3 years ago

Intramolecular Cross-Linking: Addressing Mechanochemistry with a Bioinspired Approach

Intramolecular Cross-Linking: Addressing Mechanochemistry with a Bioinspired Approach
Arad Lang, Charles E. Diesendruck, Avishai Levy, Feng Wang, Or Galant
Many of the attractive properties in polymers are a consequence of their high molecular weight and therefore, scission of chains due to mechanochemistry leads to deterioration in properties and performance. Intramolecular cross-links are systematically added to linear chains, slowing down mechanochemical degradation to the point where the chains become virtually invincible to shear in solution. Our approach mimics the immunoglobulin-like domains of Titin, whose structure directs mechanical force towards the scission of sacrificial intramolecular hydrogen bonds, absorbing mechanical energy while unfolding. The kinetics of the mechanochemical reactions supports this hypothesis, as the polymer properties are maintained while high rates of mechanochemistry are observed. Our results demonstrate that polymers with intramolecular cross-links can be used to make solutions which, even under severe shear, maintain key properties such as viscosity. Unbreakable polymers: Random covalent intramolecular cross-links in single-chain polymer nanoparticles break preferably during ultrasonication, making the polymers resistant to mechanochemistry in solution. Above a certain cross-link density, the nanoparticles become virtually invincible to shear in solution.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201612242

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