电化学发光淬灭法测定脑白金胶囊中的褪黑素

在硼酸缓冲溶液(pH 6.7)介质中,H2O2对鲁米诺的电化学发光有敏化作用,而褪黑素(MLT)因具有对自由基的湮灭作用而对此敏化的电化学发光具有淬灭作用,该发光体系的ECL光强与MLT的浓度成线性关系,检测灵敏度极高,检测下限可达到1×10-14mol/L,用于脑白金胶囊中MLT的测定得到满意结果,为MLT的测定提供了一种灵敏、可靠的测定方法。     

磺酸基卟啉的电化学发光研究及应用

以四(4-磺酸基苯基)卟啉（TSPP）为发光体,过硫酸钾（K₂S₂O₈）为共反应剂,构建了一个新的电化学发光（ECL）体系. 在扫描范围为0~-1.5V时,该体系出现两个阴极ECL峰,分别为TSPP的还原峰（-0.8V）和K₂S₂O₈ 的还原峰 (-1.2V). 亚甲基蓝能有效猝灭四(4-磺酸基苯基)卟啉的电化学发光,根据猝灭效率与亚甲基蓝浓度的线性关系,建立了一种测定亚甲基蓝含量的新方法.     

基于氮硫掺杂的石墨烯量子点电化学发光传感器的构建及检测铜离子的研究

石墨烯量子点（GQDs）作为一种新型的纳米材料,由于其低毒性、易于表面功能化等优点而受到广 泛关注。该文通过一步溶剂热法合成了氮硫共掺杂石墨烯量子点（N,S－GQDs）,与未掺杂的GQDs相比,其 电化学发光（ECL）信号得到极大增强。在外电压作用下,N,S－GQDs由基态跃迁到激发态,在返回基态的 过程中释放出光能。加入Cu2+ 后,Cu2+ 与N,S－GQDs发生络合作用,使可被激发的N,S－GQDs减少,ECL 信号降低,Cu2+ 浓度越大,ECL降低程度越大。利用Cu2+ 对N,S－GQDs ECL信号的降低作用,以壳聚糖为连 接剂,构建了用于检测铜离子的新型 N,S－GQDs ECL 传感器。考察了缓冲溶液种类与 pH 值,共反应剂 S2O2 - 8 浓度对ECL信号强度的影响。在优化条件下（60 mmol/L pH 7. 5 Tris－HCl,50 mmol/L S2O2 - 8 ）,Cu2+ 的线 性范围为0. 01～35 μmol/L,检出限为1. 7 nmol/L。方法可实现对工业废水中铜离子的快速、灵敏、选择性检测。 该研究为实际样品中重金属离子的快速检测做了铺垫,拓宽了纳米材料在电化学发光传感领域中的应用。     

二氧化钛-硒化镉修饰电极电化学发光法测定甘氨酸

以二氧化钛和硒化镉复合膜修饰的玻碳电极(TiO_2/CdSe/GCE)作为工作电极,建立了一种测定甘氨酸的电化学发光(ECL)新方法。在强碱性溶液中,TiO_2/CdSe/GCE在鲁米诺溶液中会产生明显的电化学发光信号,而甘氨酸对该体系的电化学发光信号有较强的增敏作用。考察了TiO_2/CdSe复合物的比例、缓冲溶液的pH、发光试剂的浓度等条件对ECL强度的影响。最佳实验条件下,甘氨酸浓度在2.5×10~(-7)~1.0×10~(-10)mol/L范围内与相对ECL强度呈现良好的线性关系,检测限(S/N=3)为3.3×10~(-11)mol/L,方法用于乳酸饮料中甘氨酸的测定,结果令人满意。     

