Looping-in complexation and ion partitioning in nonstoichiometric polyelectrolyte mixtures

A wide variety of intracellular membraneless compartments are formed via liquid-liquid phase separation of charged proteins and nucleic acids. Understanding the stability of these compartments, while accounting for the compositional heterogeneity intrinsic to cellular environments, poses a daunting challenge. We combined experimental and theoretical efforts to study the effects of nonstoichiometric mixing on coacervation behavior and accurately measured the concentrations of polyelectrolytes and small ions in the coacervate and supernatant phases. For synthetic polyacrylamides and polypeptides/DNA, with unequal mixing stoichiometry, we report a general “looping-in” phenomenon found around physiological salt concentrations, where the polymer concentrations in the coacervate initially increase with salt addition before subsequently decreasing. This looping-in behavior is captured by a molecular model that considers reversible ion binding and electrostatic interactions. Further analysis in the low-salt regime shows that the looping-in phenomenon originates from the translational entropy of counterions that are needed to neutralize nonstoichiometric coacervates.

Space Electroosmotic Thrusters in Ion Partitioning Soft Nanochannels

Space electroosmotic thrusters (EOTs) are theoretically investigated in a soft charged nanochannel with a dense polyelectrolyte layer (PEL), which is considered to be more realistic than a low-density PEL. When the PEL is dense, its permittivity is smaller than the one of the electrolyte solution layer, leading to rearrangement of ions in the channel, which is denoted as the ion partitioning effect. It is noted that fluid viscosity becomes high within the PEL owing to the hydration effect. An analytical solution for electroosmotic velocity through the channel is obtained by utilizing the Debye–Hückel linearization assumption. Based on the fluid motion, thruster performances, including thrust, specific impulse, thrust-to-power ratio, and efficiency, are calculated. The ion partitioning effect leads to enhancement of the thruster velocity, while increase of the dynamic viscosity inside the PEL reduces the flow rate of the fluid. Therefore, these performances are further impacted by the dense soft material, which are discussed in detail. Moreover, changes or improvements of the thruster performances from the dense PEL to the weak PEL are presented and compared, and distributions of various energy items are also provided in this study. There is a good result whereby the increase in electric double layer thickness promotes the development of thruster performances. Ultimately, the simulated EOTs produce thrust of about 0 to 20 μN and achieve thruster efficiency of 90.40%, while maintaining an appropriate thrust–power ratio of about 1.53 mN/W by optimizing all design parameters.