Soft Matter, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Although polymer-based coacervates have long been a research focus, their large molecular weight and sluggish response to external stimuli motivate the study of simpler micelle-small molecule systems. Here, we use coarse-grained simulations with umbrella sampling-explicitly incorporating solvent water-to investigate coacervation charged amphiphile multivalent countercharged compound, elucidating both kinetic pathways thermodynamic driving forces. Our results show that proceeds through initial pairing ions self-assembled micelles, followed by Brownian motion-driven coalescence-rather than Ostwald ripening, dominant growth mechanism in traditional micellization systems monovalent counterions. Both stages are primarily governed entropy rather enthalpy. This gain arises from release counterions hydration shells, as well dehydration coacervate complex, marked contact first water shell. The consequent reduction ion-solvent interactions incurs unfavorable ion-dipole contributions overall In highlighting water's critical role, our findings shed light on how details govern phase behavior physical properties

Язык: Английский