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Direct-Ink Write 3D Printing Multistimuli-Responsive Hydrogels and Post-Functionalization Via Disulfide Exchange
Christopher R Fellin1, Alshakim Nelson1
1Department of Chemistry, University of Washington, Seattle, Washington 98105, USA.
Summary
This study introduces a novel multi-stimuli-responsive hydrogel, 3D printable using direct-ink writing. The material allows for post-functionalization, enabling diverse applications through its adaptable properties.
Area of Science:
- Materials Science
- Polymer Chemistry
- Biotechnology
Background:
- Developing advanced hydrogels for 3D printing requires materials with tunable properties and post-fabrication modification capabilities.
- Stimuli-responsive polymers are crucial for creating dynamic and adaptable materials for various applications.
Purpose of the Study:
- To synthesize and characterize a multi-stimuli-responsive hydrogel suitable for direct-ink write (DIW) 3D printing.
- To enable post-functionalization of the 3D printed hydrogel networks with thiol-bearing molecules.
- To demonstrate the hydrogel's responsiveness to temperature and its utility in fabricating functional constructs.
Main Methods:
- Synthesis of poly(alkyl glycidyl ether)s with methacrylate termini for hydrogel formation.
- Incorporation of pyridyl disulfide urethane methacrylate (PDS-UM) for thiol-reactive post-functionalization.
- Characterization of stimuli-responsive behaviors (temperature, shear-thinning) and crosslinking capabilities.
- Investigation of hydrogel reactivity with glutathione and other thiol-containing probes at varying conditions.
- Fabrication of a 3D printed object using a customized DIW printer and subsequent conjugation.
Main Results:
- Successfully developed a stimuli-responsive hydrogel exhibiting sol-gel transition, shear-thinning, and photochemical crosslinking.
- Demonstrated temperature-dependent swelling behavior consistent with Lower Critical Solution Temperature (LCST) properties.
- Achieved efficient post-functionalization of the hydrogel network with diverse thiol-bearing molecules (proteins, polymers, small molecules) under various conditions.
- Fabricated a 3D printed construct that could be fluorescently tagged and exhibited temperature-induced size changes.
Conclusions:
- The developed hydrogel platform is highly versatile for 3D printing and post-functionalization.
- The multi-stimuli-responsive nature allows for dynamic control over material properties and functions.
- This technology holds promise for applications requiring adaptable and functional 3D printed materials.

