A Bioinspired Hybrid Polymer Network Fusing Supramolecular and Mechanically Interlocked [ a n]Daisy Chains

Abstract Heterodimeric assembly in microtubules (MTs) unifies two functionally complementary tubulin subunits that form similar long-range supramolecular assemblies yet exhibit distinct dynamic behaviors, enabling sophisticated biological functions and providing a powerful paradigm for artificial material design. However, recapitulating such heterodimeric assembly using fully synthetic building blocks remains highly challenging. Here we report a bioinspired heterodimeric A2BB′ assembly approach based on molecular [an]daisy chains ([an]DCs) capable of forming long-range assembled structures, giving rise to a hybrid polymer network (DCHPN) integrating supramolecular and mechanically interlocked [an]DCs. The two structurally similar [an]DC assemblies act as a coupled pair with distinct yet cooperative functions in governing the network dynamics: supramolecular [an]DCs confer dynamic instability analogous to β-tubulin subunits through reversible dissociation, whereas mechanically interlocked [an]DCs function as persistent structural anchors that stabilize the system reminiscent of α-tubulin subunits. Compared with its structurally analogous but purely supramolecular cross-linked control sample, DCHPN exhibits more complex stimuli-responsive behavior, characterized by pronounced dynamic disassembly under external stimuli while retaining polymer-like integrity and enhanced resistance to complete viscous flow upon further activation. This bioinspired strategy offers a prospective pathway for advancing artificial supramolecular assembled materials toward higher-order structural and functional integration.