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

Förster resonance energy transfer (FRET) is a powerful tool for measuring distances between two molecules (donor and acceptor) in close proximity (1-10 nm), which can be employed for determining polymer end-to-end distances (R_ee). However, previous works for labeling FRET pairs on chain-ends often involve relatively complex steps for materials preparation, potentially limiting their broad use in synthetic polymer systems. In this work, we introduce an anthracene-functionalized chain-transfer agent for reversible addition-fragmentation chain-transfer (RAFT) polymerizations, which can directly yield polymers containing FRET donor and acceptor molecules on respective chain-ends. This approach enables the direct use of FRET for characterizing the averaged R_ee of polymers. Building on this platform, we investigate the averaged R_ee of polystyrene (PS) and poly(methyl methacrylate) (PMMA) in a good solvent as a function of their molecular weight. Notably, the FRET results show good agreement with simulation results obtained from all-atom molecular dynamics, confirming its measurement accuracy. Overall, this work provides a facile and broadly applicable platform to directly determine the R_ee of low molecular weight polymers by using FRET-based methods.