基于一次性薄层色谱电极高选择电化学发光分析法测定Ni(II)的研究

基于一种新的电极制作方法, 研制了具有薄层色谱分离功能的一次性薄层色谱电极. 结合该电极的分离、保留分析物于电极表面一定空间区域的色谱分离能力与电极表面电化学发光信号的空间分辨能力, 实现了分析物的高效分离与原位高灵敏度电化学发光(ECL)检测, 建立了电化学发光分析方法与薄层色谱分离方法联用的新技术. 并以Ni^2＋离子为代表探讨了这一方法的可行性和分析特性. 在最佳的实验条件下, 该方法测定Ni^2＋离子的线性范围为5.0× 10^－9～5.0×10^－6 g/mL, 检出限为1.5×10^－9 g/mL, 相对标准偏差为2.8% (c＝1.0×10^－6 g/mL, n＝11).     

Highly Sensitive Determination of Concanavalin A Lectin Based on Silver-Enhanced Electrogenerated Chemiluminescence of Luminol

A highly sensitive bioassay based on silver-enhanced luminol electrogenerated chemiluminescence (ECL) is reported for the determination of concanavalin A lectin. A gold electrode modified with the mixed self-assembled monolayer of thiolated mannoside and mercaptohexanol was used to selectively capture a target lectin, concanavalin A, through the specific interaction between mannoside and concanavalin A. Mannoside-functionalized gold nanoparticles were further introduced to the opposite binding sites of the tetrameric concanavalin A to form a sandwich-type complex. Silver enhancement step was performed to coat the surface of mannose-stabilized gold nanoparticles with silver. The deposited silver was dissolved in an acidic solution and further neutralized. The resulting silver ions were finally detected with luminol electrogenerated chemiluminescence, in which the silver ions greatly enhanced the chemiluminescence intensity. The present electrogenerated chemiluminescence bioassay detected concanavalin A from 0.190 to 10.0?µg/mL (r²?=?0.999) with a detection limit of 0.146?µg/mL (signal to noise ratio?=?3), which is much lower compared to previously reported methods such as microgravimetry, surface plasmon resonance, and colorimetry. Furthermore, the present bioassay showed good selectivity over possible interfering lectin proteins.     

流动注射电化学发光测定潘生丁

设计了一种应用于流通体系的电解池,以恒电流电解的方法,在线定量电生化学发光反应试剂次溴酸根。其可在碱性介质理米诺而产生强的化学发光。发现潘生丁对该电化学发光有很强的抑制作用。并建立了潘生丁的电化学发光方法。对影响潘生丁测定的实验条件进行了考察和优化。该方法测定潘生丁的一性范围为０．０１－２ｍｇ／Ｌ,检出限为０．００４ｍｇ／Ｌ,相对标准偏差为４．１％。雇学成功地用于片剂潘生丁样品的分析。     

Flow Injection Chemiluminescence Determination of Isoniazid Using On-Line Electrogenerated Manganese(III) as Oxidant

A novel flow injection chemiluminescence (CL) system for the determination of isoniazid has been proposed. It is based on the direct CL reaction of isoniazid and Mn(III) in sulfuric acid medium. The unstable Mn(III) was on-line electrogenerated by constant current electrolysis. The CL emission intensity was linear with isoniazid concentration in the range 0.1–10 μg/mL; the detection limit was 3.2 × 10⁻² μg/mL. The whole process could be completed in 1 min with a relative standard deviation of less than 5%. The proposed method is suitable for automatic and continuous analysis and has been applied successfully to the analysis of isoniazid in pharmaceutical preparation.     

Flow Injection Chemiluminescence Determination of Gentamycin Using On-Line Electrogenerated Co(III) As the Oxidant

ABSTRACT

A novel flow-injection Chemiluminescence (CL) system for the determination of gentamycin is described, based on the direct chemiluminescence reaction of gentamycin and Co(III) in sulfuric acid media. The unstable strongly oxidative Co(III) was electrogenerated on-line with constant current electrolysis. The chemiluminescence intensity was linear with gentamycin concentrations of 0.01～80μg/ml, the detection limit being 0.005μg/ml. The whole process could be completed in 1 min with a relative standard deviation of less than 3.2%. The proposed method is rapid and simple and is suitable for automatic and continuous analysis. This method has been applied satisfactorily to the analysis of gentamycin in pharmaceutical preparations.     

