Stereocomplexed and homocrystalline thermo-responsive physical hydrogels with a tunable network structure and thermo-responsiveness

J Mater Chem B. 2020 Sep 21;8(35):7947-7955. doi: 10.1039/d0tb01484b. Epub 2020 Aug 5.

Abstract

The widespread application of thermo-responsive hydrogels requires materials with robust mechanical properties and tunable responsiveness. Herein, we report robust thermo-responsive physical hydrogels with a tunable network structure and responsiveness by controlling the manner of crystallization of hydrophobic blocks. Biocompatible, stereocomplexable poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) were introduced into thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) to obtain the enantiomeric grafted copolymers PNIPAM-g-PLLA and PNIPAM-g-PDLA and their corresponding hydrogels. The hydrophobic PLLA/PDLA domains served as physical crosslinking junctions in the hydrogels. The crystalline structure of the hydrogels can be facilely tuned by varying the ratio of PLLA/PDLA enantiomeric blocks. Stereocomplex (SC) crystallization between PLLA and PDLA facilitates the formation of H-bonded hydrophobic domains with denser chain packing, which endows the racemic hydrogels with a stronger network structure, higher mechanical strength, and better solvent resistance compared to enantiopure examples. The hydrogels exhibit good thermo-sensitivity in water; the stronger racemic hydrogel network restricts volume shrinkage and water desorption at high temperatures, enabling the facile control of thermo-responsiveness. The crystallization-tuned thermo-responsiveness of racemic and enantiopure hydrogels also allows for the design of assembled bilayer hydrogels capable of thermally triggered reversible shape morphing.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrylic Resins / chemistry
  • Hydrogels / chemistry*
  • Hydrophobic and Hydrophilic Interactions
  • Polyesters / chemistry
  • Stereoisomerism
  • Temperature*

Substances

  • Acrylic Resins
  • Hydrogels
  • Polyesters
  • poly-N-isopropylacrylamide
  • poly(lactide)