Light-Induced Living Polymer Networks with Adaptive Functional Properties

Shixuan Wei; Julian Smith-Jones; Remy F Lalisse; Julia C Hestenes; Danyang Chen; Scott P O Danielsen; Rowina C Bell; Emily M Churchill; Naiara A Munich; Lauren E Marbella; Osvaldo Gutierrez; Michael Rubinstein; Alshakim Nelson; Luis M Campos

doi:10.1002/adma.202313961

Light-Induced Living Polymer Networks with Adaptive Functional Properties

Adv Mater. 2024 Apr 9:e2313961. doi: 10.1002/adma.202313961. Online ahead of print.

Authors

Shixuan Wei¹, Julian Smith-Jones², Remy F Lalisse³, Julia C Hestenes⁴, Danyang Chen^{5

6}, Scott P O Danielsen^{5

6}, Rowina C Bell², Emily M Churchill¹, Naiara A Munich⁷, Lauren E Marbella⁸, Osvaldo Gutierrez³, Michael Rubinstein^{5

6

9

10}, Alshakim Nelson², Luis M Campos¹

Affiliations

¹ Department of Chemistry, Columbia University, New York, NY, 10027, USA.
² Department of Chemistry, University of Washington, Seattle, WA, 98195, USA.
³ Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA.
⁴ Program of Materials Science and Engineering, Department of Applied Physics and Applied Mathematics, Columbia University, New York, NY, 10027, USA.
⁵ NSF Center for the Chemistry of Molecularly Optimized Networks, Duke University, Durham, NC, 27708, USA.
⁶ Thomas Lord Department of Mechanical Engineering and Materials Science, Duke University, Durham, NC, 27708, USA.
⁷ Department of Chemistry, Barnard College, New York, NY, 10027, USA.
⁸ Department of Chemical Engineering, Columbia University, New York, NY, 10027, USA.
⁹ Departments of Chemistry, Biomedical Engineering, and Physics, Duke University, Durham, NC, 27708, USA.
¹⁰ Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, 001-0021, Japan.

PMID: 38593210
DOI: 10.1002/adma.202313961

Abstract

The advent of covalent adaptable networks (CANs) through the incorporation of dynamic covalent bonds has led to unprecedented properties of macromolecular systems, which can be engineered at the molecular level. Among the various types of stimuli that can be used to trigger chemical changes within polymer networks, light stands out for its remote and spatiotemporal control under ambient conditions. However, most examples of photoactive CANs need to be transparent and they exhibit slow response, side reactions, and limited light penetration. In this vein, it is interesting to understand how molecular engineering of optically active dynamic linkages that offer fast response to visible light can impart "living" characteristics to CANs, especially in opaque systems. Here, the use of carbazole-based thiuram disulfides (CTDs) that offer dual reactivity as photoactivated reshuffling linkages and iniferters under visible light irradiation is reported. The fast response to visible light activation of the CTDs leads to temporal control of shape manipulation, healing, and chain extension in the polymer networks, despite the lack of optical transparency. This strategy charts a promising avenue for manipulating multifunctional photoactivated CANs in a controlled manner.

Keywords: covalent adaptable networks; dynamic covalent polymer networks; living polymer networks; photopolymerization; photoresponsive polymers; self‐healing polymers; thiurams.

Grants and funding

R35GM137797/GM/NIGMS NIH HHS/United States