Research output: Contribution to journal › Article › peer-review
Photosensitized isomerization of resveratrol: Evaluation of energy and electron transfer pathways. / Neyra Recky, Jael R.; Gaspar Tosato, Maira; Буглак, Андрей Андреевич; Dantola, Laura; Lorente, Carolina.
In: Free Radical Biology and Medicine, Vol. 216, 01.04.2024, p. 50-59.Research output: Contribution to journal › Article › peer-review
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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 -
ID: 117103816