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)₂(mcbpy)²⁺-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)₂(mcbpy)²⁺, 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)₂(mcbpy)²⁺ (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 [email protected] 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 0.5 pg mL⁻¹ to 7.2 ng mL⁻¹ with an estimated detection limit of 0.17 pg mL⁻¹. 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）是提高ECL效率的两种主要方法。在这项工作中，一种新型三（联吡啶）钌（II）衍生物（Ru（bpy）₂（mcbpy）²⁺ -PEI-ABEI）由于具有分子内共反应的二元分子内ECL自催化性能而具有很高的ECL效率并制备了分子内ECL-RET用于免疫传感器的构建。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）₂（mcbpy）²⁺的ECL强度，但也改善了N-（氨基丁基）-N-（乙基异鲁米诺）（ABEI）的ECL信号。同时，作为有效的能量转移供体的ABEI可以进一步提高Ru（bpy）₂（mcbpy）²⁺的ECL强度。（作为能量转移受体）通过分子内ECL-RET。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ECL效率的提高更为有效，这将明显提高免疫传感器的灵敏度。因此，使用凸六面体[受电子邮件保护的]核壳纳米晶体（Pd-Au HCD）作为固定平台的拟议ECL信号传感器显示了IV型胶原蛋白（Col IV）的检测范围，该胶原蛋白是糖尿病性肾病（DN）的典型生物标志物），从0.5 pg mL ^-1到7.2 ng mL ^-1，估计检出限为0.17 pg mL ^-1。所开发的策略将分子内共反应与分子内ECL-RET相结合，为ECL方法学提高ECL效率提供了有效手段，也为DN的早期诊断和治疗监测提供了可能的途径。