Expanding the stoichiometric window for metal cross-linked gel assembly using competition

Abstract

Polymer networks with dynamic cross-links have generated widespread interest as tunable and responsive viscoelastic materials. However, narrow stoichiometric limits in cross-link compositions are typically imposed in the assembly of these materials to prevent excess free cross-linker from dissolving the resulting polymer networks. Here we demonstrate how the presence of molecular competition allows for vast expansion of the previously limited range of cross-linker concentrations that result in robust network assembly. Specifically, we use metal-coordinate cross-linked gels to verify that stoichiometric excessive metal ion cross-linker concentrations can still result in robust gelation when in the presence of free ion competing ligands, and we offer a theoretical framework to describe the coupled dynamic equilibria that result in this effect. We believe the insights presented here can be generally applied to advance engineering of the broadening class of polymer materials with dynamic cross-links.

Document Details

Document Type
Pub Defense Publication
Publication Date
Oct 07, 2019
Source ID
10.1073/pnas.1906349116

Entities

People

  • Niels Holten-Andersen
  • Seth A Cazzell

Organizations

  • Massachusetts Institute of Technology
  • National Science Foundation
  • Office of Naval Research

Tags

Readers

  • Polymer Science and Engineering.
  • Quantum spin resonance or Electron Paramagnetic Resonance spectroscopy.
  • Systems Analysis and Design