高灵敏ECL－RET传感器的构建及其用于血清前列腺特异性抗原检测的研究

肿瘤标志物在癌症早期诊断与预后监测中具有非常重要意义。前列腺癌作为男性泌尿生殖系统中最常见的恶性肿瘤,其血清前列腺特异性抗原（PSA）是最重要的早期检测指标。该研究以制备的四元Cu－Zn－In－S纳米晶（NCs）作为发光体,金纳米星（AuNSs）作为猝灭探针,利用K2S2O8作为共反应剂,发展了一种基于量子点电化学发光共振能量转移的免疫传感器（ECL－RET）用于血清中PSA的高灵敏检测。固定在传感器上的NCs表现出极强的初始ECL信号和较低的ECL电位。作为固定基底的多壁碳纳米管（MWNTs）不仅加速了NCs与S2O2?8之间的反应,获得了较高的ECL信号,而且作为载体可以固定大量的抗体,提高传感器检测PSA的灵敏度。采用电化学交流阻抗法（EIS）对组装过程进行跟踪,证实了该传感器组装的可行性。采用电化学发光法研究了传感器对底液中不同浓度PSA的响应,结果显示,随着体系中PSA浓度的增加,电极上结合AuNSs的标记抗体（Ab2－AuNSs）越多,触发的猝灭效果越明显,ECL信号降低越明显。因此,该传感器表现出对PSA较好的分析性能,其线性范围为0.01～150 ng/mL,检出限为0.03 ng/mL。用于血清样品的检测,该传感器的测试结果与常用的化学发光法基本吻合,相对误差仅为-7.2%～6.0%,结果准确度良好,为临床检测PSA提供了准确可靠的新方法。     

基于碳纳米管修饰电极的胆碱电化学发光生物传感器研制

在碳纳米管(CNTs)和K3Fe(CN)6修饰的铂电极上吸附固定胆碱氧化酶,以鲁米诺为发光试剂,研制了胆碱电化学发光(ECL)生物传感器.CNTs可有效提高电极表面的电荷传输能力、提高电极表面的生物相容性和对酶分子的固载能力;K3Fe(CN)6对酶活性具有激活作用,同时对H2O2增敏的鲁米诺ECL有增强作用,均有利于提...     

CdS修饰玻碳电极电化学发光法检测三聚氰胺

本文将CdS纳米棒修饰到玻碳电极上制作了CdS修饰玻碳电极(CdS/GCE)并研究了其在K2S2O8溶液中的电化学发光(ECL)性能.基于三聚氰胺能淬灭CdSK2s2O8电化学发光的性质建立了一种检测三聚氰胺的方法.在最优条件下,体系的ECL强度与三聚氰胺浓度在1.0×10-9～1.0×10-7 mol/L范围内与EC...     

基于fl-TiO2/Pt NPs/RuSi NPs的去氧肾上腺素电化学发光传感器的构建和应用

该文采用溶剂热法制备了高度有序的花状分级二氧化钛微/纳米粒子（fl-TiO2）,以（3-氨基丙基）三乙氧基硅烷（APTES）做偶联剂,采用简单的合成后接枝方法制备氨基功能化的fl-TiO2（fl-TiO2-NH2）。随后,通过静电作用将铂纳米粒子（Pt NPs）组装在fl-TiO2-NH2表面,制备了一种新型的fl-TiO2/Pt NPs复合材料。最后,将fl-TiO2/Pt NPs与RuSi NPs混合形成均匀的分散溶液,并将其固定在玻碳电极（GCE）表面,制备了一种新型的电化学发光（ECL）传感器（fl-TiO2/Pt NPs/RuSi NPs/GCE）。采用扫描电镜、紫外－可见吸收光谱、X射线衍射和能谱等技术对不同材料的形貌、结构、物理性质和化学组成进行表征,循环伏安法、交流阻抗法和ECL法对所研制ECL传感器的电化学行为和ECL性能进行研究。实验结果表明,Pt NPs优异的电催化活性显著提高了RuSi NPs－三丙胺（TPrA）体系的ECL信号强度。而fl-TiO2的巨大比表面积为Pt NPs和RuSi NPs提供了丰富的结合位点。因此,fl-TiO2/Pt NPs可作为一种新型的共反应剂加速器和ECL信号放大器,用于提高RuSi NPs－TPrA体系的ECL发射效率。在优化实验条件下,fl-TiO2/Pt NPs/RuSi NPs的ECL强度分别为fl-TiO2/RuSi NPs和RuSi NPs的1.5倍和1.8倍。在去氧肾上腺素（PHE）存在下,fl-TiO2/Pt NPs/RuSi NPs－TPrA体系的ECL信号发生猝灭,且ECL猝灭信号与PHE浓度的对数在1.0 × 10－7～8.0 × 10－5 mol/L范围内呈良好的线性关系（r2 = 0.998 4）,检出限（S / N = 3）为2.5 × 10－8 mol/L。该方法用于盐酸去氧肾上腺素注射液中PHE的测定,回收率为99.2%～108%。该传感器具有良好的稳定性和重现性、较高的选择性。该研究为ECL传感平台的构建提供了一种新的ECL信号放大策略,并拓宽了ECL传感器在药物分析中的应用。     

