Deciphering ion concentration polarization-based electrokinetic molecular concentration at the micro-nanofluidic interface: theoretical limits and scaling laws

The electrokinetic molecular concentration (EMC) effect at the micro–nanofluidic interface, which enables million-fold preconcentration of biomolecules, is one of the most compelling yet least understood nanofluidic phenomena. Despite the tremendous interests in EMC and the substantial efforts devoted, the detailed mechanism of EMC remains an enigma so far owing to its high complexity, which gives rise to the significant scientific controversies outstanding for over a decade and leaves the precise engineering of EMC devices infeasible. We report a series of experimental and theoretical new findings that decipher the mechanism of EMC. We demonstrate the first elucidation of two separate operating regimes of EMC, and establish the first theoretical model that analytically yet concisely describes the system. We further unveil the dramatically different scaling behaviors of EMC in the two regimes, thereby clarifying the long-lasting controversies. We believe this work represents important progress towards the scientific understanding of EMC and related nano-electrokinetic systems, and would enable the rational design and optimization of EMC devices for a variety of applications.