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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Free-Radical-Initiated Phospholipid Oxidations at the Air–Water Interface: The Oxidation of Unsaturated and Saturated Fatty Acid Chains
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Free-Radical-Initiated Phospholipid Oxidations at the Air–Water Interface: The Oxidation of Unsaturated and Saturated Fatty Acid Chains

机译：空气 - 水界面的自由基引发的磷脂氧化：不饱和饱和脂肪酸链的氧化

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Lipid oxidations initiated by free radicals are usually considered to undergo peroxidation, a chain process starting with hydrogen abstraction by an initiator, followed by O_(2) uptake. While this peroxidation mechanism is widely accepted and sometimes taken for granted, here we provide evidence of the oxidation of both of the unsaturated and saturated fatty acid chains in phospholipids initiated by photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TMDPO) at the air–water interface, and no peroxidation products are observed in these reactions. A unique field-induced droplet ionization mass spectrometry (FIDI-MS) methodology which is capable of the selective online sampling of monolayers of molecules that reside at the air–water interface is employed to detect the products. We have shown that the double bonds on the oleyl chains of the lipids are first oxidized into epoxides, after which other saturated carbon atoms are oxidized into carbonyl groups. We anticipate that this work will draw more attention to the complexity of the lipid oxidation chemistry initiated by free radicals.
机译：由自由基引发的脂质氧化通常被认为是经历过氧化作用，这是一个链过程，从引发剂提取氢开始，然后吸收O_2。虽然这种过氧化机制被广泛接受，有时被认为是理所当然的，但我们在这里提供了证据，证明了由光引发剂2,4,6-三甲基苯甲酰二苯基氧膦（TMDPO）在空气-水界面引发的磷脂中的不饱和和饱和脂肪酸链的氧化，并且在这些反应中未观察到过氧化产物。采用一种独特的场致液滴电离质谱（FIDI-MS）方法来检测产物，该方法能够对驻留在空气-水界面的分子单层进行选择性在线采样。我们已经证明，脂类油基链上的双键首先被氧化成环氧化物，然后其他饱和碳原子被氧化成羰基。我们预计这项工作将引起人们对自由基引发的脂质氧化化学的复杂性的更多关注。

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