Hydrophilic nanoparticles stabilising mesophase curvature at low concentration but disrupting mesophase order at higher concentrations

Abstract

Using high pressure small angle X-ray scattering (HP-SAXS), we have studied monoolein (MO) mesophases at 18 wt% hydration in the presence of 10 nm silica nanoparticles (NPs) at NP–lipid number ratios (ν) of 1 × 10⁻⁶, 1 × 10⁻⁵ and 1 × 10⁻⁴ over the pressure range 1–2700 bar and temperature range 20–60 °C. In the absence of the silica NPs, the pressure–temperature (p–T) phase diagram of monoolein exhibited inverse bicontinuous cubic gyroid (Q^G_II), lamellar alpha (L_α), and lamellar crystalline (L_c) phases. The addition of the NPs significantly altered the p–T phase diagram, changing the pressure (p) and the temperature (T) at which the transitions between these mesophases occurred. In particular, a strong NP concentration effect on the mesophase behaviour was observed. At low NP concentration, the p–T region pervaded by the Q^G_II phase and the L_α–Q^G_II mixture increased, and we attribute this behaviour to the NPs forming clusters at the mesophase domain boundaries, encouraging transition to the mesophase with a higher curvature. At high NP concentrations, the Q^G_II phase was no longer observed in the p–T phase diagram. Instead, it was dominated by the lamellar (L) phases until the transition to a fluid isotropic (FI) phase at 60 °C at low pressure. We speculate that NPs formed aggregates with a “chain of pearls” structure at the mesophase domain boundaries, hindering transitions to the mesophases with higher curvatures. These observations were supported by small angle neutron scattering (SANS) and scanning electron microscopy (SEM). Our results have implications to nanocomposite materials and nanoparticle cellular entry where the interactions between NPs and organised lipid structures are an important consideration.