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Thermo-responsive 3D-printed hydrogels that are composed of methylated α-cyclodextrin polyrotaxanes have been synthesized through post-3D-printing methylation. With a high methylation degree of the threaded α-cyclodextrins, the fabricated monolith exhibits a two-stage thermo-induced aggregation behavior, in which a second micro-crystallization process was identified for the first time. The methylated polyrotaxane monoliths possess reversible temperature-dependent size, transparency, and elastic moduli switching in an aqueous environment. Through dual-material 3D printing, the 3D-printed monolith actuates back-and-forth at different temperatures.

Graphical abstract: Thermo-responsive 3D-printed polyrotaxane monolith

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