Rupturing Polymeric Micelles with Cyclodextrins

Small-angle neutron scattering has been used to investigate the associative structures formed by triblock copolymers of poly(ethylene oxide) (PEO)−polypropylene oxide (PPO)−poly(ethylene oxide) (PEO) (also known as Pluronics) and to monitor the structural changes occurring upon complexation with heptakis(2,6-di-O-methyl)-β-cyclodextrin (hβ-CD) over the temperature range from 5 to 70 °C. At low temperature, the Pluronics are dispersed as unimers. Close to ambient temperature, the hydrophobicity of PPO causes the aggregation of the polymers into spherical micelles with core sizes between 40 and 50 Å and a high inclusion of solvent. The aggregation number increases with temperature as the hydrophobicity of the core is gradually enhanced. hβ-CD spontaneously forms pseudopolyrotaxanes with the triblock copolymers either when in their unimer form or micellized. The complexation results in an increase in the effective critical micellar concentration. It is suggested that the cyclodextrins thread onto the polymer backbone to localize preferentially on the central PPO block, therefore improving its water solubility. At temperatures where the polymers exist in micellar form, complexation with hβ-CD gives rise to a complete disruption of the aggregates. These processes are highly temperature-dependent. Above 50 °C, the break-up of the aggregates is inhibited, and large-scale aggregation is observed.