G-Quadruplex-Filtered Selective Ion-to-Ion Current Amplification for Non-Invasive Ion Monitoring in Real Time.

Living cells efflux intracellular ions for maintaining cellular life, so intravital measurements of specific ion signals are of significant importance for studying cellular functions and pharmacokinetics. In this work, de novo synthesis of artificial K+ -selective membrane and its integration with polyelectrolyte hydrogel-based open-junction ionic diode (OJID) is demonstrated, achieving a real-time K+ -selective ion-to-ion current amplification in complex bioenvironments. By mimicking biological K+ channels and nerve impulse transmitters, in-line K+ -binding G-quartets are introduced across freestanding lipid bilayers by G-specific hexylation of monolithic G-quadruplex, and the pre-filtered K+ flow is directly converted to amplified ionic currents by the OJID with a fast response time at 100 ms intervals. By the synergistic combination of charge repulsion, sieving, and ion recognition, the synthetic membrane allows K+ transport exclusively without water leakage; it is 250× and 17× more permeable toward K+ than monovalent anion, Cl- , and polyatomic cation, N-methyl-d-glucamine+ , respectively. The molecular recognition-mediated ion channeling provides a 500% larger signal for K+ as compared to Li+ (0.6× smaller than K+ ) despite the same valence. Using the miniaturized device, non-invasive, direct, and real-time K+ efflux monitoring from living cell spheroids is achieved with minimal crosstalk, specifically in identifying osmotic shock-induced necrosis and drug-antidote dynamics.

Reversible Crosslinking of Polymer/Metal-Ion Complexes for a Microfluidic Switch.

The importance of chitosan has been strongly emphasized in literature because this natural polymer could not only remove heavy metal ions in water but also have the potential for recyclability. However, reversible phase transition and its dynamics, which are highlighting areas of a recycle process, have not been studied sufficiently. Here, we present dynamic studies of the dissolution as well as the gelation of a physically crosslinked chitosan hydrogel. Specifically, a one-dimensional gel growth system and an acetate buffer solution were prepared for the precise analysis of the dominant factors affecting a phase transition. The dissolution rate was found to be regulated by three major factors of the pH level, Cu2+, and NO2 -, while the gelation rate was strongly governed by the concentration of OH-. Apart from the gelation rate, the use of Cu2+ led to the rapid realization of gel characteristics. The results here provide strategies for process engineering, ultimately to determine the phase-transition rates. In addition, a microfluidic switch was successfully operated based on a better understanding of the reversible crosslinking of the chitosan hydrogel. Rapid gelation was required to close the channel, and a quick switchover was achieved by a dissolution enhancement strategy. As a result, factors that regulated the rates of gelation or dissolution were found to be useful to operate the fluidic switch.