Ring buckling and C=N isomerization pathways for efficient photoprotection in two nature-inspired UVA sunscreens revealed through ultrafast dynamics and high-level calculations.

Sunscreens provide a frontline defense for our DNA against the damage caused by ultraviolet (UV) radiation. The active ingredients in topically applied sunscreens that provide this defense are UV filters, which preferentially absorb or reflect UV radiation before it penetrates the skin and interacts with photosensitive nucleic acids. However, there are concerns related to human and environmental toxicity of current UV filters, and consequently a shift toward nature-inspired, particularly microbial, UV filters. In this paper, new physical insight is provided into the fundamental mechanisms of photoprotection in two synthetic analogs of mycosporine-like amino acid-type UV filters, demonstrating new methods of protection that are distinct from those of current commercial sunscreens, extending previous work in this area. Transient absorption measurements (both transient electronic absorption spectroscopy and transient vibrational absorption spectroscopy) are combined with steady-state studies and high-level computational results to aid our mapping of the experimentally derived lifetimes to real-time photodynamic processes. The conclusions reached here pave the way toward developing new and more efficient biomimetic DNA photoprotectant materials.