Persistent Micelle Corona Chemistry Enables Constant Micelle Core Size with Independent Control of Functionality and Polyelectrolyte Response.

Polymer micelles have found significant uses in areas such as drug/gene delivery, medical imaging, and as templates for nanomaterials. For many of these applications, the micelle performance depends on its size and chemical functionalization. To date, however, these parameters have often been fundamentally coupled since the equilibrium size of a micelle is a function of the chemical composition in addition to other parameters. Here, we demonstrate a novel processing pathway allowing for the chemical modification to the corona of kinetically trapped "persistent" polymer micelles, termed Persistent Micelle Corona Chemistry (PMCC). Judicious planning is crucial to this size-controlled functionalization where each step requires all reagents and polymer blocks to be compatible with (1) the desired chemistry, (2) micelle persistency, and (3) micelle dispersion. A desired functionalization can be implemented with PMCC by pairing the synthetic planning with polymer solubility databases. Specifically, poly(cyclohexyl methacrylate-b-(diethoxyphosphoryl)methyl methacrylate) (PCHMA-b-PDEPMMA) was prepared to combine a glassy-core block (PCHMA) for kinetic control with a block (PDEPMMA) that is able to be hydrolyzed to yield acid groups. The processing sequence determines the resulting micelle size distribution where the hydrolyzed-then-micellized sequence yields widely varying micelle dimensions due to equilibration. In contrast, the micellized-then-hydrolyzed sequence maintains kinetically trapped micelles throughout the PMCC process. Statistically significant transmission electron microscopy (TEM) measurements demonstrate that PMCC uniquely enables this functionalization with constant average micelle core dimensions. Furthermore, these kinetically trapped micelles also subsequently maintain constant micelle core size when modifying the Coulombic interactions of the micelle corona via pH changes.