空间分辨测量解析三(2,2'-联吡啶)钌(Ⅱ)电化学发光机理的研究进展

电化学发光(ECL)是由电化学反应引发,通过一系列化学反应产生激发态发光体进而辐射发光的过程,其产生的方式主要有湮灭型电化学发光和共反应剂型电化学发光.ECL是一种表面限域的发光过程,其发光层的厚度主要由反应中间体在电极表面的分布决定.空间分辨测量能够直接测得激发态发光体、共反应剂自由基等中间体在电极表面附近的分布,进...     

流动注射电化学发光测定动物饲料中6-丙基-2-硫脲嘧啶含量的研究

基于6-丙基-2-硫脲嘧啶（PTU）对三联吡啶钌(Ru（bpy）₃²⁺)电化学发光（ECL）有强烈的增敏作用,建立了流动注射电化学发光（FI-ECL）检测PTU的新方法。通过考察影响体系电化学发光的因素(如电压信号类型及电位、缓冲溶液pH值、载液流速及Ru（bPY）₃²⁺浓度等),得到FI-ECL测定PTU的最佳条件,并提出了可能的反应机理。研究结果表明,在0.1 mol/L pH 12.0的H₃PO₄-NaOH缓冲介质中,控制恒电位为+1.50 V,Ru（bpy）₃²⁺浓度为1.0×10^-4mol/L,载液流速为1.5 mL/min,PTU对Ru（bpy）₃²⁺的电化学发光具有最大的增敏作用。在此条件下,测得PTU的线性范围为2.0×10^-71.0×10^-4mol/L（r²=0.998 6）,检出限（S/N=3）为1.3×10^-8mol/L,对7份浓度均为1.0×10^-6mol/L的PTU标准溶液进行测定,所得结果的相对标准偏差为1.2%。该方法简便、快速、灵敏,用于模拟动物饲料中PTU含量的检测,结果满意。     

Enhanced electrochemiluminescence from luminol at multi-walled carbon nanotubes decorated with palladium nanoparticles: a novel route for the fabrication of an oxygen sensor and a glucose biosensor

Incorporation of palladium nanoparticles on the surface of multi-walled carbon nanotubes and modification of glassy carbon electrode with the prepared nano-hybrid material led to the fabrication of a novel electrode. The modified electrode showed attractive electrocatalytic activity and sensitizing effect on luminol-O(2) and luminol-H(2)O(2) electrochemiluminescence (ECL) reactions at neutral media. The sensitized luminol-O(2) and luminol-H(2)O(2) reactions were successfully applied for the ECL determination of dissolved O(2) and glucose, respectively. Under the optimal conditions for luminol-O(2) system, the ECL signal intensity of luminol was linear with the concentration of dissolved oxygen in the range between 0.08 and 0.94 mM (r=0.9996) and for luminol-H(2)O(2) system, the ECL signal intensity of luminol was linear with the concentration of glucose in the range between 0.1 and 1000 μM (r=0.9998). The limits of detection (S/N=3) for dissolved oxygen and glucose were 0.02 mM and 54 nM, respectively. The relative standard deviations (RSD) for repetitive measurements of 0.50 mM oxygen (n=10) and 10 μM glucose (n=30) were 3.5% and 0.3%, respectively. Also, under the optimal conditions for luminol-H(2)O(2) system, the ECL signal intensity of luminol was linear with the concentration of H(2)O(2) in the range between 1 nM and 0.45 mM (r=0.9997). The limit of detection (S/N=3) for H(2)O(2) detection was 0.5 nM and the relative standard deviation for repetitive measurements of 10 μM H(2)O(2) (n=10) was 0.8%.     

