Core-Shell Interface-Oriented Synthesis of Bowl-Structured Hollow Silica Nanospheres Using Self-Assembled ABC Triblock Copolymeric Micelles.

Abstract

Hollow porous silica nanospheres (HSNs) are emerging classes of cutting-edge nanostructured materials. They have elicited much interest as carriers of active molecule delivery due to their amorphous chemical structure, nontoxic nature, and biocompatibility. Structural development with hierarchical morphology is mostly required to obtain the desired performance. In this context, large through-holes or pore openings on shells are desired so that the postsynthesis loading of active-moleculeonto HSNs via a simple immersion method can be facilitated. This study reports the synthesis of HSNs with large through-holes or pore openings on shells, which are subsequently termed bowl-structured hollow porous silica nanospheres (BHSNs). The synthesis of BHSNs was mediated by the core-shell interfaces of the core-shell corona-structured micelles obtained from a commercially available ABC triblock copolymer (polystyrene- b-poly(2-vinylpyridine)- b-poly(ethylene oxide) (PS-P2VP-PEO)). In this synthesis process, polymer@SiO2 composite structure was formed because of the deposition of silica (SiO2) on the micelles' core. The P2VP block played a significant role in the hydrolysis and condensation of the silica precursor, i.e., tetraethylorthosilicate (TEOS) and then maintaining the shell's growth. The PS core of the micelles built the void spaces. Transmission electron microscopy (TEM) images revealed a spherical hollow structure with an average particle size of 41.87 ± 3.28 nm. The average diameter of void spaces was 21.71 ± 1.22 nm, and the shell thickness was 10.17 ± 1.68 nm. According to the TEM image analysis, the average large pore was determined to be 15.95 nm. Scanning electron microscopy (SEM) images further confirmed the presence of large single pores or openings in shells. These were formed as a result of the accumulated ethanol on the PS core acting to prevent the growth of silica.