Identification of free radicals of glycerophosphatidylcholines containing ω-6 fatty acids using spin trapping coupled with tandem mass spectrometry

Identification of free radicals of glycerophosphatidylcholines containing ω-6 fatty acids using spin trapping coupled with tandem mass spectrometry
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使用自旋捕获和串联质谱法鉴定含有 ω-6 脂肪酸的甘油磷脂酰胆碱的自由基

DOI:
10.1080/10715760601118353
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发表时间:
2007
影响因子:
3.3
通讯作者:
M. Domingues
M. Domingues
中科院分区:
生物学3区
文献类型:
--
作者:
A. Reis;P. Domingues;A. Ferrer;M. Domingues

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研究了ω-6酰基多不饱和脂肪酸(PAPC,棕榈酰-花生四烯酰-甘油磷脂酰胆碱和PLPC,棕榈酰-亚麻酰-甘油磷脂酰胆碱)对二酰基甘油磷脂酰胆碱(GPC)的金属催化自由基氧化反应。自由基氧化产物用5,5-二甲基-1-吡咯烷-N-氧化物(DMPO)自旋捕集,电喷雾质谱(ES-MS)鉴定。含有一个和两个氧原子和一个和两个DMPO分子的氧化GPC的自旋加合物被观察到作为双电荷离子。通过串联质谱法(MS/MS)对这些离子进行结构表征,结果显示产物离子对应于酰基链(亚麻酰基或花生四烯酰基的sn-1-棕榈酰基和sn-2-氧化自旋加合物)的损失、自旋陷阱(DMPO)的损失和归因于氧化sn-2脂肪酸自旋加合物(亚麻酰基和花生四烯酰基)的产物离子。通过自旋阱附近的均裂和涉及sn-2脂肪酸自旋加合物中羟基的1,4氢消除裂解形成的产物离子可以推断自由基的性质。总之,GPC羟基烷基/DMPO和羟基烷氧基/DMPO自旋加合物的存在被提出。
Metal-catalysed radical oxidation of diacyl-glycerophosphatidylcholines (GPC) with ω-6 acyl polyunsaturated fatty acids (PAPC, palmitoyl-arachidonoyl-glycerophosphatidylcholine and PLPC, palmitoyl-lineloyl-glycerophosphatidylcholine) was studied. Free radical oxidation products were trapped by spin trapping with 5,5-dimethyl-1-pyrrolidine-N-oxide (DMPO) and identified by electrospray mass spectrometry (ES-MS). The spin adducts of oxidised GPC containing one and two oxygen atoms and one and two DMPO molecules were observed as doubly charged ions. Structural characterisation by tandem mass spectrometry (MS/MS) of these ions revealed product ions corresponding to loss of the acyl chains (sn-1-palmitoyl and sn-2-oxidised spin adduct of lineloyl or arachidonoyl), loss of the spin trap (DMPO) and product ions attributed to oxidised sn-2 fatty acid spin adduct (lineloyl and arachidonoyl). Product ions formed by homolytic cleavages near the spin trap and also from 1,4 hydrogen elimination cleavages involving the hydroxy group in the sn-2 fatty acid spin adduct allowed to infer the nature of the radical. Altogether, the presence of GPC hydroxy-alkyl/DMPO and hydroxy-alkoxyl/DMPO spin adducts was proposed.
DOI: 10.1089/152308604773934396
发表时间: 2004-07
影响因子: 6.6
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通讯作者: S. Venkataraman;Freya Q. Schafer;G. Buettner
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发表时间: 2000
影响因子: 3.6
作者:
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影响因子: 7.4
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