Nanoparticle-polymer hybrids are becoming increasingly important because seemingly contrasting properties, such as mechanical stability and high elasticity, can be combined into one material. In particular, hybrids made of self-assembled polymers are of growing interest since they exhibit high structural precision and diversity and the subsequent reorganization of the nanoparticles is possible. In this work, we show, for the first time, how hybrids of silica nanoparticles and self-assembled vesicles of polystyrene-block-polyacrylic acid can be prepared using the simple and inexpensive method of co-precipitation, highlighting in particular the challenges of using silica instead of other previously well-researched materials, such as gold. The aim was to investigate the influence of the type of modification and the particle size of the silica nanoparticles on the encapsulation and structure of the polymer vesicles. For this purpose, we first needed to adjust the surface properties of the nanoparticles, which we achieved with a two-step modification procedure using APTES and carboxylic acids of different chain lengths. We found that silica nanoparticles modified only with APTES could be successfully encapsulated, while those modified with APTES and decanoic acid resulted in vesicle agglomeration and poor encapsulation due to their strong hydrophobicity. In contrast, no negative effects were observed when different particle sizes (20 nm and 45 nm) were examined.
Keywords: block copolymer; co-precipitation; encapsulation; fusion; modification; nanoparticle–polymer hybrid; self-assembly; synthesis; vesicle.