Controlling Size and Fluorescence of Dye-Loaded Polymer Nanoparticles through Polymer Design

Nanoprecipitation is a straightforward yet powerful technique to synthesize polymer nanoparticles loaded with various biologically active compounds or contrast agents. Particle formation in this approach is kinetically controlled, and various assembly parameters have been used to control the size distribution and properties of the formed nanoparticles. Here, the influence of the nature of the polymer on the formation of nanoparticles in nanoprecipitation is studied systematically by varying its hydrophobicity and charge over a broad range. For this, methacrylate copolymers with different types and fractions of hydrophobic, hydrophilic, and charged side groups are synthesized. Nanoprecipitation of these polymers shows that particle size increases with increasing global hydrophobicity of the polymers. At the same time, both hydrophilic and charged groups reduce particle size. In this way, we achieve control over particle size from ∼10 to 200 nm. Furthermore, the effect of the polymer nature on the photophysical properties of nanoparticles loaded with a fluorescent dye, a rhodamine B derivative with a bulky hydrophobic counterion (fluorinated tetraphenylborate), is studied. It is found that the hydrophobic/hydrophilic balance of the polymer modulates to a large extent the spectral properties and fluorescence quantum yield of the dye encapsulated at high concentration, which reflects changes in the dye aggregation within the polymer matrix. Thus, we show how polymer chemistry can tune kinetically controlled formation of nanoparticles and encapsulation of the load. The concepts introduced here should be valuable tools for the design of nanoparticles for imaging and drug-delivery applications.