Flow Injection Analysis of Histidine with Enhanced Electrogenerated Chemiluminescence of Luminol

Histidine is one of the necessary basic amino acids in biological bases, which often controls the catalytic activity of enzymes and acts in holding the higher structure of proteins. Furthermore, it is also an important ingredient in pharmaceutical preparations used for treatment of hetpatosis and nephropathy. Therefore, the determination of histidine in biological fluids and pharmaceutical preparations is of great importance. Various methods have been proposed for the detection of histidine …     

Energy Transfer Electrogenerated Chemiluminescence for the Determination of Sulfite

A simple and novel electrogenerated chemiluminescence (ECL) method for the determination of sulfite has been developed based on the energy transfer ECL process. It was found that a weak ECL signal of sulfite was electrochemically generated on a platinum electrode in neutral aqueous solution. The signal was strongly enhanced by rhodamine B as an energy receptor and further enhanced by the neutral surfactant Tween 80. In 0.10M phosphate buffer solution (pH=7.5) containing 2.0×10^–6gmL^–1 rhodamine B and 0.4% (v/v) Tween 80, the ECL response to the concentration of sulfite at a potential of 0.82V was linear over a range of 1.0×10^–7gmL^–1 to 8.0×10^–6gmL^–1, and the detection limit was 5×10^–8gmL^–1. The relative standard deviation (n=11, 1.0×10^–6gmL^–1) was 3.8%. The proposed method has been successfully applied to the determination of sulfite in pharmaceutical injections and white sugar samples.     

Electrogenerated Chemiluminescence Based on Tris(2,2′-bipyridyl) Ruthenium(II) with Hydroxyl Carboxylic Acid

Upon the electrochemical oxidation of tris(2,2′-bipyridyl) ruthenium(II) [Ru(bpy)²⁺₃] and hydroxyl carboxylic acids, for instance, citric acid, tartaric acid, malic acid, and -gluconic acid, bright electrochemiluminescences (ECLs) were observed. Different luminescent reactions were presented depending on the applied potential. The light emission was mainly caused by the reaction between alkoxide radical ion and Ru(bpy)³⁺₃below the potential +1.80 V (vs Ag/AgCl). The luminescence intensity obviously increased because of the more complex reaction process. The luminescence wavelength of 608 nm, which could be found either at higher potential than +1.80 V or in the potential range from +1.30 to +1.80 V, confirmed that ECL was caused by Ru(bpy)²⁺₃*. The factors which affect the determination and HPLC separation of the four acids were also investigated.     

A Novel Enhancing Flow-Injection Chemiluminescence Method for the Determination of Glutathione Using the Reaction of Luminol with Hydrogen Peroxide

 A rapid flow-injection method with chemiluminescence (CL) detection is described for the determination of glutathione (GSH). The method is based on the CL reaction of luminol and hydrogen peroxide. GSH can greatly enhance the chemiluminescence intensity in 0.1 mol/L borax–sodium hydroxide buffer solution (pH = 9.7). The maximum CL intensity was directly proportional to the concentration of GSH in the range 3.0 × 10⁻⁷–2.0 × 10⁻⁵ mol/L, and the detection limit was 6.8 × 10⁻⁸ mol/L. The relative standard deviation was 3.4% for 5.0 × 10⁻⁶ mol/L of GSH (n = 11). Received October 23, 2001; accepted June 18, 2002     

Enhanced Sensitivity of the Tris(Bipyridine)Ruthenium(II) Chloride Electrogenerated Chemiluminescence Sensor with Porous Silica Nanoparticles

Mass transfer in electrogenerated chemiluminescence affects the sensitivity of sensors involving this technique. Herein, the characteristics of the porous Ru(bpy)₃²⁺/silica nanoparticles were investigated by transmission electron microscopy, fluorescence spectroscopy, ultraviolet-visible absorption spectroscopy, and electrogenerated chemiluminescence. The results showed that the pores inside the porous nanoparticles provided efficient mass transfer, resulting in significant enhancement of electrogenerated chemiluminescence. Consequently, a novel electrogenerated chemiluminescence sensor was developed and is reported herein. The sensitivity for tripropylamine was more than one order of magnitude higher compared to previously reported similar sensors, with a limit of detection of 3.3 × 10^?12 moles per liter.     

Determination of Picogram-Levels of Acetylspiramycin in Human Urine and Serum by Flow Injection Chemiluminescence

A sensitive chemiluminescence method for the determination of acetylspiramycin is presented. It is based on the greatly enhancive effect of acetylspiramycin on the chemiluminescence reaction between luminol and hydrogen peroxide in the flow system. The increase in chemiluminescence intensity was linearly proportional to the acetylspiramycin concentration in the range from 10pg·mL^–1 to 2.0ng·mL^–1 (r²=0.9979). The detection limit was 3pg·mL^–1 (3). At a flow rate of 2.0mL·min^–1, the process of determination, including sampling and washing, could be performed in 0.5 min, and the relative standard deviations of seven replicates are less than 5.0%. The proposed method was applied successfully to the determination of acetylspiramycin in pharmaceutical preparations, human urine and serum without pre-treatment. It was found that the excretive ratio of acetylspiramycin reached its maximum 2.0 hours after having been administered orally, and the excretive ratio in 12.0 hours was 8.4.     

