Generation and esterification of electrophilic fatty acid nitroalkenes in triacylglycerides
Generation and esterification of electrophilic fatty acid nitroalkenes in triacylglycerides
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DOI：
10.1016/j.freeradbiomed.2015.05.033
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发表时间：
2015-10-01
影响因子：
7.4
通讯作者：
Schopfer, Francisco J.
中科院分区：
文献类型：
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作者：
Fazzari, Marco;Khoo, Nicholas;Schopfer, Francisco J.
亲电脂肪酸硝基烯（NO2-EA）是一氧化氮和亚硝酸盐介导的不饱和脂肪酸硝化反应的产物。在细胞和动物模型中，这些亲电产物诱导调节代谢和炎症反应的多效信号传导作用。NO2-FA的代谢包括通过前列腺素还原酶-1、线粒体β -氧化和低分子量亲核氨基酸的Michael加成来还原乙烯基硝基部分。脂肪酸硝基烯烃的复杂脂质反应还没有很好的定义。本文报道了基于质谱的方法检测和表征含no2 - fa -三酰基甘油酯（NO2-FA-TAG）。因此，日粮甘油三酯中的不饱和脂肪酸是胃酸化过程中硝化反应的靶点，口服硝基油酸（NO2-OA）后，大鼠血浆中可检测到NO2-FA-TAG。此外，这些物种的特征和特征，包括β氧化和脱氢产物的产生，可以在no2 - oa补充的脂肪细胞中检测到。这些数据表明，NO2-FA-TAG，由酯化不饱和脂肪酸的直接硝化或将硝化的游离脂肪酸并入三酰基甘油酯中形成，有助于这些反应性亲电介质的全身分布，并可能作为脂肪酶随后动员的储存库，进而影响脂肪细胞稳态和组织信号事件。(C) 2015爱思唯尔公司版权所有。
Electrophilic fatty acid nitroalkenes (NO2-EA) are products of nitric oxide and nitrite-mediated unsaturated fatty acid nitration. These electrophilic products induce pleiotropic signaling actions that modulate metabolic and inflammatory responses in cell and animal models. The metabolism of NO2-FA includes reduction of the vinyl nitro moiety by prostaglandin reductase-1, mitochondrial beta-oxidation, and Michael addition with low molecular weight nucleophilic amino acids. Complex lipid reactions of fatty acid nitroalkenes are not well defined. Herein we report the detection and characterization of NO2-FA-containing triacylglycerides (NO2-FA-TAG) via mass spectrometry-based methods. In this regard, unsaturated fatty acids of dietary triacylglycerides are targets for nitration reactions during gastric acidification, where NO2-FA-TAG can be detected in rat plasma after oral administration of nitro-oleic acid (NO2-OA). Furthermore, the characterization and profiling of these species, including the generation of beta oxidation and dehydrogenation products, could be detected in NO2-OA-supplemented adipocytes. These data revealed that NO2-FA-TAG, formed by either the direct nitration of esterified unsaturated fatty acids or the incorporation of nitrated free fatty acids into triacylglycerides, contribute to the systemic distribution of these reactive electrophilic mediators and may serve as a depot for subsequent mobilization by lipases to in turn impact adipocyte homeostasis and tissue signaling events. (C) 2015 Elsevier Inc. All rights reserved.