Cation Dependent Surface Charge Regulation in Gated Nanofluidic Devices

Surface charge governs nanoscale aqueous electrolyte transport, both in engineered analytical systems and in biological entities such as ion channels and ion pumps as a function of ion type and concentration. Embedded electrodes in a nanofluidic channel, isolated from the fluid in the channel by a dielectric layer, act as active, tunable gates to systematically modify local surface charge density at the interface between the nanochannel surface and the aqueous electrolyte solution, causing significant changes in measured nanochannel conductance. A systematic comparison of transport of monovalent electrolytes [potassium chloride (KCl), sodium chloride (NaCl)], 2:1 electrolytes [magnesium chloride (MgCl₂), calcium chloride (CaCl₂)], and electrolyte mixtures (KCl + CaCl₂) through a gated nanofluidic device was performed. Ion-surface interactions between divalent Ca²⁺ and Mg²⁺ ions and the nanochannel walls reduced the native surface charge density by up to ∼4-5 times compared to the monovalent cations. In electrolyte mixtures, Ca²⁺ was the dominating cation with nanochannel conductance independent of KCl concentration. Systematic changes in local electrostatic surface state induced by the gate electrode are impacted by the divalent cation-surface interactions, limiting modulation of the local surface potential by the gate electrode and resulting in cation dependent nanoscale ion transport as seen through conductance measurements and numerical models.