The physical properties of nanoscale materials often vary with their size, unlike the corresponding bulk material properties, which can only be changed by modifying the material composition. In particular, it is believed that hydration phenomena are length scale dependent. The manifestation of hydrophobicity over multiple length scales plays a crucial role in self-assembly processes such as protein folding and colloidal stability. In the case of particles composed of a bulk hydrophobic material, it is well known that the free energy of hydration monotonically increases with particle size. However, the size-dependent free energy of hydration for particles composed of a bulk hydrophilic material has not been studied. Here we show that the free energy of hydration is not a monotonic function of particle size, but rather, changes sign from positive to negative as the particle size increases. In other words, the particle is hydrophobic at small size and hydrophilic at large size. This behavior arises from a purely geometrical effect caused by the curvature of the particle-water interface. We explore the consequences of this phenomenon on colloidal stability and find that it dictates the shape of colloidal aggregates.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry