Spatio-temporal electrochemiluminescence dynamics for engineering high-efficiency biosensors

At its core, this thesis is a journey through the mechanisms of electrochemiluminescence, explored across diverse formats and with distinct objectives. From microelectrode arrays to mesoporous matrices and bead-based biosensors, each chapter explores a unique configuration. Yet a unifying thread runs through the narrative: the quest for a deeper understanding and strategic optimization of the processes that lead to light emission. This mechanistic focus guides the narrative arc of the work, offering the reader a coherent exploration of the ECL’s evolving landscape. The chapters follow a deliberate progression, from designing systems that guide ECL pathways, to dissecting a mature platform constrained to a single mechanism. This dual approach allowed us to examine ECL from two complementary angles: I. Chapters 2 and 3 investigate how the design of electrode architectures—ranging from microelectrode arrays to mesoporous matrices—can be used as proof-of-concept platforms to steer ECL mechanisms. By modulating spatial confinement, material properties, and diffusion regimes, these systems allow us to selectively activate different reaction routes, eventually tailoring them to specific analytical or imaging applications. II. Chapter 4 shifts the focus to a well-established biosensing system that operates through a single, dominant mechanism. Within this controlled framework, we systematically probe the key parameters that influence signal generation and decay. This targeted analysis reveals how subtle changes in coreactant delivery, beads’ chemistry, and luminophore properties can be leveraged to enhance performance and stability. Together, these strategies offer a complementary view: one that builds mechanisms from the ground up through design, and another that deconstructs them within a mature platform. This interplay between innovation and refinement forms the backbone of the thesis and opens new avenues for advancing ECL-based technologies.