Measuring single-nanoparticle wetting properties by freeze-fracture shadow-casting cryo-scanning electron microscopy

Nanoparticles at fluid interfaces are central to a rapidly increasing range of cutting-edge applications, including drug delivery, uptake through biological membranes, emulsion stabilization and the fabrication of nanocomposites. Understanding nanoscale wetting is a challenging issue, still unresolved for individual nanoparticles, and is essential in designing nanoparticle-building blocks with controlled surface properties. The core information about the structural and thermodynamic properties of particles at fluid interfaces is enclosed in the three-phase contact angle θ. Here we present a novel in situ method, on the basis of freeze-fracture shadow-casting cryo-scanning electron microscopy, that allows the measurement of contact angles of individual nanoparticles with 10 nm diameter, and thus greatly surpasses the current state of the art. We study hydrophilic and hydrophobic, organic and inorganic nanoparticles, demonstrating general applicability to systems of fundamental and applied nanotechnological interest. Significant heterogeneity in the wetting of nanoparticles is observed.