Biodegradable nanoarchitectures,
with well-defined morphological
features, are of great importance for nanomedical research; however,
understanding (and thereby engineering) their formation is a substantial
challenge. Herein, we uncover the supramolecular potential of PEG–PDLLA
copolymers by exploring the physicochemical determinants that result
in the transformation of spherical polymersomes into stomatocytes.
To this end, we have engineered blended polymersomes (comprising copolymers
with varying lengths of PEG), which undergo solvent-dependent reorganization
inducing negative spontaneous membrane curvature. Under conditions
of anisotropic solvent composition across the PDLLA membrane, facilitated
by the dialysis methodology, we demonstrate osmotically induced stomatocyte
formation as a consequence of changes in PEG solvation, inducing negative
spontaneous membrane curvature. Controlled formation of unprecedented,
biodegradable stomatocytes represents the unification of supramolecular
engineering with the theoretical understanding of shape transformation
phenomena