微芯片毛细管电泳电化学/电化学发光同时检测药物分子

提出了基于毛细管电泳芯片的电化学和电化学发光同时检测技术.在此芯片系统中,三联吡啶钌Ru(bpy)₃²⁺[Tris(2,2'-bypiridyl) ruthenium(Ⅱ)]既作为电化学发光(ECL)检测所需的发光试剂与被分析物反应,生成激发态的Ru(bpy)₃^2+*,从而产生电化学发光信号;又具有催化作用参与电极表面的电化学反应,从而得到增强的电流响应.电化学信号与电化学发光信号同时产生并被分别纪录,从而实现了电化学和电化学发光的同时检测.这种芯片由两部分构成,分别是带有分离和进样通道的聚二甲基硅氧烷(PDMS)层和ITO(Indium tin oxide)工作电极底片.PDMS层与ITO电极底片采用可逆键合的方式组成芯片,该芯片大大简化了操作过程,提髙了发光信号的采集效率.在整个实验过程中,ITO电极表现出良好的稳定性,可长时间多次使用.选用山莨菪碱和氧氟沙星两种药物分子作为被分析物,对芯片系统性能进行了表征.     

基于电化学双共价键法构建可再生高灵敏的电化学发光适体传感器检测可卡因

基于点击化学和重氮盐法的双共价键固定化方法,制备了一种高灵敏、可重复使用的电化学发光(ECL)适体传感器. 该方法以可卡因为分析物,以可卡因适体为分子识别物质,以钌联吡啶衍生物为ECL信号物质. 采用电化学方法在玻碳电极表面重氮化叠氮苯胺,通过点击反应连接炔基功能化的钌联吡啶衍生物标记可卡因适体,获得适体传感器. 该传感器在共反应剂存在下,产生弱的电化学发光信号,可卡因存在下,电化学发光信号增加. 基于此,建立了“信号增强”型检测可卡因的电化学发光分析新方法. 电化学发光信号与可卡因浓度在0.1 nmol·L^-1 ~ 100 nmol·L^-1范围内呈良好的线性关系,检出限为60 pmol·L^-1. 该传感器具有良好的稳定性,可重复多次使用. 该双共价键法在构建ECL传感器方面具有很好的应用前景.     

免标记自增强电化学发光免疫传感器超灵敏检测河豚毒素

以Nafion固定钌联吡啶Au纳米颗粒(Ru(bpy)2+3-Au NPs)于玻碳电极(GCE),借助Au—N共价键固定河豚毒素抗体(anti-TTX),通过抗原抗体的特异性结合构建了超灵敏检测河豚毒素(TTX)的免标记自增强电化学发光(ECL)免疫传感器。当目标物TTX被特异性捕获到修饰电极表面后,可以作为Ru(bpy)2+3的共反应物增强ECL信号。与共反应物存在于溶液中或标记于二抗上相比,其优点在于发光体和共反应物之间的电子转移距离更短,可有效改善电化学发光效率,降低实验成本。最佳条件下,TTX质量浓度在0.01~1 000μg·L-1范围内与ECL信号呈良好的线性关系,检出限(LOD)为0.01μg·L-1。此免标记自增强型ECL免疫传感器显示出优异的稳定性、重现性和灵敏度,对实际样品中TTX的回收率为98.0%~104.0%,表明其具有较好的实用价值。     

纳米金/碳纳米管复合材料修饰电极催化鲁米诺电致发光体系的研究

制备了纳米金/多壁碳纳米管(MWNT)复合材料修饰电极,并将此电极应用于鲁米诺电化学发光体系.电化学发光实验表明,此复合材料修饰电极同时具备了纳米金和碳纳米管的催化性能.此外通过电极活性表面积测算、电化学交流阻抗实验等方法研究了纳米金和碳纳米管在此体系催化过程中的作用.纳米金/碳纳米管修饰电极具有良好的重现性,可以广泛应用于鲁米诺电化学发光测定体系.     

