Dynamic Nuclear Polarization of Selectively ²⁹Si-Enriched Core@shell Silica Nanoparticles

²⁹Si silica nanoparticles (SiO₂ NPs) are promising magnetic resonance imaging (MRI) probes that possess advantageous properties for in vivo applications, including suitable biocompatibility, tailorable properties, and high water dispersibility. Dynamic nuclear polarization (DNP) is used to enhance ²⁹Si MR signals via enhanced nuclear spin alignment; to date, there has been limited success employing DNP for SiO₂ NPs due to the lack of endogenous electronic defects that are required for the process. To create opportunities for SiO₂-based ²⁹Si MRI probes, we synthesized variously featured SiO₂ NPs with selective ²⁹Si isotope enrichment on homogeneous and core@shell structures (shell thickness: 10 nm, core size: 40 nm), and identified the critical factors for optimal DNP signal enhancement as well as the effective hyperpolarization depth when using an exogenous radical. Based on the synthetic design, this critical factor is the proportion of ²⁹Si in the shell layer regardless of core enrichment. Furthermore, the effective depth of hyperpolarization is less than 10 nm between the surface and core, which demonstrates an approximately 40% elongated diffusion length for the shell-enriched NPs compared to the natural abundance NPs. This improved regulation of surface properties facilitates the development of isotopically enriched SiO₂ NPs as hyperpolarized contrast agents for in vivo MRI.