Stratum-Confined Solid-State Reaction (SC-SSR) toward Colloidal Silicon-Based Hollow Nanostructures for Bioapplications.

Silicon nanostructures (SiNSs) can provide multifaceted bioapplications; but preserving their subhundred nm size during high-temperature silica-to-silicon conversion is the major bottleneck. The SC-SSR utilizes an interior metal-silicide stratum space at a predetermined radial distance inside silica nanosphere to guide the magnesiothermic reduction reaction (MTR)-mediated synthesis of hollow and porous SiNSs. In depth mechanistic study explores solid-to-hollow transformation encompassing predefined radial boundary through the participation of metal-silicide species directing the in-situ formed Si-phase accumulation within the narrow stratum. Evolving thin-porous Si-shell remains well protected by the in-situ segregated MgO emerging as a protective cast against the heat-induced deformation and interparticle sintering. Retrieved hydrophilic SiNSs (<100 nm) can be conveniently processed in different biomedia as colloidal solutions and endocytosized inside cells as photoluminescence (PL)-based bioimaging probes. Inside the cell, rattle-like SiNSs encapsulated with Pd nanocrystals can function as biorthogonal nanoreactors to catalyze intracellular synthesis of probe molecules through C-C cross coupling reaction.