Schmidt Dawn M Z, McCafferty Dewey G
Department of Chemistry, B120 Levine Science Research Center, Box 90317, Duke University, Durham, North Carolina 27708, USA.
Biochemistry. 2007 Apr 10;46(14):4408-16. doi: 10.1021/bi0618621. Epub 2007 Mar 17.
The catalytic domain of the flavin-dependent human histone demethylase lysine-specific demethylase 1 (LSD1) belongs to the family of amine oxidases including polyamine oxidase and monoamine oxidase (MAO). We previously assessed monoamine oxidase inhibitors (MAOIs) for their ability to inhibit the reaction catalyzed by LSD1 [Lee, M. G., et al. (2006) Chem. Biol. 13, 563-567], demonstrating that trans-2-phenylcyclopropylamine (2-PCPA, tranylcypromine, Parnate) was the most potent with respect to LSD1. Here we show that 2-PCPA is a time-dependent, mechanism-based irreversible inhibitor of LSD1 with a KI of 242 microM and a kinact of 0.0106 s-1. 2-PCPA shows limited selectivity for human MAOs versus LSD1, with kinact/KI values only 16-fold and 2.4-fold higher for MAO B and MAO A, respectively. Profiles of LSD1 activity and inactivation by 2-PCPA as a function of pH are consistent with a mechanism of inactivation dependent upon enzyme catalysis. Mass spectrometry supports a role for FAD as the site of covalent modification by 2-PCPA. These results will provide a foundation for the design of cyclopropylamine-based inhibitors that are selective for LSD1 to probe its role in vivo.
黄素依赖性人组蛋白去甲基化酶赖氨酸特异性去甲基化酶1(LSD1)的催化结构域属于胺氧化酶家族,包括多胺氧化酶和单胺氧化酶(MAO)。我们之前评估了单胺氧化酶抑制剂(MAOIs)抑制LSD1催化反应的能力[Lee, M. G., 等人(2006年)《化学生物学》13, 563 - 567],证明反式-2-苯基环丙胺(2-PCPA,反苯环丙胺,帕罗西汀)对LSD1的抑制作用最强。在此我们表明,2-PCPA是LSD1的一种时间依赖性、基于机制的不可逆抑制剂,其抑制常数(KI)为242微摩尔,失活速率常数(kinact)为0.0106 s⁻¹。2-PCPA对人MAO与LSD1的选择性有限,对MAO B和MAO A的kinact/KI值分别仅高16倍和2.4倍。2-PCPA导致LSD1活性丧失和失活的情况随pH值变化的曲线与依赖酶催化的失活机制一致。质谱分析支持黄素腺嘌呤二核苷酸(FAD)作为2-PCPA共价修饰位点的作用。这些结果将为设计对LSD1具有选择性的基于环丙胺的抑制剂以探究其在体内的作用奠定基础。