Endogenous dynamic nuclear polarization NMR of hydride-terminated silicon nanoparticles

Silicon nanoparticles (SiNPs) are intriguing materials and their properties fascinate the broader scientific community; they are also attractive to the biological and materials science sub-disciplines because of their established biological and environmental compatibility, as well as their far-reaching practical applications. While characterization of the particle nanostructure can be performed using ²⁹Si solid-state nuclear magnetic resonance (NMR) spectroscopy, poor sensitivity due to low Boltzmann population and long acquisition times hinder in-depth studies of these potentially game-changing materials. In this study, we compare two dynamic nuclear polarization (DNP) NMR protocols to boost ²⁹Si sensitivity in hydride-terminated SiNPs. First, we assess a traditional indirect DNP approach, where a nitroxide biradical (AMUPol or bCTbk) is incorporated into a glassing agent and transferred through protons (e^- → ¹H → ²⁹Si) to enhance the silicon. In this mode, electron paramagnetic resonance (EPR) spectroscopy demonstrated that the hydride-terminated surface was highly reactive with the exogenous biradicals, thus decomposing the radicals within hours and resulting in an enhancement factor, ε, of 3 (T_B = 15 s) for the 64 nm SiNP, revealing the surface components. Secondly, direct DNP NMR methods were used to enhance the silicon without the addition of an exogenous radical (i.e., use of dangling bonds as an endogenous radical source). With radical concentrations <1 mM, ²⁹Si enhancements were obtained for the series of SiNPs ranging from 3 to 64 nm. The ability to use direct ²⁹Si DNP transfer (e^- → ²⁹Si) shows promise for DNP studies of these inorganic nanomaterials (ε = 6 (T_B = 79 min) for 64 nm SiNPs) with highly reactive surfaces, showing the sub-surface and core features. These preliminary findings lay a foundation for future endogenous radical development through tailoring the surface chemistry, targeting further sensitivity gains.