AIMMS-Division of Molecular Toxicology, Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit , De Boelelaan 1108, 1081 HZ Amsterdam, The Netherlands.
Chem Res Toxicol. 2018 Feb 19;31(2):116-126. doi: 10.1021/acs.chemrestox.7b00289. Epub 2018 Jan 11.
Detoxicating enzymes NAD(P)H:quinone oxidoreductase 1 (NQO1) and NRH:quinone oxidoreductase 2 (NQO2) catalyze the two-electron reduction of quinone-like compounds. The protective role of the polymorphic NQO1 and NQO2 enzymes is especially of interest in the liver as the major site of drug bioactivation to chemically reactive drug metabolites. In the current study, we quantified the concentrations of NQO1 and NQO2 in 20 human liver donors and NQO1 and NQO2 activities with quinone-like drug metabolites. Hepatic NQO1 concentrations ranged from 8 to 213 nM. Using recombinant NQO1, we showed that low nM concentrations of NQO1 are sufficient to reduce synthetic amodiaquine and carbamazepine quinone-like metabolites in vitro. Hepatic NQO2 concentrations ranged from 2 to 31 μM. NQO2 catalyzed the reduction of quinone-like metabolites derived from acetaminophen, clozapine, 4'-hydroxydiclofenac, mefenamic acid, amodiaquine, and carbamazepine. The reduction of the clozapine nitrenium ion supports association studies showing that NQO2 is a genetic risk factor for clozapine-induced agranulocytosis. The 5-hydroxydiclofenac quinone imine, which was previously shown to be reduced by NQO1, was not reduced by NQO2. Tacrine was identified as a potent NQO2 inhibitor and was applied to further confirm the catalytic activity of NQO2 in these assays. While the in vivo relevance of NQO2-catalyzed reduction of quinone-like metabolites remains to be established by identification of the physiologically relevant co-substrates, our results suggest an additional protective role of the NQO2 protein by non-enzymatic scavenging of quinone-like metabolites. Hepatic NQO1 activity in detoxication of quinone-like metabolites becomes especially important when other detoxication pathways are exhausted and NQO1 levels are induced.
解毒酶 NAD(P)H:醌氧化还原酶 1 (NQO1) 和 NRH:醌氧化还原酶 2 (NQO2) 催化醌类似物的两电子还原。多态 NQO1 和 NQO2 酶的保护作用在肝脏中尤为重要,因为肝脏是药物生物活化产生化学活性药物代谢物的主要部位。在目前的研究中,我们定量测定了 20 名人类肝供体中 NQO1 和 NQO2 的浓度,并测定了醌类似物药物代谢物的 NQO1 和 NQO2 活性。肝 NQO1 浓度范围为 8 至 213 nM。使用重组 NQO1,我们表明,低 nM 浓度的 NQO1 足以在体外还原合成的氨苯砜和卡马西平醌类似物代谢物。肝 NQO2 浓度范围为 2 至 31 μM。NQO2 催化了来自对乙酰氨基酚、氯氮平、4'-羟基双氯芬酸、甲芬那酸、氨苯砜和卡马西平的醌类似物代谢物的还原。氯氮平亚硝鎓离子的还原支持关联研究表明,NQO2 是氯氮平引起的粒细胞缺乏症的遗传危险因素。先前表明被 NQO1 还原的 5-羟基双氯芬酸醌亚胺,未被 NQO2 还原。他克林被鉴定为一种有效的 NQO2 抑制剂,并被应用于进一步确认 NQO2 在这些测定中的催化活性。虽然 NQO2 催化的醌类似物代谢物还原的体内相关性仍需通过鉴定生理相关的辅酶来确定,但我们的结果表明 NQO2 蛋白通过非酶促清除醌类似物而发挥额外的保护作用。当其他解毒途径耗尽且 NQO1 水平被诱导时,肝 NQO1 对醌类似物代谢物的解毒活性变得尤为重要。