A smart thermoresponsive macroporous 4D structure by 4D printing of Pickering-high internal phase emulsions stabilized by plasma-functionalized starch nanomaterials for a possible delivery system

Hierarchically porous structures combine microporosity, mesoporosity, and microporosity to enhance pore accessibility and transport, which are crucial to develop high performance materials for biofabrication, food, and pharmaceutical applications. This work aimed to develop a 4D-printed smart hierarchical macroporous structure through 3D printing of Pickering-type high internal phase emulsions (Pickering-HIPEs). The key was the utilization of surface-active (hydroxybutylated) starch nanomaterials, including starch nanocrystals (SNCs) (from waxy maize starch through acid hydrolysis) or starch nanoparticles (SNPs) (obtained through an ultrasound treatment). An innovative procedure to fabricate the functionalized starch nanomaterials was accomplished by grafting 1,2-butene oxide using a cold plasma technique to enhance their surface hydrophobicity, improving their aggregation, and thus attaining a colloidally stabilized Pickering-HIPEs with a low concentration of each surface-active starch nanomaterial. A flocculation of droplets in Pickering-HIPEs was developed after the addition of modified SNCs or SNPs, leading to the formation of a gel-like structure. The 3D printing of these Pickering-HIPEs developed a highly interconnected large pore structure, possessing a self-assembly property with thermoresponsive behavior. As a potential drug delivery system, this thermoresponsive macroporous 3D structure offered a lower critical solution temperature (LCST)-type phase transition at body temperature, which can be used in the field of smart releasing of bioactive compounds.