High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms

Mesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature for biomedical application of MSNs is limiting MSN size in the sub-micrometer regime to control uptake and cell viability. However, careful size tuning in such a regime remains still challenging. We aim to tackling this issue by developing two synthetic procedures for MSN size modulation, performed in homogenous aqueous/ethanol solution or two-phase aqueous/ethyl acetate system. Both approaches make use of tetraethyl orthosilicate as precursor, in the presence of cetyltrimethylammonium bromide, as structure-directing agent, and NaOH, as base-catalyst. NaOH catalyzed syntheses usually require high temperature (>80 °C) and large reaction medium volume to trigger MSN formation and limit aggregation. Here, a successful modulation of MSNs size from 40 up to 150 nm is demonstrated to be achieved by purposely balancing synthesis conditions, being able, in addition, to keep reaction temperature not higher than 50 °C (30 °C and 50 °C, respectively) and reaction mixture volume low. Through a comprehensive and in-depth systematic morphological and structural investigation, the mechanism and kinetics that sustain the control of MSNs size in such low dimensional regime are defined, highlighting that modulation of size and pores of the structures are mainly mediated by base concentration, reaction time and temperature and ageing, for the homogenous phase approach, and by temperature for the two-phase synthesis. Finally, an in vitro study is performed on bEnd.3 cells to investigate on the cytotoxicity of the MNSs.     

Templated Synthesis and Assembly of Two-, Three- and Six-Patch Silica Nanoparticles with a Controlled Patch-to-Particle Size Ratio

We report a fabrication route of silica nanoparticles with two, three or six patches with an easily tunable patch-to-particle size ratio. The synthetic pathway includes two main stages: the synthesis of silica/polystyrene multipod-like templates and the selective growth of their silica core through an iterative approach. Electron microscopy of the dimpled nanoparticles obtained after dissolution of the polystyrene nodules of the multipod-like nanoparticles provides evidence of the conformational growth of the silica core. Thanks to the presence of some polymer chains, which remained grafted at the bottom of the dimples after the dissolution of the PS nodules, the solvent-induced assembly of the patchy nanoparticles is performed. Chains, hexagonal suprastructures and cubic lattices are obtained from the assembly of two-, three- and six-patch silica nanoparticles, respectively. Our study can guide future work in both patchy nanoparticle synthesis and self-assembly. It also opens new routes towards the fabrication of specific classes of one-, two- and three-dimensional colloidal lattices, including complex tilings.