A crystal engineering approach for rational design of curcumin crystals for Pickering stabilization of emulsions

Emulsions stabilized via Pickering particles are becoming more and more popular due to their high stability and biocompatibility. Hence, developing new ways to produce effective Pickering particles is essential. In this work, we present a crystal engineering approach to obtain precise control over particle properties such as size, shape, and crystal structure, which may affect wettability and surface chemistry. A highly reproducible synthesis method via anti-solvent crystallization was developed to produce sub-micron sized curcumin crystals of the metastable form III, to be used as Pickering stabilizers. The produced crystals presented a clear hydrophobic nature, which was demonstrated by their preference to stabilize water-in-oil (W/O) emulsions. A comprehensive experimental and computational characterization of curcumin crystals was performed to rationalize their hy- drophobic nature. Analytical techniques including Raman spectroscopy, powder X-ray diffraction (PXRD), Solid- State Nuclear Magnetic Resonance (SSNMR), scanning electron microscopy (SEM), Differential Scanning Calo- rimetry (DSC), confocal fluorescence microscopy and contact angle measurements were used to characterize curcumin particles in terms of shape, size and interfacial activity. The attachment energy model was instead applied to study relevant surface features of curcumin crystals, such as topology and facet-specific surface chemistry. This work contributes to the understanding of the effect of crystal properties on the mechanism of Pickering stabilization, and paves the way for the formulation of innovative products in fields ranging from pharmaceuticals to food science.