From the Max Delbrueck Center for Molecular Medicine, 13125 Berlin, Germany.
Lipidomix GmbH, 13125 Berlin, Germany.
J Biol Chem. 2010 Oct 22;285(43):32720-32733. doi: 10.1074/jbc.M110.118406. Epub 2010 Aug 23.
Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) protect against cardiovascular disease by largely unknown mechanisms. We tested the hypothesis that EPA and DHA may compete with arachidonic acid (AA) for the conversion by cytochrome P450 (CYP) enzymes, resulting in the formation of alternative, physiologically active, metabolites. Renal and hepatic microsomes, as well as various CYP isoforms, displayed equal or elevated activities when metabolizing EPA or DHA instead of AA. CYP2C/2J isoforms converting AA to epoxyeicosatrienoic acids (EETs) preferentially epoxidized the ω-3 double bond and thereby produced 17,18-epoxyeicosatetraenoic (17,18-EEQ) and 19,20-epoxydocosapentaenoic acid (19,20-EDP) from EPA and DHA. We found that these ω-3 epoxides are highly active as antiarrhythmic agents, suppressing the Ca(2+)-induced increased rate of spontaneous beating of neonatal rat cardiomyocytes, at low nanomolar concentrations. CYP4A/4F isoforms ω-hydroxylating AA were less regioselective toward EPA and DHA, catalyzing predominantly ω- and ω minus 1 hydroxylation. Rats given dietary EPA/DHA supplementation exhibited substantial replacement of AA by EPA and DHA in membrane phospholipids in plasma, heart, kidney, liver, lung, and pancreas, with less pronounced changes in the brain. The changes in fatty acids were accompanied by concomitant changes in endogenous CYP metabolite profiles (e.g. altering the EET/EEQ/EDP ratio from 87:0:13 to 27:18:55 in the heart). These results demonstrate that CYP enzymes efficiently convert EPA and DHA to novel epoxy and hydroxy metabolites that could mediate some of the beneficial cardiovascular effects of dietary ω-3 fatty acids.
二十碳五烯酸 (EPA) 和二十二碳六烯酸 (DHA) 通过尚不清楚的机制来预防心血管疾病。我们检验了这样一个假说,即 EPA 和 DHA 可能与花生四烯酸 (AA) 竞争细胞色素 P450 (CYP) 酶的转化,从而形成替代的、具有生理活性的代谢物。肾脏和肝脏微粒体以及各种 CYP 同工酶在代谢 EPA 或 DHA 而不是 AA 时显示出相等或升高的活性。将 AA 转化为环氧化二十碳三烯酸 (EETs) 的 CYP2C/2J 同工酶优先环氧化 ω-3 双键,从而从 EPA 和 DHA 中产生 17,18-环氧二十碳四烯酸 (17,18-EEQ) 和 19,20-环氧二十二碳五烯酸 (19,20-EDP)。我们发现,这些 ω-3 环氧化物作为抗心律失常剂具有很高的活性,以低纳摩尔浓度抑制 Ca(2+)诱导的新生大鼠心肌细胞自发搏动率的增加。CYP4A/4F 同工酶 ω-羟基化 AA 对 EPA 和 DHA 的区域选择性较低,主要催化 ω-和 ω-1 羟基化。给予饮食补充 EPA/DHA 的大鼠在血浆、心脏、肾脏、肝脏、肺和胰腺的膜磷脂中,AA 被 EPA 和 DHA 大量替代,而大脑中的变化则不那么明显。脂肪酸的变化伴随着内源性 CYP 代谢物谱的同时变化(例如,在心脏中,将 EET/EEQ/EDP 比值从 87:0:13 改变为 27:18:55)。这些结果表明,CYP 酶有效地将 EPA 和 DHA 转化为新型的环氧和羟基代谢物,这些代谢物可能介导饮食 ω-3 脂肪酸的一些有益的心血管作用。