Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, PR China; Chongqing key Laboratory of Soil Multi-scale Interfacial Process, College of Resources and Environment, Southwest University, Chongqing 400715, PR China.
Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, PR China.
Biosens Bioelectron. 2018 Feb 15;100:35-40. doi: 10.1016/j.bios.2017.08.054. Epub 2017 Aug 26.
Electrochemiluminescence (ECL) co-reaction and ECL resonance energy transfer (ECL-RET) are two main methods for enhancing the ECL efficiency. In this work, a novel tris(bipyridine) ruthenium(II) derivative (Ru(bpy)(mcbpy)-PEI-ABEI) with high ECL efficiency due to the binary intramolecular ECL self-catalyzed property including intramolecular co-reaction and intramolecular ECL-RET, was prepared for the construction of immunosensor. Firstly, through intramolecular co-reaction, polyethyleneimine (PEI) with large amount of amine co-reactive groups (primary, secondary and tertiary amine) not only increased the ECL intensity of Ru(bpy)(mcbpy), but also improved the ECL signal of N-(aminobutyl)-N-(ethylisoluminol) (ABEI). Meanwhile, ABEI, as an effective energy transfer donor, could further increase the ECL intensity of Ru(bpy)(mcbpy) (as energy transfer receptor) by intramolecular ECL-RET. It is worth noting that the strategy combined intramolecular co-reaction and intramolecular ECL-RET in the same ECL process was more effective for ECL efficiency enhancement compared with the traditional intermolecular interaction or individual intramolecular interaction, which would improve the sensitivity of immunosensor obviously. Thus, the proposed signal-on ECL immunosensor using convex hexoctahedral Pd@Au core-shell nanocrystals (Pd-Au HCDs) as immobilized platform exhibited a detected range for collagen type IV (Col IV), a typical biomarker of diabetic nephropathy (DN), from 0.5pgmL to 7.2ngmL with an estimated detection limit of 0.17pgmL. The developed strategy combined intramolecular co-reaction with intramolecular ECL-RET offered an effective mean for ECL methodology in ECL efficency enhancement and also provided possible road for early diagnosis and treatment monitoring of DN.
电化学发光（ECL）共反应和 ECL 共振能量转移（ECL-RET）是增强 ECL 效率的两种主要方法。在这项工作中，由于包括分子内共反应和分子内 ECL-RET 在内的二元分子内 ECL 自催化特性，制备了一种新型三（联吡啶）钌（II）衍生物（Ru（bpy）（mcbpy）-PEI-ABEI），具有很高的 ECL 效率。用于构建免疫传感器。首先，通过分子内共反应，具有大量胺共反应基团（伯、仲和叔胺）的聚乙烯亚胺（PEI）不仅增加了 Ru（bpy）（mcbpy）的 ECL 强度，而且提高了 N-（氨丁基）-N-（乙基异鲁米诺）（ABEI）的 ECL 信号。同时，ABEI 作为一种有效的能量转移供体，通过分子内 ECL-RET 可以进一步增加 Ru（bpy）（mcbpy）（作为能量转移受体）的 ECL 强度。值得注意的是，与传统的分子间相互作用或单个分子内相互作用相比，在同一 ECL 过程中结合分子内共反应和分子内 ECL-RET 的策略对于 ECL 效率的增强更为有效，这将明显提高免疫传感器的灵敏度。因此，使用凸八面体钯@金核壳纳米晶体（Pd-Au HCDs）作为固定化平台的基于信号开启的 ECL 免疫传感器，用于检测糖尿病肾病（DN）的典型生物标志物 IV 型胶原（Col IV），检测范围为 0.5pgmL 至 7.2ngmL，估计检测限为 0.17pgmL。该策略结合了分子内共反应和分子内 ECL-RET，为 ECL 方法在提高 ECL 效率方面提供了一种有效的手段，也为 DN 的早期诊断和治疗监测提供了可能的途径。
