Confined microenvironments in biomacromolecules arising from molecular crowding account for their well‐defined biofunctions and  bioactivities. To mimick this, synthetic polymers to form confined structures or microenvironments are of key scientific value, which have received  significant attention recently. To create synthetic confined microenvironments, molecular crowding effects and topological cooperative effects have been applied successfully, and the key is balance between self‐association of structural units and self‐repulsion from crowding‐induced steric hindrance. In this article, formation of confined microenvironments from stimuli‐responsive dendronized polymers carrying densely dendritic oligoethylene glycols (OEGs) moieties in their pendants is presented. These wormlike thick macromolecules exhibit characteristic thermoresponsive properties, which can provide constrained microenvironments to encapsulate effectively guest molecules including dyes, proteins, or nucleic acids to prevent their protonation or biodegradation. This efficient shielding effect can also mediate chemical reactions in aqueous phase, and even enhance chirality transferring efficiency. All of these can be switched off simply through the thermally‐induced dehydration and collapse of OEG dendrons due to the amphiphilicity of OEG chains. Furthermore, the switchable encapsulation and release of guests can be greatly enhanced when these dendronized polymers are used as major constituents for fabricating bulkhydrogels or nanogels, which provide a higher‐level confinement.

该文受邀作为Feature article发表在Macromolecular  Rapid Communications上 https://doi.org/10.1002/marc.202000325