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The incorporation of mechanosensitive linkages into polymers has led to materials with dynamic force responsivity. Here we report oxanorbornadiene cross-linked double network hydrogels that release molecules through a force-mediated retro Diels–Alder reaction. The molecular design and tough double network of polyacrylamide and alginate promote significantly higher activation at substantially less force than pure polymer systems. Activation at physiologically relevant forces provides scope for instilling dynamic mechanochemical behavior in soft biological materials.
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Preferential Mechanochemical Activation of Short Chains in Bidisperse Triblock Elastomers
Polymer mechanochemistry offers attractive opportunities for using macroscopic forces to drive molecular-scale chemical transformations, but achieving efficient activation in bulk polymeric materials has remained challenging. Understanding how the structure and topology of polymer networks impact molecular-scale force distributions is critical for addressing this problem. Here we show that in block copolymer elastomers the molecular-scale force distributions and mechanochemical activation yields are strongly impacted by the molecular weight distribution of the polymers. We prepare bidisperse triblock copolymer elastomers with spiropyran mechanophores placed in either the short chains, the long chains, or both and show that the overall mechanochemical activation of the materials is dominated by the short chains. Molecular dynamics simulations reveal that this preferential activation occurs because pinning of the ends of the elastically effective midblocks to the glassy/rubbery interface forces early extension of the short chains. These results suggest that microphase segregation and network strand dispersity play a critical role in determining molecular-scale force distributions and suggest that selective placement of mechanophores in microphase-segregated polymers is a promising design strategy for efficient mechanochemical activation in bulk materials.
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- PAR ID:
- 10491288
- Publisher / Repository:
- ACS Macro Lett
- Date Published:
- Journal Name:
- ACS Macro Letters
- Volume:
- 12
- Issue:
- 9
- ISSN:
- 2161-1653
- Page Range / eLocation ID:
- 1213 to 1217
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/acsmacrolett.3c00366
