College of Science, Northeast Forestry University, Harbin 150040, China.
College of Chemistry, Chemical Engineering and Resource Utilization, Northeast Forestry University, Harbin 150040, China; Key Laboratory of Forest Plant Ecology, Ministry of Education, Northeast Forestry University, Harbin 150040, China; Heilongjiang Provincial Key Laboratory of Ecological Utilization of Forestry-Based Active Substances, Northeast Forestry University, Harbin 150040, China.
J Photochem Photobiol B. 2024 Sep;258:112996. doi: 10.1016/j.jphotobiol.2024.112996. Epub 2024 Jul 31.
Exploring antioxidant potential of flavonoid derivatives after ESIPT process provides a theoretical basis for discovering compounds with higher antioxidant capacity. In this work, employing the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods, the antioxidant potential of two citrus-derived naringenin flavonoids after ESIPT process is explored. Based on studies of ESIPT process including IMHB intensity variations, potential energy curves, and transition state, these molecules exist only in enol and keto forms due to ultra-fast ESIPT. The HOMOs are utilized to explore electron-donating capacity, demonstrating that the molecules in keto form is stronger than that in enol form. Furthermore, the atomic dipole moment corrected Hirshfeld population (ADCH) and Fukui functions indicate that the sites attacked by the electrophilic free radical of the two molecules in the keto form are O and O respectively, and both are more active than in the enol form. Overall, a comprehensive consideration of the ESIPT process and antioxidant potential of flavonoid derivatives will facilitate the exploration and design of substances with higher antioxidant capacity.
探索 ESIPT 过程后黄酮衍生物的抗氧化潜力为发现具有更高抗氧化能力的化合物提供了理论依据。在这项工作中，采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）方法，研究了 ESIPT 过程后两种柑橘衍生的柚皮素类黄酮的抗氧化潜力。基于对 ESIPT 过程的研究，包括 IMHB 强度变化、势能曲线和过渡态，这些分子由于超快 ESIPT 仅以烯醇和酮形式存在。利用 HOMO 来探索供电子能力，表明酮式分子比烯醇式分子更强。此外，原子偶极矩校正的 Hirshfeld 布居（ADCH）和 Fukui 函数表明，两种分子在酮式中，亲电自由基攻击的位点分别为 O 和 O，且均比烯醇式更活跃。总的来说，全面考虑黄酮衍生物的 ESIPT 过程和抗氧化潜力将有助于探索和设计具有更高抗氧化能力的物质。
