Natural-Product-Tailored Polyurethane: Size-Dictated Construction of Polypseudorotaxanes with...

Cyclodextrin (CD)-based polyrotaxanes (PRs) and polypseudorotaxanes (PPRs) have attracted considerable attention due to their unique topological structures and functions. However, limited by the simple chemical structures and the single functionalization of guest polymer units like poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG), to date the construction of CD-based PRs and PPRs with precisely controllable supramacromolecular structures is fairly rare. In this work, two kinds of molecular necklace-like PPRs with CD-triterpenoid pairs were prepared via the size-dictated construction, where the threaded guest polymer was a natural product-tailored polyurethane (PU-PEG-GA) with the alternating structure of triterpenoid and PEG segments via a simple step-growth polymerization. Taking advantage of the differentiation in host-guest interactions between β/γ-CD and triterpenoid pairs, β-CD simultaneously located on both PEG segments and triterpenoid units in PU-PEG-GA, while γ-CD selectively recognized triterpenoid units. Consequently, the assembly morphology of PU-PEG-GA was adjusted hierarchically from micelles to worms and vesicles upon addition of β-CD, whereas they gradually collapsed to disappear in the presence of γ-CD. Our biocompatible PPRs with precisely controllable supramacromolecular structures may lead to the exploration on understanding and simulating macromolecular recognition using natural products.