Excitation Wavelength Dependence of Solvation Dynamics in a Supramolecular Assembly: PEO−PPO−PEO Triblock Copolymer and SDS

Abstract

The triblock copolymer (PEO)20-(PPO)70-(PEO)20 (P123) forms a supramolecular aggregate with sodium dodecyl sulfate (SDS). The solvation dynamics and anisotropy decay of coumarin 480 (C480) in different regions of a P123-SDS aggregate are studied through variation of the excitation wavelength (lambdaex) using femtosecond upconversion. In a P123 micelle, because of the drastic differences in polarity between the hydrophilic corona region (PEO block) and the hydrophobic PPO core, C480 exhibits a pronounced red edge excitation shift (REES) of emission maximum by 24 nm. In the P123-SDS aggregate, SDS penetrates the core of the P123 micelle. This increases the polarity of the core and reduces the difference in the polarity between the core and the corona region. In a P123-SDS aggregate, the REES is much smaller (5 nm) which suggests a reduced difference between the core and the corona. Solvation dynamics in a P123 micelle displays a bulklike ultrafast component (<0.3 and 1 ps) in the PEO corona region, a 200 ps component arising from dynamics of polymer segments, and a very long component (5000 or 3000 ps) due to the highly restricted PPO core. In a P123-SDS aggregate, at lambdaex = 375 and 405 nm, the solvation dynamics is found to be faster than that in P123 micelle. In this case, the component (3000 ps) arising from the core region is faster than that (5000 ps) in P123 micelle. In both P123 micelle and P123-SDS aggregate, the relative contribution of the core region decreases and that of the corona region increases with an increase in lambdaex. At lambdaex = 435 nm, which probes the hydrophilic corona, the solvation dynamics for both P123 micelle and P123-SDS aggregate are almost similar.