甲醇在Pt表面电化学氧化过程中的化学振荡

基于甲醇电化学氧化的双途径机理,建立了能够表征甲醇电化学氧化过程电位振荡的非线性动力学模型.所建甲醇氧化系统动力学演化模型涉及三个主要的变量:电极电位(e),毒性中间体CO的表面覆盖度(x),含氧物种H2Oa的表面覆盖度(y).通过反应速率常数ki=exp(ai(e-ei))实现了化学反应与电极电位的耦合.研究发现,在不同的电流密度范围内甲醇电化学氧化呈现不同的动力学特征.甲醇电化学氧化时出现的电位振荡现象可以归因为:一是氧化过程中生成了毒性中间体CO,这是产生电化学振荡的诱因;二是强烈依赖于电极电位的非电化学反应,即,含氧物种H2Oa在Pt表面的生成与消失,则是维系振荡的直接原因.而甲醇电化学氧化体系复杂的动力学行为根源在于电极电位e对CO和含氧物种H2Oa所参与反应的耦合反馈作用.对所建模型的数值分析成功地解释了为什么甲醇电化学氧化时出现的电位振荡现象只发生在一定的电流密度范围.     

电化学发光免疫传感器检测甲磺隆的研究

电化学发光 ( Electrochemiluminescence,ECL)分析是对电极施加一定的电压进行电化学反应 ,反应的产物之间或与体系中某种组分发生化学发光 ,用普通光学手段测量发光光谱和强度从而对物质进行痕量分析的一种方法 .与其它检测方法相比 ,它具有一些明显的优势 :标记物的检出限低 ( 2 0 0fmol/L ) ;动力学范围宽达 6个数量级 ;标记物比大多数化学发光标记物稳定 ;由于是电促发光 ,只有靠近电极表面的带有标记物的部分才能被检测到 ,所以分离或非分离体系均可应用此方法 .电化学发光常用的标记试剂分子是联吡啶钌 [Ru( bpy) 2 + 3].Ru( bpy) …     

基于CdSe@CdS/壳聚糖/gC3N4复合物的卡那霉素电化学发光适配体传感器

利用核壳型的CdSe@CdS量子点作为发光物质,并用壳聚糖(CS)、类石墨烯氮化碳(gC₃N₄)与CdSe@CdS量子点合成了CdSe@CdS/CS/gC₃N₄复合物,将该复合物修饰至玻碳电极(GCE)表面,将适配体(Apt)的互补DNA链(cDNA)通过化学反应连接到量子点上,Apt与cDNA发生杂交反应而被修饰至电极表面。将辣根过氧化物酶(HRP)固定到该修饰电极表面,构建了检测卡那霉素(Kana)的电化学发光(ECL)适配体传感器。通过生物催化沉淀(BCP)方法实现Kana的检测,溶液中无Kana时,在H₂O₂的存在下,修饰在电极上的HRP可以催化氧化4-氯-1-萘酚(4-CN),在电极表面产生不导电的苯并-4-氯己二烯酮沉淀,导致电化学发光信号明显降低。溶液中存在Kana时,Kana会与Apt特异性结合,部分dsDNA解旋,导致部分HRP从电极表面脱落,BCP反应减弱,导致ECL信号增强,实现目标物质的特异性检测。计算适配体传感器在Kana溶液中的...     

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...     

量子点电化学发光及其在生物分析中的应用

量子点作为一种新型的电化学发光体具有独特的理化性质,是电化学发光分析领域的研究热点之一.本文简要介绍了量子点电化学发光的机理,回顾了近几年来功能化量子点作为电化学发光体在免疫分析、核酸分析、适体分析、细胞表面聚糖分析等方面的应用,并对其今后的发展方向作了展望.     

共晶诱导增强的电化学发光9,10-二苯基蒽-苝微晶构建高效尿酸传感器

采用表面活性剂辅助自组装方法, 制得非共平面分子9,10-二苯基蒽(DPA)与平面型分子苝(Pe)形成的具有共晶诱导增强效应的电化学发光(ECL)新材料. DPA的引入不仅可以有效降低Pe分子因π-π作用聚集 引起的聚集诱导猝灭(ACQ)效应, 导致Pe分子的ECL发射从二聚体或多聚体激发态(¹Pe^2*)转变为单体激 发态(¹Pe^*); 还发挥了供体分子的作用, 为受体分子Pe提供了有效的能量传递, 进一步增强了ECL响应. 将该共晶发光材料修饰到玻碳电极表面构建了新型ECL尿酸传感器, 其对尿酸检测的线性范围为0.01 μmol/L~ 5.0 mmol/L, 检出限为4.0 nmol/L, 具有良好的选择性和稳定性.     

