Tandem mass spectrometry for sequencing proanthocyanidins
Tandem mass spectrometry for sequencing proanthocyanidins
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DOI：
10.1021/ac061823v
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发表时间：
2007-02-15
影响因子：
7.4
通讯作者：
Deinzer, Max L.
中科院分区：
文献类型：
--
作者：
Li, Hui-Jing;Deinzer, Max L.
原花青素（PAs）是一类以儿茶素单体为基础的生物类黄酮低聚物。这些多酚类化合物广泛存在于高等植物中，是人类饮食的重要组成部分。本文描述了一种在正离子模式下对这些普遍存在且非常有益的抗氧化剂进行测序的灵敏LC-串联质谱（LC/ESI-MSn）方法。A型和b型PAs的羟基化模式和类黄酮间链由来自逆转录diels - alder （RDA）裂变、杂环裂变（HRF）、本文首次描述的新型苯并呋喃形成（BFF）裂变和醌类甲基（QM）裂变的片段离子确定。通过HRF/RDA裂变、HRF/BFF裂变、RDA/HRF裂变和QM裂变产生的诊断离子确定PAs的亚基序列。用新建立的串联质谱法对26个PAs进行了可靠的测序。结果表明，基于这些不同碎片模式组合的协议允许唯一地识别PA低聚物。
Proanthocyanidins (PAs) are a group of bioflavonoids consisting of oligomers based on catechin monomeric units. These polyphenolic compounds are widely distributed in higher plants and are an integral part of the human diet. A sensitive LC-tandem mass spectrometric (LC/ESI-MSn) method in the positive ion mode for sequencing these ubiquitous and highly beneficial antioxidants is described. The hydroxylation patterns and interflavanoid linkage for A- and B-type PAs were determined by fragment ions derived from a retro-Diels-Alder (RDA) fission, heterocyclic ring fission (HRF), a novel benzofuran-forming (BFF) fission described here for the first time, and a quinone methide (QM) fission. The subunit sequence of the PAs was determined by diagnostic ions derived from HRF/RDA fission, HRF/BFF fission, and RDA/HRF fission together with QM fission. A total of 26 PAs were reliably sequenced by the newly established tandem mass spectrometric protocol. It is shown that the protocol based on a combination of these different fragmentation patterns allows for uniquely identifying PA oligomers.