Sunscreens are aimed at protecting skin from solar ultraviolet (UV) irradiation. By utilizing femtosecond transient absorption spectroscopy and time-dependent density functional theory, we explain nature's selection of sinapoyl malate rather than sinapic acid as the plant sunscreen molecule. In physiological pH conditions, the two molecules are deprotonated, and their excited ππ* states are found to relax to the ground states in a few tens of picoseconds via a barrierless trans-cis photoisomerization. After the cis-photoproduct is formed, the efficacy of sinapic acid is greatly reduced. In contrast, the efficacy of sinapoyl malate is affected only slightly because the cis-product still absorbs UV light strongly. In addition, protonated sinapic acid is found to be a good potential sunscreen molecule.

A great deal of thermally instable cis form photoisomerization products will be formed from the thermally stable trans form of the plant sunscreens sinapate esters upon ultraviolet radiation. To reveal the photoisomerization mechanism of the cis-isomer, we explore the photodynamics of a model plant sunscreen methyl sinapate (MS) in the cis form in organic solution. The high photoisomerization quantum yield of the cis-isomer results in the relatively higher photostability of trans-MS. By utilizing femtosecond transient absorption spectroscopy and quantum chemical calculation, we propose that an adiabatic relaxation competes with nonadiabatic relaxation for the excited-state cis form of methyl sinapate. These results suggest that the photoprotection mechanism of the cis form of sinapate esters is significantly different from that of the trans form of sinapate esters and plays an important role in the overall photoprotection effect.