Author:

Keywords:

Science & Technology, Physical Sciences, Technology, Chemistry, Physical, Nanoscience & Nanotechnology, Materials Science, Multidisciplinary, Physics, Atomic, Molecular & Chemical, Chemistry, Science & Technology - Other Topics, Materials Science, Physics, PLANT SUNSCREEN, ULTRAVIOLET, ABSORPTION, DAMAGE, PHOTOISOMERIZATION, PHOTOPROTECTION, SPECTROSCOPY, AVOBENZONE, Biomimetic Materials, Humans, Models, Molecular, Molecular Conformation, Radiation-Protective Agents, Skin, Ultraviolet Rays, 02 Physical Sciences, 03 Chemical Sciences, 34 Chemical sciences, 51 Physical sciences

Abstract:

The sparsity of efficient commercial ultraviolet-A (UV-A) filters is a major challenge toward developing effective broadband sunscreens with minimal human- and eco-toxicity. To combat this, we have designed a new class of Meldrum-based phenolic UV-A filters. We explore the ultrafast photodynamics of coumaryl Meldrum, CMe, and sinapyl Meldrum (SMe), both in an industry-standard emollient and on a synthetic skin mimic, using femtosecond transient electronic and vibrational absorption spectroscopies and computational simulations. Upon photoexcitation to the lowest excited singlet state (S1), these Meldrum-based phenolics undergo fast and efficient nonradiative decay to repopulate the electronic ground state (S0). We propose an initial ultrafast twisted intramolecular charge-transfer mechanism as these systems evolve out of the Franck-Condon region toward an S1/S0 conical intersection, followed by internal conversion to S0 and subsequent vibrational cooling. Importantly, we correlate these findings to their long-term photostability upon irradiation with a solar simulator and conclude that these molecules surpass the basic requirements of an industry-standard UV filter.