Intrinsic Nature of the Ultrafast Deexcitation Pathway of Mycosporine-like Amino Acid Porphyra-334

Porphyra-334 is a member of natural UV-screening compounds named mycosporine-like amino acids found in several marine organisms. The UV excited porphyra-334 has been identified to deexcite quickly by puckering the intramolecular cyclohexenimine ring; however, the reason for such a ring-puckering occurrence is yet unclear. In this study, we show the ring-puckering to be the relaxation pathway of the UV excited pi electron which shifts from the in-ring bond to the out-of-ring bond. The ring-puckering is characterized by the torsion among the in-ring and out-of ring bonds. Since the pi electron shift is possible in two different directions at the Franck-Condon UV excited state, it enables two ring-puckering pathways: the previously reported pathway and another one newly identified at present. We also examine the ring-unpuckering pathways which are an analogy of cis/trans photoisomerization, and we find them to be not suited for the pi electron shift character of the UV excited state and thus not related to the deexcitation pathway. The present study provides insight into how porphyra-334 exerts the UV-screening ability based on its cyclohexenimine ring structure.