Ratiometric Flapping Force Probe That Works in Polymer Gels

J Am Chem Soc. 2022 Feb 16;144(6):2804-2815. doi: 10.1021/jacs.1c12955. Epub 2022 Feb 2.

Abstract

Polymer gels have recently attracted attention for their application in flexible devices, where mechanically robust gels are required. While there are many strategies to produce tough gels by suppressing nanoscale stress concentration on specific polymer chains, it is still challenging to directly verify the toughening mechanism at the molecular level. To solve this problem, the use of the flapping molecular force probe (FLAP) is promising because it can evaluate the nanoscale forces transmitted in the polymer chain network by ratiometric analysis of a stress-dependent dual fluorescence. A flexible conformational change of FLAP enables real-time and reversible responses to the nanoscale forces at the low force threshold, which is suitable for quantifying the percentage of the stressed polymer chains before structural damage. However, the previously reported FLAP only showed a negligible response in solvated environments because undesirable spontaneous planarization occurs in the excited state, even without mechanical force. Here, we have developed a new ratiometric force probe that functions in common organogels. Replacement of the anthraceneimide units in the flapping wings with pyreneimide units largely suppresses the excited-state planarization, leading to the force probe function under wet conditions. The FLAP-doped polyurethane organogel reversibly shows a dual-fluorescence response under sub-MPa compression. Moreover, the structurally modified FLAP is also advantageous in the wide dynamic range of its fluorescence response in solvent-free elastomers, enabling clearer ratiometric fluorescence imaging of the molecular-level stress concentration during crack growth in a stretched polyurethane film.

Publication types

  • Research Support, Non-U.S. Gov't
  • Video-Audio Media

MeSH terms

  • Cyclooctanes / chemical synthesis
  • Cyclooctanes / chemistry*
  • Fluorescence
  • Fluorescent Dyes / chemical synthesis
  • Fluorescent Dyes / chemistry*
  • Gels / chemistry*
  • Molecular Conformation
  • Phenazines / chemical synthesis
  • Phenazines / chemistry*
  • Polyurethanes / chemistry*
  • Stress, Mechanical

Substances

  • Cyclooctanes
  • Fluorescent Dyes
  • Gels
  • Phenazines
  • Polyurethanes