Recent advances in electrochemiluminescence immunoassay based on multiple-signal strategy

Electrochemiluminescence (ECL) has been widely applied in immunoassays because of low background, high sensitivity, and excellent spatiotemporal controllability. In order to meet the increasing demand for high efficiency and accuracy of immunoassays in complex conditions, considerable efforts have been devoted to ECL strategies with multiple-signal outputs. In this short review, we summarize the recent advances of ECL strategies based on multiple-signal outputs, which includes ratiometric ECL, ECL multiplex immunoassay (MIA), and ECL imaging. Their signal generation strategies and analysis applications for immunoassay are discussed in detail. Moreover, the challenges and prospects in this field from us are addressed.     

Effect of Ionic Strength on the Electrochemiluminescence Generation by Tris(2,2'-bipyridyl)ruthenium(II)/Tri-n-propylamine

Electrochemiluminescence(ECL) is a powerful transduction technique used in biosensing and in vitro diagnosis, while the mechanism of ECL generation is complicated and affected by various factors. Herein the effect of ionic strength on ECL generation by the classical tris(2,2'-bipyridyl)ruthenium(II)[Ru(bpy)₃²⁺]/tri-n-propylamine(TPrA) system was investigated. It is clear that the ECL intensity decreases significantly with the increase of ionic strength, most likely arising from the reduced deprotonation rate of TPrA^+·. We further combined microtube electrode(MTE) with ECL microscopy to unravel the evolution of ECL layer with the variation of ionic strength. At a low concentration of Ru(bpy)₃²⁺, the thickness of ECL layer(TEL) nearly kept unchanged with the ionic strength, indicating the surface-confined ECL generation is dominated by the oxidative-reduction route. While at a high concentration of Ru(bpy)₃²⁺, ECL generation is dominated by the catalytic route and TEL increases remarkably with the increase of ionic strength, because of the extended diffusion length of Ru(bpy)₃³⁺ at a reduced concentration of TPrA^·.     

Highly sensitive analysis strategies of microRNAs based on electrochemiluminescence

The ultrasensitive detection of microRNAs (miRNAs) is currently pursued for the diagnosis of diseases. Due to its outstanding sensitivity, electrochemiluminescence (ECL) is expected to be very effective toward the above goal. In this short review, bioanalytical strategies currently employed in ECL detections of miRNAs are summarized. ECL sensors based on electrochemiluminescent resonance energy transfer (ERET), hybridization chain reaction (HCR), strand displacement reaction (SDR), and other strategies, have an extremely low detection limit of 10^?18 M miRNA. In particular, the establishment of miniaturized ECL sensors has shown great potential for point-of-need testing of diseases.     

Color‐Tunable Electrogenerated Chemiluminescence of Ruthenium N‐Heterocyclic Carbene Complexes

Ru(II) complexes 1 – 3 bearing various N‐heterocyclic carbene (NHC) ligands were synthesized, and their photophysical, electrochemical, and electrogenerated chemiluminescence (ECL) properties were discussed to evaluate a potential of their use as multicolor ECL labels. Interestingly, they exhibited ECL emission ranging from greenish‐yellow to red both in nonaqueous and mixed aqueous solutions, which might show the potential of the Ru(II) complexes as multicolor ECL labels.     

Preparation of Luminol-doped Nanoparticle and Its Application in DNA Hybridization Analysis

Introduction The analysis of DNA sequence and DNA mutant detection play fundamental roles in the rapid development of molecular diagnostics and in the anticancer drug screening. Therefor many detection techniques of DNA sequence have been developed in recent years. These techniques mainly depend on the nucleic acid hybridization1 and their sensitivities are related to the specific activity of the label linked to the DNA probe. The degree of hybridization of probe to its complementary DN…     

Synthesis, properties, and electrogenerated chemiluminescence (ECL) of a novel carbazole-based chromophore

A novel molecule containing electron-rich carbazole and electron-deficient pyrimidine moieties exhibits useful and intriguing physical properties, including promising reversible redox behavior that gives rise to electrogenerated chemiluminescence (ECL).     

Theory of transient and steady-state ECL generation at double-hemicylinder assemblies using conformal mapping and simulations

Rigorous analytical expressions for steady-state currents and electrogenerated chemiluminescence (ECL) intensities are derived for two-hemicylinder assemblies operating in the ECL generation mode based on a specific conformal mapping transform. This transform is also used for fast and accurate simulations of transient currents and ECL intensities leading to an excellent agreement at long times with the analytical steady state solutions. These results are compared to those relative to two-band assemblies to investigate the effect of hemicylindrical electrode protuberance on ECL efficiencies. This evidence that electrode protuberance results in a drastic increase of the ECL generation and shortening of commutation times when the gap is not too large as compared to the electrode radii.     

