Polymer nanoparticle sizes from dynamic light scattering and size exclusion chromatography: the case study of polysilanes.

Dynamic light scattering (DLS) and size exclusion chromatography (SEC) are among the most popular methods for determining polymer sizes in solution. Taking dendritic and network polysilanes as a group of least soluble polymer substances, we critically compare and discuss the difference between nanoparticle sizes, obtained by DLS and SEC. Polymer nanoparticles are typically in poor solution conditions below the theta point and are therefore in the globular conformation. The determination of particle sizes in the presence of attractive interactions is not a trivial task. The only possibility to measure, aggregation-free, the true molecular size of polymer nanoparticles in such a solution regime, is to perform the experiment with a dilute solution of globules (below the theta point and above the miscibility line). Based on the results of our polysilane measurements, we come to a conclusion that DLS provides more reliable results than SEC for dilute solutions of globules. General implications for the size measurements of polymer nanoparticles in solution are discussed.