Engineering Pore‐Like Topographies in Liquid‐Core Soft Compartments via Compositional Tuning of Aqueous Immiscible Systems

ABSTRACT The processing of materials at aqueous interfaces has enabled the generation of compartmentalized structures with broad biomedical interest. Controlling the porous structure of soft materials remains largely limited to post‐processing strategies or cytotoxic conditions, while it is still underexplored in all‐aqueous interface‐assembled membranes. Nevertheless, distinct topographies and porosity features that may modulate cell response and enable cellular outward invasion are crucial for tissue development and regeneration. Here, we present liquid‐core soft compartments formed via interfacial complexation between natural polyelectrolytes, in which membrane architecture is tailored by adjusting the composition of the prototypical aqueous two‐phase system. This method enables the generation of asymmetric interfacial membranes featuring an internal microporous structure and a thinner homogeneous outer layer, in a single‐step manner and under a fully aqueous and mild environment. Fiber‐shaped tubular compartments with distinct luminal porous topographical features influence cell‐mediated fiber deformation capacity and facilitate cell spreading from the fiber compartment to surrounding tissue‐like environments, particularly in conditions with larger internal pore structures. The explored approach enables generating interfacial materials with tailorable morphologies that may find applications in cellular migration, with impact in the fields of tissue engineering and regeneration, such as vascularization or immune cell migration disease modeling.