All-oil Constructs Stabilized by Cellulose Nanocrystal Surfactants

Constructing all-oil systems with desired geometries and responsiveness would produce a new class of reconfigurable materials that can be used for applications that are not compatible with water or aqueous systems, a fascinating goal to achieve but severely limited by the lack of surfactants. Here, we demonstrate an efficient strategy to stabilize oil–oil interfaces by using the co-assembly between the cellulose nanocrystal and amine-functionalized polyhedral oligomeric silsesquioxane (POSS-NH 2 ). Cellulose nanocrystal surfactants (CNCSs) form and assemble in situ at the interface, showing significantly enhanced binding energy and acid-dependent interfacial activity. When CNCSs jam at the interface, a robust assembly with exceptional mechanical properties can be achieved, allowing the 3D printing of all-oil devices on demand. Using CNCSs as emulsifiers, oil-in-oil high internal phase emulsions can be prepared by one-step homogenization and, when used as templates, porous materials that require water-sensitive monomers can be synthesized. These results open a new platform for stabilizing and structuring all-oil systems, providing numerous applications for microreactors, encapsulation, delivery, and tissue engineering scaffolds.