NMR Characterization of Nanoscale Surface Patterning in Mixed Ligand Nanoparticles

Spontaneous phase separation in binary mixed ligand shells is a proposed strategy to create patchy nanoparticles. The surface anisotropy, providing directionality along with interfacial properties emerging from both ligands, is highly desirable for targeted drug delivery, catalysis, and other applications. However, characterization of phase separation on the nanoscale remains quite challenging. Here we have adapted solid-state ¹H spin diffusion NMR experiments designed to detect and quantify spatial heterogeneity in polymeric materials to nanoparticles (NPs) functionalized with mixed short ligands. Janus NPs and physical mixtures of homoligand 3.5 nm diameter ZrO₂ NPs, with aromatic (phenylphosphonic acid, PPA) and aliphatic (oleic acid, OA) ligands, were used to calibrate the ¹H spin diffusion experiments. The Janus NPs, prepared by a facile wax/water Pickering emulsion method, and mixed ligand NPs, produced by ligand exchange, both with 1:1 PPA:OA ligand compositions, display strikingly different solvent and particle-particle interactions. ¹H spin diffusion NMR experiments are most consistent with a lamellar surface pattern for the mixed ligand ZrO₂ NPs. Solid-state ¹H spin diffusion NMR is shown to be a valuable additional characterization tool for mixed ligand NPs, as it not only detects the presence of nanoscale phase separation but also allows measurement of the domain sizes and geometries of the surface phase separation.