TY - JOUR

T1 - Photosensitized isomerization of resveratrol: Evaluation of energy and electron transfer pathways

AU - Neyra Recky, Jael R.

AU - Gaspar Tosato, Maira

AU - Буглак, Андрей Андреевич

AU - Dantola, Laura

AU - Lorente, Carolina

PY - 2024/4/1

Y1 - 2024/4/1

N2 - Resveratrol (3,5,4′-trihydroxystilbene) is a natural stilbene synthetized as trans-isomer in plants exposed to oxidative stress. In order to understand the mechanism involved during photosensitized degradation of trans-resveratrol, steady-state and time-resolved experiments were performed and compared with quantum-chemical calculations using density functional theory (DFT). Pterin (Ptr), a well-known photosensitizer, under UV-A radiation induces the oxidation of several biomolecules mainly through electron-transfer mechanisms. On the one hand, it was observed that trans-RSV participates in an energy-transfer pathway with 3Ptr* forming 3trans-RSV*, which dissipates the energy by isomerization to cis-RSV. On the other hand, RSV neutral radical (trans-RSV(-H)•) was detected in laser flash photolysis experiments, indicating an electron-transfer mechanism. The electron-transfer from 3Ptr* to trans-RSV is a barely feasible reaction, however, more favorable is the formation of trans-RSV(-H)• in a reaction between trans-RSV and Ptr radical cation (Ptr•+), which is produced during irradiation. The combination of experimental and theoretical approaches evidences the capability of trans-RSV to undergo energy-transfer (feasible by DFT calculations) and/or one-electron transfer pathways with Ptr triplet excited state. These findings reveal the mechanisms involved in the interaction of trans-RSV and pterin excited states and provide information on the antioxidant action of resveratrol during photosensitized oxidation of biomolecules.

AB - Resveratrol (3,5,4′-trihydroxystilbene) is a natural stilbene synthetized as trans-isomer in plants exposed to oxidative stress. In order to understand the mechanism involved during photosensitized degradation of trans-resveratrol, steady-state and time-resolved experiments were performed and compared with quantum-chemical calculations using density functional theory (DFT). Pterin (Ptr), a well-known photosensitizer, under UV-A radiation induces the oxidation of several biomolecules mainly through electron-transfer mechanisms. On the one hand, it was observed that trans-RSV participates in an energy-transfer pathway with 3Ptr* forming 3trans-RSV*, which dissipates the energy by isomerization to cis-RSV. On the other hand, RSV neutral radical (trans-RSV(-H)•) was detected in laser flash photolysis experiments, indicating an electron-transfer mechanism. The electron-transfer from 3Ptr* to trans-RSV is a barely feasible reaction, however, more favorable is the formation of trans-RSV(-H)• in a reaction between trans-RSV and Ptr radical cation (Ptr•+), which is produced during irradiation. The combination of experimental and theoretical approaches evidences the capability of trans-RSV to undergo energy-transfer (feasible by DFT calculations) and/or one-electron transfer pathways with Ptr triplet excited state. These findings reveal the mechanisms involved in the interaction of trans-RSV and pterin excited states and provide information on the antioxidant action of resveratrol during photosensitized oxidation of biomolecules.

UR - https://www.mendeley.com/catalogue/eb5f9c40-b614-3c1c-a246-b7567db0f0d3/

U2 - 10.1016/j.freeradbiomed.2024.01.038

DO - 10.1016/j.freeradbiomed.2024.01.038

M3 - Article

VL - 216

SP - 50

EP - 59

JO - Free Radical Biology and Medicine

JF - Free Radical Biology and Medicine

SN - 0891-5849

ER -