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Efficient Exchange in a Bioinspired Dynamic Covalent Polymer Network via a Cyclic Phosphate Triester Intermediate.

Soumabrata MajumdarBrahim MezariHuiyi ZhangJeroen van AartRolf A T M van BenthemJohan P A HeutsRint P Sijbesma
Published in: Macromolecules (2021)
Bond exchange via neighboring group-assisted reactions in dynamic covalent networks results in efficient mechanical relaxation. In Nature, the high reactivity of RNA toward nucleophilic substitution is largely attributed to the formation of a cyclic phosphate ester intermediate via neighboring group participation. We took inspiration from RNA to develop a dynamic covalent network based on β-hydroxyl-mediated transesterifications of hydroxyethyl phosphate triesters. A simple one-step synthetic strategy provided a network containing phosphate triesters with a pendant hydroxyethyl group. 31P solid-state NMR demonstrated that a cyclic phosphate triester is an intermediate in transesterification, leading to dissociative network rearrangement. Significant viscous flow at 60-100 °C makes the material suitable for fast processing via extrusion and compression molding.
Keyphrases
  • solid state
  • magnetic resonance
  • physical activity
  • high resolution
  • single molecule
  • transition metal