UV filters can initiate redox reactions of oxygen and water when exposed to sunlight, generating reactive oxygen species (ROS) that deteriorate the products containing them and cause biological damages. This photochemical reactivity originates from the high chemical potential of UV filters, which also determines the optical properties desirable for sunscreen applications. We hypothesize that this dilemma can be alleviated if the photochemical pathway of UV filters is altered to coupling with redox active molecules. Here, we employ tannic acid (TA) as a key molecule for controlling the photochemical properties of titanium dioxide nanoparticles (TiO NPs). TA provides an unusual way for layer-by-layer assembly of TiO NPs by the formation of a ligand-to-metal charge transfer complex that alters the nature of UV absorption of TiO NPs. The galloyl moieties of TA efficiently scavenge ROS due to the stabilization of ROS by intramolecular hydrogen bonding while facilitating UV screening through direct charge injection from TA to the conduction band of TiO. The TiO-TA multilayers assembled in open porous polymer microspheres substantially increased sun protection while dramatically reducing ROS under UV exposure. The assembled structure exhibits excellent in vivo anti-UV skin protection against epidermal hyperplasia, inflammation, and keratinocyte apoptosis without long-term toxicity.

As a main component of the stratum corneum, ceramides can construct protective lamellae to provide an epidermal barrier against dehydration or external microorganisms. However, as ceramide molecules can easily form the isolated crystalline phase through self-assembly due to the amphipathic nature of bioactive lipids, the effective incorporation of ceramides into liquid media is the remaining issue for controlled release. Here, we report an unprecedented effective strategy to fabricate a completely amorphous and highly sustainable hierarchical ceramide polymer microcapsule for promising epidermal barrier by using the interpenetrating and cooperative self-construction of conical amphiphiles with a different critical packing parameter. The self-constructed amorphous architecture of ceramides in polymer microcapsule is achieved by the facile doping of conical amphiphiles and subsequent in situ polymerization of shell polymer in the core-shell geometry. It is experimentally revealed that an irregular cooperative packing structure formed by adaptive hydrophobic–hydrophilic interactions of cylindrical ceramides and conical amphiphiles in the confined microcapsule geometry enables a completely amorphous morphology of ceramides to be realized during the spontaneous encapsulation process. Furthermore, this elegant approach affords a highly dispersible and uniform hierarchical amorphous ceramide microcapsule with a greatly enhanced long-term stability compared to conventional crystalline ceramides.