基于聚合物点的电致化学发光生物传感器用于葡萄糖检测

羧基功能化的聚[(9,9-二辛基芴基-2,7-二基)-co-(1,4-苯并-{2,1′,3}-噻二唑)]聚合物点(PFBT-COOH)在无外加共反应试剂的条件下具有高的电致化学发光(ECL)信号,且过氧化氢(H_2O_2)对其ECL具有高效猝灭作用。采用PFBT-COOH修饰玻碳电极,进一步交联葡萄糖氧化酶(GOD)以构建酶传感器(GOD/PFBT-COOH/GCE)。随着检测底液中葡萄糖浓度的增加,葡萄糖在GOD催化下原位产生的H_2O_2量增加,导致传感器的ECL信号逐渐减弱,从而实现葡萄糖的准确、快速、灵敏检测。此方法测得葡萄糖的线性范围为1.0×10~(-7)～3.0×10~(-3) mol/L,检出限为3.0×10~(-8) mol/L。血清样品中葡萄糖的加标回收率为98.5%～106%。该策略为酶传感器的构建提供了新思路,为葡萄糖的检测提供了新方法。     

Generation of gold nanostructures at the surface of platinum electrode by electrodeposition for ECL detection for CE

In this paper, we report a sensitive method for ECL detection for CE based on generation of gold nanostructures at the surface of Pt electrode by electrodeposition. Difenidol hydrochloride was used as a model analyte. With the increase of electrodeposition amount, the morphology of gold nanostructures changed from discrete nanoflowers to dense nanoparticle array. Interestingly, the variation of deposition amount also greatly affected the ECL intensity of difenidol. The ECL intensity increased remarkably with deposition amount and reached the maximum value at the deposition amount of 7.0×10^?8C; further increasing the deposition amount, however, caused the ECL intensity to decrease. Other conditions, including applied potential, injection time and voltage, buffer pH, were also optimized in detail. Under the optimized conditions, the linear response range of difenidol is from 1.0×10^?8 to 5.0×10^?5 M, and the detection limit was 4.0×10^?9 M (S/N=3). The RSDs of ECL intensity and migration time were 2.0 and 1.6%, respectively (n=5, at 7.5 μM difenidol). Compared with using bare electrode, the detection sensitivity was significantly improved by ca. two orders of magnitude. Notably, the nanogold was prepared at the surface of electrode and no nanogold was added to the electrophoretic buffer or detection cell, thus causing no interference to the separation. Finally, the proposed method was successfully applied to the analysis of difenidol in tablets and urine samples. With high sensitivity and good reproducibility, this method provides a promising platform for the determination of pharmaceuticals that have a tertiary amine group such as difenidol.     

Polymer Electrochemiluminescence Featuring Thermally Activated Delayed Fluorescence

Electrochemiluminescence (ECL) based on conjugated polymers or oligomers is persistently being pursued owing to its huge application scope ranging from ultra-sensitive bioanalysis to ultra-resolution imaging and spectroscopy. Because of the theoretical limit in radiative exciton generation yield (typically ∼25 %) of those polymers or oligomers, the corresponding ECL efficiency is still limited, which hampers its ECL performance and its related applications. Herein, we report ECL based on a thermally activated delayed fluorescence (TADF) polymer scaffold, which is characteristic of all-exciton harvesting in the ECL process, and thus potentially capable of achieving ∼100 % ECL efficiency. These desired properties of the TADF polymer ECL is attributed to a fast and efficient up-conversion process from non-radiative triplet to radiative singlet states under thermal activation, which is absent in conventional fluorescent polymers/oligomers, such as F8BT. In this study, various ECL modes, including annihilation or co-reactant mode using TPrA or S₂O₈²⁻ as co-reactant, are confirmed for our model TADF polymer ECL system, which was different from fluorescent polymer ECL counterpart. Furthermore, solid-state ECL sensing on L-cysteine (an important marker of disease) is also evaluated by using the model TADF polymer. Ultralow detection limit in combination with high sensitivity and good specificity are achieved for this model system, indicative of a high potential of the TADF polymer scaffold for applications in the broad field of ECL.