Singlet Oxygen Quenching by Resveratrol Derivatives †
Singlet Oxygen Quenching by Resveratrol Derivatives †
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DOI：
10.1111/php.13704
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发表时间：
2022-08
影响因子：
3.3
通讯作者：
Charlotte G Monsour;Abegail B Tadle;Bliss J Tafolla-Aguirre;Nidhi Lakshmanan;Jin Hyeok Yoon;Rhemrose B Sabio;M. Selke
中科院分区：
文献类型：
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作者：
Charlotte G Monsour;Abegail B Tadle;Bliss J Tafolla-Aguirre;Nidhi Lakshmanan;Jin Hyeok Yoon;Rhemrose B Sabio;M. Selke
我们研究了反式白藜芦醇的几种衍生物的单线态氧淬灭能力，这些衍生物已被报道具有显着的抗氧化能力，包括光保护活性。我们测量了甲基化的白藜芦醇衍生物1，3-二甲氧基-5-[（E）-2-（4-甲氧基苯基）乙烯基]苯和部分甲基化的白藜芦醇衍生物4-（（E）-2-（3，5-二甲氧基苯基）乙烯基）苯酚（紫檀芪）、5-[（E）-2-（4-甲氧基苯基）乙烯基]苯-1，3-二醇和（2 R，3R）-3，5，7-三羟基-2-（3，4，5-三羟基苯基）-2，3-二氢苯并吡喃-4-酮（二氢杨梅素）。质子溶剂系统导致较高的kT值，除了完全甲基化的衍生物。我们还研究了反式白藜芦醇直接作为光敏剂（而不是通过其他初级光化学反应产生的次级光产物）产生单线态氧的能力，但发现白藜芦醇及其任何衍生物都不能这样做。然后，我们研究了甲基化衍生物与单线态氧的化学反应。主要途径由涉及反式双键和帕拉取代苯环的[4 + 2]环加成反应组成，类似于反式白藜芦醇的观察结果。与反式白藜芦醇不同，初级单线态氧产物与单线态氧进行第二次[4 + 2]环加成，导致形成双内过氧化物。反式白藜芦醇和甲基化衍生物的第二种反应途径导致通过瞬时二氧杂环丁烷的裂解形成醛。
We investigated the singlet oxygen quenching ability of several derivatives of trans‐resveratrol which have been reported to have significant antioxidant ability, including photoprotective activity. We measured the total rate constants of singlet oxygen removal (kT) by the methylated resveratrol derivative 1,3‐dimethoxy‐5‐[(E)‐2‐(4‐methoxyphenyl)ethenyl]benzene, and the partially methylated resveratrol derivatives 4‐((E)‐2‐(3,5‐dimethoxyphenyl)ethenyl)phenol (pterostilbene), 5‐[(E)‐2‐(4‐methoxyphenyl)ethenyl]benzene‐1,3‐diol and (2R,3R)‐3,5,7‐trihydroxy‐2‐(3,4,5‐trihydroxyphenyl)‐2,3‐dihydrochromen‐4‐one (dihydromyricetin). A protic solvent system results in higher kT values, except for the completely methylated derivative. We also investigated the ability of trans‐resveratrol to directly act as a photosensitizer (rather than via secondary photoproducts resulting from other primary photochemical reactions) for the production of singlet oxygen but found that neither resveratrol nor any of its derivatives are able to do so. We then studied the chemical reactions of the methylated derivative with singlet oxygen. The main pathway consists of a [4 + 2] cycloaddition reaction involving the trans‐double bond and the para‐substituted benzene ring similar to what has been observed for trans‐resveratrol. Unlike trans‐resveratrol, the primary singlet oxygen product undergoes a second [4 + 2] cycloaddition with singlet oxygen leading to the formation of diendoperoxides. A second reactivity pathway for both trans‐resveratrol and the methylated derivative leads to the formation of aldehydes via cleavage of a transient dioxetane.