关键词: Cyclolinopeptide Flaxseed oil Methionine sulfoxide Tryptophan

Mesh : Tryptophan / chemistry Linseed Oil / chemistry gamma-Tocopherol / chemistry Oxidation-Reduction Antioxidants / chemistry Tandem Mass Spectrometry Flax / chemistry

来  源:   DOI:10.1016/j.foodchem.2024.139026

Abstract:
Linusorbs (LOs), significantly influence oil quality and sensory properties of flaxseed oil. Trp-containing LOs exhibit distinct oxidative behavior when γ-tocopherol (γ-T) is present. Polar fractions of crude flaxseed oil were stripped via silica absorption, and reintroduced (LO and γ-T) separately into the oil matrix to investigate their interaction during storage. Compared with crude oil, LOs account for 18.49% reduction of p-anisidine value, while LOs with γ-T contributed to most of the endogenous antioxidant effect in crude oil. γ-T was found to suppress oxidation of Trp-containing LO at early stage (Met form), while facilitate oxidation while at their mid-stage (MetO form, Methionine sulfoxide). In vitro oxidation shows that CLD more likely cleaved into peptide fragments, while few products retain intact ring structures. LC-MS/MS analysis and silicon simulation revealed proximity between MetO and Trp residues, facilitating inter- or intra-molecular reactions and ring structure rupture. Remarkably, the presence of γ-T facilitate these phenomena.
摘要:
Linusorbs(LO),影响亚麻籽油的油脂品质和感官特性。当存在γ-生育酚(γ-T)时,含Trp的LO表现出明显的氧化行为。通过二氧化硅吸收汽提粗亚麻籽油的极性馏分,并将(LO和γ-T)分别重新引入油基质中,以研究它们在储存过程中的相互作用。与原油相比,LOs占对茴香胺值减少18.49%,而具有γ-T的LOs贡献了原油中大部分的内源性抗氧化作用。发现γ-T在早期抑制含Trp的LO的氧化(Met形式),同时在中期促进氧化(MetO形式,甲硫氨酸亚砜)。体外氧化表明,CLD更有可能被切割成肽片段,而很少有产品保留完整的环结构。LC-MS/MS分析和硅模拟揭示了MetO和Trp残基之间的接近,促进分子间或分子内反应和环结构破裂。值得注意的是,γ-T的存在促进了这些现象。
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