Bipolar electrochemiluminescence: from fundamentals to emerging trends

The combination of electrochemiluminescence (ECL) and bipolar electrochemistry (BE) has advanced the development of a new generation of optical devices, offering new possibilities for high-efficiency detection and sensing applications. ECL, a luminescent phenomenon triggered at the electrode surface and driven by redox reactions, has become a versatile technique for highly sensitive detection. Meanwhile, BE enables the remote activation of electrochemical processes without the need for a direct electric connection to the electrodes, thus simplifying the design and miniaturization of electrochemical systems. The integration of both technologies optimizes the interaction between luminophores and bipolar electrodes, improving the efficiency of analyte detection and facilitating the implementation of parallel or multiplexed detection strategies, thus increasing precision and repeatability. This synergy has extended the application scope in areas such as bioanalysis, environmental analysis, and pollutant detection. This review analyzes the fundamental principles of ECL and BE, as well as their synergy in advanced systems, covering the design of spatially confined structures that improve the polarization of bipolar electrodes, thus reducing the threshold energy required to activate ECL and enhancing its efficiency. Additionally, the incorporation of dynamic elements, such as rotating electrodes and microfluidic platforms, has facilitated real-time analysis and the visualization of electrochemical processes at both macroscopic and microscopic levels. The combination of ECL and BE technologies has not only expanded diagnostic and monitoring possibilities in autonomous systems, but has also paved the way for the development of the next generation of analytical technologies, with a significant impact on various scientific challenges.