UHPLC-ESI-MS 研究白藜芦醇二聚体异构体和类似物选择性猝灭单线态氧的机制。
Mechanism of isomers and analogues of resveratrol dimers selectively quenching singlet oxygen by UHPLC-ESI-MS.
机构信息
College of Food Engineering and Nutritional Science, Shaanxi Normal University, Xi'an 710062, China; Shaanxi Engineering Laboratory for Food Green Processing and Safety Control, Xi'an 710062, China.
College of Food Engineering and Nutritional Science, Shaanxi Normal University, Xi'an 710062, China.
出版信息
Food Chem. 2017 Dec 15;237:1101-1111. doi: 10.1016/j.foodchem.2017.06.021. Epub 2017 Jun 15.
Stilbenoids, in particular, resveratrol and its dimers are abundantly present in Vitis vinifera and proved to be quenchers with selective singlet oxygen. However, only a few mechanisms are reported for their complex molecular architectures. Hence, UHPLC combined with accurate MS is employed to investigate the photo-radiation mechanism of resveratrol dimers systematically. Ⅰ: Resorcinol ring exists in Scirpusin A 1, Trans-ε-viniferin 2 and Trans-σ-viniferin 3. The photochemical products were 14Da or 16Da higher than reagents and underwent an endoperoxide intermediate to quinones; Ⅱ: [2+2] cyclization of intra-molecular trans-double bond. The products were 18Da greater than substrates thereby cycloaddited to oxygen heterocyclic; Ⅲ : [4+1], [4+2] cyclization of oxetane formed products were 28Da and 44Da higher than 3, 2 and 1. Ⅳ : 5-phenol-2,3-dihydrobenzofuran ring exists in 2 been oxidized, causing the products at 16Da, 32Da higher than 2. This is the first to reveal the generally regular mechanism of stilbenoids quenching singlet oxygen.
芪类物质，特别是白藜芦醇及其二聚体，在葡萄属植物中大量存在，被证明是具有选择性单重态氧猝灭剂。然而，对于其复杂的分子结构，仅有少数机制被报道。因此，采用超高效液相色谱法结合精确质量质谱法，系统地研究了白藜芦醇二聚体的光辐射机制。Ⅰ：Scirpusin A 1、反式-ε-viniferin 2 和反式-σ-viniferin 3 中存在间苯二酚环。光化学反应产物比试剂高 14Da 或 16Da，并经历过环氧化物中间体到醌；Ⅱ：分子内反式双键的[2+2]环化。产物比底物高 18Da，因此与氧杂环发生环加成；Ⅲ：氧杂环丁烷的[4+1]、[4+2]环化形成的产物比 3、2 和 1 分别高 28Da 和 44Da；Ⅳ：2 中的 5-苯并二氢呋喃环被氧化，导致产物比 2 高 16Da 和 32Da。这是首次揭示芪类物质猝灭单线态氧的普遍规律机制。
Zotero 插件