College of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, P. R. China.
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, P. R. China.
Anal Chem. 2023 Jul 4;95(26):10096-10104. doi: 10.1021/acs.analchem.3c01820. Epub 2023 Jun 23.
In this work, a potential-resolved electrochemiluminescence (ECL) multiplex immunoassay (MIA) was developed using zirconium-based metal-organic framework (MOF) nanoparticles with intense self-ECL as an anodic ECL tag and CdTe nanocrystals (NCs) as a cathodic ECL tag. ECL luminophore 5,5'-(anthracene-9,10-diyl)diisophthalic acid (HADIP) and coreactant hexamethylenetetramine (HMT) bound to zirconium nodes in the MOF, giving Zr-ADIP-HMT nanoparticles. Benefiting from the intrareticular charge transfer (ICT) between the oxidized ligands of HADIP and HMT via hydrogen bonds, the intense self-ECL from Zr-ADIP-HMT was applied to the potential-resolved ECL MIA without an exogenous anodic coreactant, which can eliminate detrimental effects of multiplex coreactants and anodic ECL emission from CdTe NCs. The ICT within Zr-ADIP-HMT nanoparticles could shorten the electron transport path and reduce the complexity of radical intermediate transport. The ECL intensity from Zr-ADIP-HMT was 18.6-fold that from the mixture of HADIP and HMT. In potential-resolved ECL MIA, two lung cancer biomarkers, carcinoembryonic antigen and neuron-specific enolase, were adopted as model analytes, with detection limits of 18 and 5.3 fg·mL, respectively. The dual-ligand Zr-ADIP-HMT nanoparticles provide a proof of concept using ICT-based self-ECL luminophores for potential-resolved ECL MIAs with isolated coreactants.
在这项工作中，开发了一种基于锆的金属-有机骨架（MOF）纳米粒子的势分辨电化学发光（ECL）多重免疫分析（MIA），该纳米粒子具有作为阳极 ECL 标记的强烈自 ECL 和碲化镉纳米晶体（NCs）作为阴极 ECL 标记。ECL 发光体 5,5'-(蒽-9,10-二基)二异酞酸（HADIP）和核心反应物六亚甲基四胺（HMT）与 MOF 中的锆节点结合，得到 Zr-ADIP-HMT 纳米粒子。受益于 HADIP 和 HMT 的氧化配体之间通过氢键的内联网电荷转移（ICT），强烈的自 ECL 来自 Zr-ADIP-HMT 用于无需外加阳极共反应物的势分辨 ECL MIA，这可以消除多重组分共反应物和 CdTe NCs 的阳极 ECL 发射的有害影响。Zr-ADIP-HMT 纳米粒子内的 ICT 可以缩短电子传输路径并减少自由基中间物传输的复杂性。来自 Zr-ADIP-HMT 的 ECL 强度是 HADIP 和 HMT 混合物的 18.6 倍。在势分辨 ECL MIA 中，两种肺癌生物标志物，癌胚抗原和神经元特异性烯醇化酶被用作模型分析物，检测限分别为 18 和 5.3 fg·mL。双配体 Zr-ADIP-HMT 纳米粒子提供了一种使用基于 ICT 的自 ECL 发光体的概念证明，用于具有隔离共反应物的势分辨 ECL MIA。
