxidation as well as reduction at electrodes surfaces,and subsequently recombine into an electronically excited state,which emits light.The intensity of the emitted light is often limited by the kinetic rate of recombination of the luminophore ion species.Recombination or annihilation rates are high ranging up to approximately 10^(10) M^(−1) s^(−1) and can be difficult to determine using scanning electrochemical microscopy or high-frequency oscillations of an electrode potential.Here,we propose determining annihilation kinetics by measuring the relative change of the emitted light intensity as a function of luminophore concentration.Using finite element simulations of annihilation ECL in a geometry of two closely spaced electrodes biased at constant potentials,we show that,with increasing concentrations,luminescence intensity crosses over from a quadratic dependence on concentration to a linear regime-depending on the rate of annihilation.Our numerical results are applicable to scanning electrochemical microscopy as well as nanofluidic electrochemical devices to determine fast ion-annihilation kinetics.

Electrogenerated chemiluminescence aptasensor for thrombin incorporating poly(pyrrole-co-pyrrole propylic acid) nanoparticles loaded with aptamer and ruthenium complex

A novel electrogenerated chemiluminescence (ECL) aptasensor for highly sensitive detection of thrombin was developed on the basis of poly(pyrrole-co-pyrrole propylic acid) nanoparticles loaded with aptamer and ruthenium complex. Thrombin binding aptamers served as the molecular recognition elements and ruthenium bis(2,2′-bipyridine) (2,2′-bipyridine-4,4′-dicarboxylic acid)-ethylenediamine (Ru1) was used as an ECL signal complex. Novel electroactive polymers poly(pyrrole-co-pyrrole propylic acid) nanoparticles (Ppy-pa NPs) were synthesized by a simple alcohol-assisted microemulsion polymerization. Ru1-Ppy-pa NPs were synthesized by covalently coupling Ru1 with the Ppy-pa NPs. Ppy-pa NPs and Ru1-Ppy-pa NPs were characterized using a fourier transform infrared spectrometer, super-conducting fourier digital NMR spectrometer, and transmission electron microscope. One ECL chemical sensor fabricated by immobilizing the Ru1-Ppy-pa NPs on PIGE was developed for the determination of TprA with a high sensitivity and stability. The ECL aptasensor was fabricated by covalently coupling the thrombin binding aptamer-I (TBA-I) onto the surface of the paraffin-impregnated graphite electrode, which had been covalently modified with a monolayer of 4-aminobenzene sulfonic acid via electrochemical oxidations, for capturing thrombin onto the electrode and then the TBA-II labeled with Ru1-Ppy-pa NPs was bound with epitope of thrombin. The ECL aptasensor showed an extremely low detection limit of 3.0×l0?16 mol/L for thrombin and a good selectivity. This work demonstrated that using Ppy-pa NPs as a carrier of ruthenium complex and molecular recognition element was a promising approach for the fabrication of ECL biosensor with high sensitivity.

联吡啶钌电化学发光研究进展

联吡啶钌电化学发光在免疫分析、核酸分析、共反应物分析和适配子传感器等方面具有广泛的应用前景,成为在诸多电化学发光体系如9,10-二苯基蒽、光泽精、联吡啶钌、过氧化草酸酯、鲁米诺、石墨烯和量子点等之中近年来国际上研究最多的电化学发光体系之一。本综述对已发表的绝大多数联吡啶钌电化学发光成果加以归纳总结,简要介绍联吡啶钌电化学发光的概况,并尝试展望其今后的研究趋势。

化学发光分析法应用新进展

评述了化学发光法在无机分析、有机分析、生物活性氧研究、免疫分析、核酸杂交分析和微全分析中的最新应用 ,引用文献 4

流动注射电化学发光分析法测定间苯三酚

基于间苯三酚对鲁米诺在铂电极上弱的电氧化发光信号的强增敏作用与流动注射技术的结合 ,建立了一种测定间苯三酚的电化学发光新方法。该法测定间苯三酚的检出限为 1.2× 10 - 4g L ;线性范围为 4 .0× 10 - 4～ 4 .0× 10 - 2 g L ;相对标准偏差为 4 .7%。

电化学发光法测定铁

基于Fe(o Phen)33+对鲁米诺电化学发光体系的电还原发光信号的增敏作用,建立了一种测定铁离子的电化学发光新方法。在最佳的实验条件下,该方法测定铁(Ⅲ)的线性范围为4.1×10-7～4.1×10-6mol/L,检出限为1.8×10-7mol/L,相对标准偏差小于5%。

流动注射电化学发光分析法测定诺氟沙星的研究

基于诺氟沙星对鲁米诺在铂电极上弱的电氧化发光信号的强增敏作用与流动注射技术的结合 ,建立了一种测定诺氟沙星的电化学发光分析新方法。该法测定诺氟沙星的检出限为 4 .0× 10 -6g/L ;线性范围为 1.0× 10 -5～ 0 .2g/L ;相对标准偏差为 1.2 % (n =11)。该法简单、快速、灵敏 ,已成功地用于药物制剂和尿样中诺氟沙星的测定。

发光分析

评述在 2 0 0 1年 1月～ 2 0 0 2年 12月间我国发光分析的发展概况 ,内容包括荧光、磷光、化学发光和电化学发光分析等。引用文献 32 9篇。

电化学发光分析研究进展

本文简要综述了电化学发光体系和分析技术以及在临床分析中应用的研究进展。

一种新的流动注射电化学发光分析方法及硫离子的分析测定研究

设计了一种用于流通体系的电解池，并以恒电流电解法与流动注射技术相结合，在线定量电解产生不稳定试剂次溴酸根，使其浓度和反应活性得以在线控制，稳定地应用于化学发光分析．在此基础上，研究了ＢｒＯ－在ｐＨ＝９．６０Ｎａ２ＣＯ３－ＮａＨＣＯ３缓冲介质中氧化鲁米诺弱化学发光反应的分析特性，并基于硫离子对该弱化学发光反应体系的发光强度的增敏作用，建立了一种新的测定Ｓ２－的流动注射电化学发光分析法．采用该方法测定Ｓ２－的线性范围为３．１０×１０－７～９．３０×１０－５ｍｏｌ／Ｌ，检出限为１．００×１０－７ｍｏｌ／Ｌ，相对标准偏差为２％［ｎ＝１１，ｃ（Ｓ２－）＝３．１０×１０－６ｍｏｌ／Ｌ］

高效液相色谱化学发光法检测牛奶中残留四环素类化合物的研究

基于四环素类抗生素药物中的四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DC)能够强烈增敏通过恒电流电解方法在线电生BrO-和鲁米诺之间产生的化学发光,提出了一种高效液相色谱(HPLC)化学发光(CL)法检测4种四环素类抗生素药物的新方法.以NucleosilRP-C18(250mm×4.6mm,i.d.,5μm,poresize,100?)为色谱柱,0.05mol?L-1磷酸二氢钾(pH2.5)-乙腈(30∶70,V∶V)为流动相,流速1.2mL/min,柱温25℃,同时分离检测四种抗生素的总时间为11min.研究并优化了流动相、电生试剂化学发光检测的条件.四种抗生素的检出限为0.002～0.008μg?mL-1(3σ),对0.01μg?mL-1的四种抗生素测定的相对标准偏差为2.0%～3.6%(n=11).该方法已成功应用于牛奶中残留四环素类抗生素含量的分析.