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.     

聚鲁米诺-金属离子复合物膜的电化学发光特性及其分析应用研究

建立了一种基于电聚合和配位效应构建聚鲁米诺-金属离子复合物膜修饰电极测定尿素的电化学发光分析新方法, 并且提出了一种优化聚鲁米诺电化学发光分析特性的新思路. 在最佳条件下, 增敏电化学发光信号与尿素的质量浓度在2.0×10-9—1.0×10-7 g/mL 范围内呈线性关系, 检出限为1.7×10-10 g/mL.     

中性微乳液介质增敏鲁米诺电化学发光研究

磷酸盐缓冲的中性溴化十六烷基三甲基铵-正戊醇-正庚烷微乳液介质体系对鲁米诺的电化学发光有显著的增敏作用,本文对此增敏作用进行了研究,并在此介质体系中采用电化学发光淬灭法测定了生物活性分子褪黑素,此法可用于测定脑白金胶囊中的褪黑素。     

Enhanced luminol electrochemiluminescence triggered by an electrode functionalized with dendrimers modified with titanate nanotubes

We have constructed a novel electrochemiluminescence (ECL) platform by functionalizing a poly(amidoamine) dendrimer (PAAD) with titanate nanotubes (TiNTs). The PAAD has an open spherical structure that possesses a high density of active groups and thus favors mass transport, while the TiNTs possess excellent electronic conductivity and thus can promote electron transfer on the surface of a glassy carbon electrode (GCE). A study on the intensity and stability of the ECL of luminol on the modified GCE revealed a substantial improvement compared to that of a bare GCE. The effects of the concentration of TiNTs, the pH value of the solution, and of electrochemical parameters on the intensity of the ECL of luminol were studied and resulted in a sensitive ECL sensor for hydrogen peroxide (H₂O₂) that works in the concentration range of 1 nM to 0.9 μM. The scavenging effect of superoxide dismutase (SOD) on the H2O2 electrode ECL was then exploited to design a biosensor for the determination of SOD in concentrations between 50 and 500 nM.

Enhanced electrochemiluminescence employed for the selective detection of methyl parathion based on a zirconia nanoparticle film modified electrode

A simple, rapid and sensitive electrochemiluminescence (ECL) sensor was proposed for direct measurements of methyl parathion (MP) based on the strong affinity of a nano zirconia particles (ZrO(2) NPs) modified film on the electrode to the phosphoric group. ZrO(2) NPs, which could provide a larger absorption area to immobilize organophosphorus, was firstly modified on the glassy carbon electrode surface to prepare the proposed ECL sensor (ZrO(2)/GC). Subsequently, the ZrO(2)/GC electrode was scanned from -0.8 to +0.6 V to obtain the background signal at 0.44 V in a luminol/KCl solution. Then, a certain concentration of MP was added to an aqueous solution for 240 s, which was absorbed onto the ZrO(2)/GC electrode surface. Moreover, the MP absorbed on the surface of the ZrO(2)/GC electrode enhanced the ECL signal of luminol in the luminol/KCl solution, which increased with the concentration of MP. As a result, a novel ECL sensor was obtained in a luminol/KCl solution. The MP was determined in the range of from 3.8 × 10(-11) to 3.8 × 10(-6) mol L(-1), with a low detection limit of 1.27 × 10(-11) mol L(-1) (S/N = 3). The proposed ECL sensor performance for MP detection will open a new field in the application of rapid and screen detection of ultra-trace amounts of organ phosphorus pesticides (OPs) of vegetables used in farm markets.     

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.     

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).     

Flow-injection electrogenerated chemiluminescence determination of isoniazid using luminol.

Based on a new electrogenerated chemiluminescence (ECL) analytical idea, this paper explains a sensitive and selective flow-injection ECL method using luminol for the determination of isoniazid, based on the sensitizing effect of isoniazid for the weak ECL emission of electrochemically oxidized luminol. Under the optimum experimental conditions, the relative ECL intensity was linear with isoniazid concentration in the range of 4.0 x 10(-8) mol/L to 8.0 x 10(-6) mol/L and with a detecting limit of 2.8 x 10(-8) mol/L.     

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.