Sliding Topological Degrees of Freedom Regulate the Micellization of Linear-Star Copolymers in Selective Solvent

Introducing dynamic molecular topology as an adjustable degree of freedom represents a promising strategy for engineering block copolymer self-assembled structures. We develop a self-consistent field theory (SCFT) for linear–star topology-transformable block copolymers (L–S BCP) in selective solvents and construct comprehensive phase diagrams spanning lamellar, cylindrical, and spherical micellization. Our analysis reveals the physical mechanisms by which topological variability regulates micelle formation, interfacial curvature, and morphological transitions. Our results reveal that varying the sliding side-chain length induces re-entrant phase behavior and that the direction of curvature regulation depends on the location of the sliding junction. Importantly, the curvature selectivity of micelles is differentially controlled by the sliding junction position: solvophilic side chains in the corona enhance interfacial curvature, whereas solvophobic side chains in the core reduce it. Unlike fixed branching topologies restricted to a single configuration, the sliding topology exhibits position-dependent self-adaptation within the inhomogeneous micellar environment. This mechanism offers a theoretical foundation for programming micelle formation thresholds and nanostructure evolution through dynamic topology design.