A surface-grafted thermoresponsive hydrogel in which the surface structure dominates the bulk properties

Abstract

A surface-grafted hydrogel was successfully synthesized by immobilization of the ATRP initiator at the surface region of the gel and the subsequent ARGET ATRP step. This is the first example of a bulk hydrogel with a dense surface-localized layer of a grafted polymer and "active" permeation control of the gel.

Transformable Materials: Structurally Tailored and Engineered Macromolecular (STEM) Gels by Controlled Radical Polymerization

“…Materials permitting such postsynthesis alteration are, however, challenging to fabricate. Polymer gels and networks present a potentially viable material for such tailorable frameworks because of their stimuli-responsive behavior , and tunable mechanical properties. − Moreover, due to their reversible swelling properties, polymer gels are “open systems,” which allow for the diffusion of nutrients or the introduction of new functionalities . Here, we show that structurally tailored and engineered macromolecular (STEM) gels prepared by controlled radical polymerization (CRP) permit facile postmodification and thus provide a route for new hierarchical, functional materials.…”

“…4−8 Moreover, due to their reversible swelling properties, polymer gels are "open systems," which allow for the diffusion of nutrients or the introduction of new functionalities. 9 Here, we show that structurally tailored and engineered macromolecular (STEM) gels prepared by controlled radical polymerization (CRP) permit facile postmodification and thus provide a route for new hierarchical, functional materials. In particular, with this level of postprocessing, the STEM gels are attractive candidates for tissue engineering, 10,11 actuators, 12,13 and 3D printing.…”

Living polymer networks prepared by controlled radical polymerization techniques

“…In 2016-17 the Yoshida group modified the surface properties of NIPAM hydrogels produced by ATRP. 44,45 They immobilized ATRP initiator sites and then used them for growth by ARGET ATRP, after which the temperature response rate and sensitivity were studied. The structure of the typical ATRP initiator results in them being positioned throughout the network as living buds on chain ends, which means that the growth tends towards meshfilling behaviors.…”

Design of biointerfaces composed of soft materials using controlled radical polymerizations

“…Matsukawa and co-workers recently reported surface-grafted thermoresponsive hydrogels, which were prepared by immobilization of the ATRP initiator on the surface of the gel network composed of NPAAm and N -(3-aminopropyl)methacrylamide (NAPMAm) with amino groups, and subsequent polymerization of PNIPAAm. 98…”