A Stochastic FRET Study on the Core Dimension of Polystyrene--Poly(Polyethylene Glycol Monomethyl Ether Acrylate) Micelles.

Polystyrene--poly(polyethylene glycol monomethyl ether acrylate) (PSt--PPEGA) copolymers featuring pyrene and perylene as the Förster resonance energy transfer (FRET) donor (denoted as D-BCP) and acceptor (denoted as A-BCP), respectively, were synthesized via the reversible addition and fragmentation chain transfer (RAFT) polymerization. These copolymers were then used to form DA-mixed micelles via a dialysis method. The micelles consisted of D-BCP (mole fraction = 0.04), A-BCP ( = 0.04), and label-free PSt--PPEGA ( = 0.92). The decrease in fluorescence intensity of pyrene in the micelles confirmed the occurrence of FRET, with an observed efficiency of 0.32. A Monte Carlo approach was employed to estimate the expected FRET efficiency, assuming the random fractional distribution of D-BCP and A-BCP, along with the random spatial distribution of pyrene and perylene within the micellar core. The observed FRET efficiency suggested a core radius () of 0.95, where was the Förster critical distance. With calculated to be 3.2 nm based on Förster theory, was determined to be approximately 3.0 nm, aligning closely with the dried-out core radius estimated from aggregation number and polystyrene density. This stochastic FRET methodology was further applied to investigate the swelling behavior of the polymer micelles in a mixture of ,-dimethylformamide (DMF) and water. Dynamic light scattering analysis revealed minimal change in core dimension below 60 vol % DMF content. However, FRET analysis provided a deeper insight, showing an increase in core radius with DMF content up to 20 vol %, followed by saturation up to 50 vol %, offering a more comprehensive understanding of the micelle swelling behavior.