Mesoscopic Supramolecular Assembly of Stereolithographically Printed Microgels

Abstract Microgels that assemble upon issuing of a trigger open up miscellaneous applications in soft robotics, drug delivery, and life‐like materials, due to their unique physical and chemical properties. In this work, a novel hydrogel photoresist system is formulated, consisting of 2‐hydroxyethyl acrylate, ethylene glycol diacrylate, and phenyl bis(2,4,6‐trimethylbenzoyl) phosphine oxide, as well as redox‐sensitive supramolecular host‐guest association motifs. Complex and multi‐compartmented geometries with precisely located recognition motifs are printed in high resolution, resulting in multifunctional structured microgel building blocks for mesoscopic self‐assembly. An enzymatic feedback system is employed to dissipatively assemble and disassemble the redox‐active microgel building blocks in a temporally and spatially controlled pathway. The self‐assembling photoresist system is characterized in terms of the lower critical solution temperature, swelling behavior, and printability. The present work provides new perspectives for the design of tailor‐made mesoscopic microgels with customizable functionality and high applicability for various technological applications.