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Direct Measurement of Polymer-Chain-End-to-End Distances by Using RAFT Chain Transfer Agent as the FRET Acceptor.

Yuming Wang1, Alexander W Fortenberry1, Wenlin Zhang2

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This study introduces a simpler method using Förster resonance energy transfer (FRET) to measure polymer chain dimensions. The new technique directly labels polymer ends, facilitating accurate polymer end-to-end distance (Ree) determination.

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Area of Science:

  • Polymer Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Förster resonance energy transfer (FRET) measures distances (1-10 nm) between donor and acceptor molecules.
  • Determining polymer end-to-end distances (Ree) is crucial for understanding polymer properties.
  • Existing FRET labeling methods for polymers are often complex, hindering widespread application.

Purpose of the Study:

  • To develop a facile and broadly applicable method for direct FRET-based characterization of polymer end-to-end distances (Ree).
  • To utilize a novel anthracene-functionalized chain-transfer agent for reversible addition-fragmentation chain-transfer (RAFT) polymerization.
  • To investigate the influence of molecular weight on the averaged Ree of polymers in solution.

Main Methods:

  • Synthesis of polymers using a novel anthracene-functionalized chain-transfer agent in RAFT polymerization.
  • Direct labeling of polymer chain ends with FRET donor and acceptor molecules.
  • Measurement of averaged polymer end-to-end distances (Ree) using FRET.
  • Validation of FRET results against all-atom molecular dynamics simulations.

Main Results:

  • Successfully synthesized polymers with FRET donor and acceptor molecules directly on their chain ends.
  • Demonstrated the direct application of FRET for characterizing averaged Ree of polymers.
  • Investigated the molecular weight dependence of Ree for polystyrene (PS) and poly(methyl methacrylate) (PMMA) in a good solvent.
  • Achieved good agreement between FRET measurements and molecular dynamics simulations, confirming accuracy.

Conclusions:

  • The developed RAFT polymerization approach provides a straightforward platform for FRET-based Ree determination.
  • This method simplifies the characterization of polymer chain dimensions, especially for low molecular weight polymers.
  • The findings confirm the utility and accuracy of FRET for probing polymer conformations in solution.