Mechanistic strategies for next-generation electrochemiluminescence biosensing

Bead-based ECL immunoassays represent a leading transduction platform in clinical diagnostic as a result of the high sensitivity, broad dynamic range, adaptability to diverse biological analytes, and the ease of use by non-expert operators. Despite being well-established, the relentless demand for more sensitive assays, capable of providing earlier and more reliable diagnosis, keeps driving research toward new frontiers. Fundamental studies have clarified the key mechanistic steps governing ECL emission in bead-based systems, laying the groundwork for strategies to fine-tune the underlying chemistry and boost signal output. Among current approaches, developing more stable luminophores, engineering coreactants and electrode materials, and modifying bead compositions and chemical environments have produced encouraging results. Nevertheless, most of these efforts rely on incremental modifications of the parent system. As the available variables become increasingly exhausted, the improvements in performance appear to be approaching a plateau. This situation highlights the need for fundamentally new reaction mechanisms capable of reshaping the field and unlocking the next generation of ECL-based diagnostics. In this Thesis, mechanistic understanding of ECL is translated into fundamentally new reaction pathways that reshape light generation in bead-based immunoassays, paving the way for next-generation diagnostic platforms with higher sensitivity, broader applicability, and more reliable performance in clinically relevant environments.