Basic Courses Department, Tianjin Sino-German University of Applied Sciences, Tianjin 300350, China.
Department of Minimally Invasive Esophagus Surgery, Tianjin's Clinical Research Center for Cancer, National Clinical Research Center of Cancer, Tianjin Medical University Cancer Institute and Hospital, Key Laboratory of Cancer Prevention and Therapy, Tianjin, 300060, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2025 Feb 5;326:125287. doi: 10.1016/j.saa.2024.125287. Epub 2024 Oct 19.
The development and enhancement of antioxidant drugs, which are aimed at mitigating DNA damage, mutations, and cancer, are of paramount significance in the biomedical sphere. In recent years, antioxidant drug molecules with photoluminescence have sprung up like mushrooms. Apigenin (AP), characterized by its distinctive property of excited state intramolecular proton transfer (ESIPT), plays a pivotal role in mediating antioxidant and anticancer activities. Despite being a representative molecule of the non-existent enol form (E*) state with ESIPT nature, there is a notable lack of theoretical investigations into its antioxidant properties. Herein, density functional theory (DFT) and time-dependent DFT methodologies were utilized to explore the effects of various functional groups on AP molecules in a methanol solvent. Studies have demonstrated that for the non-existent E* state fluorescence molecule AP, the ESIPT process can significantly enhance the antioxidant potency of AP and its derivatives. However, the introduction of electron-withdrawing groups significantly accelerated the ESIPT process while simultaneously suppressing the antioxidant activity of AP-CN. Conversely, the incorporation of electron-donating groups effectively inhibited the ESIPT process, yet markedly enhanced the antioxidant activity of AP-NH. This investigation furnishes vital perspectives and sources of reference for the conception and advancement of groundbreaking antioxidant medications that aim to tackle non-existent E* state molecules.
抗氧化药物的开发和增强对于生物医学领域至关重要，旨在减轻 DNA 损伤、突变和癌症。近年来，具有光致发光的抗氧化药物分子如雨后春笋般涌现。芹菜素 (AP) 具有独特的激发态分子内质子转移 (ESIPT) 性质，在介导抗氧化和抗癌活性方面发挥着关键作用。尽管它是具有 ESIPT 性质的不存在烯醇形式 (E*) 状态的代表性分子，但对其抗氧化性质的理论研究却明显不足。在此，我们采用密度泛函理论 (DFT) 和含时密度泛函理论 (TD-DFT) 方法研究了在甲醇溶剂中各种官能团对 AP 分子的影响。研究表明，对于不存在 E* 状态荧光分子 AP，ESIPT 过程可以显著增强 AP 及其衍生物的抗氧化能力。然而，引入吸电子基团会显著加速 ESIPT 过程，同时抑制 AP-CN 的抗氧化活性。相反，引入供电子基团可以有效抑制 ESIPT 过程，但显著增强 AP-NH 的抗氧化活性。这项研究为设计和开发旨在解决不存在 E* 状态分子的开创性抗氧化药物提供了重要的视角和参考来源。