Flow Injection Chemiluminescence Determination of Pipemidic Acid Using On-Line Electrogenerated Cobalt(III) as Oxidant

 A novel flow injection chemiluminescence (CL) system for the determinati on of pipemidic acid is described. It is based on the direct CL reaction of pipemidic acid and Co(III) in acid medium. The unstable Co(III) was on-line electrogenerated by constant current electrolysis. The CL intensity was linear with pipemidic acid concentration in the range of 0.01∼100 μg/ml, the determination limit was 3.3×10⁻⁹ g/mL. The whole process could be complete d in 1 min with a relative standard deviation of 3.2%. The proposed method is suitable for automatic and continuous analysis and has been applied successfully to the analysis of pipemidic acid in a pharmaceutical preparation. Received November 22, 1999. Revision March 24, 2000.     

低压离子色谱-化学发光联用在线检测水中痕量铜

低压离子色谱化学发光方法在线检测Cu^2 ，利用草酸作为色谱柱的洗脱液，研究了分离条件、发光条件及二者的匹配方式等因素对分离检测的影响，测定Cu^2 的线性范围为0．4－6mg／L；检测限为0．1mg/L，方法用自来水及地表水中Cu^2 的分析测定。     

在线电生锰(Ⅲ)流动注射化学发光法测定地塞米松磷酸钠

采用在线恒电流电解产生Mn(Ⅲ)与流动注射化学发光法相结合,基于地塞米松磷酸钠可使Mn*#-Na2SO3新体系化学发光大大加强的现象,建立了测定地塞米松磷酸钠的新分析方法.其线性范围为1×10-4～1×10-2 g/L;检出限为7×10-5 g/L;RSD为1.2%.该法成功地应用于针剂中地塞米松磷酸钠的测定.     

基于Ru(bpy)32+-SiO2纳米颗粒的核酸适配体传感器对凝血酶的电致化学发光检测

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。     

A Novel Electrogenerated Chemiluminescence (ECL) Sensor Based on Ru(bpy)32+‐Doped Titania Nanoparticles Dispersed in Nafion on Glassy Carbon Electrode

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.     

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S^2-的流动注射电化学发光分析法.采用该方法测定S^2-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(S^2-)=3.10×10^-6mol/L]     

Luminol-K_3[Fe(CN)_6]流动注射化学发光体系检测头孢吡肟

在碱性介质中,头孢吡肟对Luminol-K3[Fe(CN)6]化学发光体系具有明显的增强作用,基于此建立了流动注射化学发光法测定头孢吡肟的新方法。在优化实验条件下,化学发光增强强度与头孢吡肟的浓度在3.0×10-6~4.0×10-5g/m L范围内呈良好的线性关系,检出限为2.8×10-6g/m L。对2.0×10-5g/m L头孢吡肟平行测定11次,相对标准偏差(RSD)为1.5%。该方法用于头孢吡肟针剂的测定,结果满意。     

Simple and Sensitive Assay for Nucleic Acids Using their Quenching Effect on the Chemiluminescence Reaction Between Luminol and Hydrogen Peroxide with Manganese-Tetrasulfonatophthalocyanine as a New Catalyst

The manganese-tetrasulfonatophthalo-cyanine (MnTSPc) catalyzed luminol-hydrogen peroxide chemiluminescence (CL) system can be quenched in the presence of nucleic acids. A new and highly sensitive CL quenching method for determining nucleic acids in aqueous solutions has been developed. Under optimum conditions, linear relationships were found between the quenched intensity of CL and the concentration of nucleic acids in the range 0.10–2.0µgmL^–1 for calf thymus DNA and 0–1.6µgmL^–1 for fish sperm DNA. The limits of detection were 14.8ngmL^–1 for calf thymus DNA and 21.7ngmL^–1 for fish sperm DNA. The relative standard deviation (RSD) of nine replicate measurements is 1.4% for 1.0µgmL^–1 calf thymus DNA. The method was applied to the analysis of nucleic acids in synthetic samples and the results are satisfactory.Received December 2, 2002; accepted June 2, 2003 published online September 1, 2003