Department of Pharmaceutical Chemistry, University of California , San Francisco, California 94158-2280, United States.
Biochemistry. 2014 Jul 22;53(28):4648-60. doi: 10.1021/bi5003234. Epub 2014 Jul 11.
Herpesviruses rely on a homodimeric protease for viral capsid maturation. A small molecule, DD2, previously shown to disrupt dimerization of Kaposi's sarcoma-associated herpesvirus protease (KSHV Pr) by trapping an inactive monomeric conformation and two analogues generated through carboxylate bioisosteric replacement (compounds 2 and 3) were shown to inhibit the associated proteases of all three human herpesvirus (HHV) subfamilies (α, β, and γ). Inhibition data reveal that compound 2 has potency comparable to or better than that of DD2 against the tested proteases. Nuclear magnetic resonance spectroscopy and a new application of the kinetic analysis developed by Zhang and Poorman [Zhang, Z. Y., Poorman, R. A., et al. (1991) J. Biol. Chem. 266, 15591-15594] show DD2, compound 2, and compound 3 inhibit HHV proteases by dimer disruption. All three compounds bind the dimer interface of other HHV proteases in a manner analogous to binding of DD2 to KSHV protease. The determination and analysis of cocrystal structures of both analogues with the KSHV Pr monomer verify and elaborate on the mode of binding for this chemical scaffold, explaining a newly observed critical structure-activity relationship. These results reveal a prototypical chemical scaffold for broad-spectrum allosteric inhibition of human herpesvirus proteases and an approach for the identification of small molecules that allosterically regulate protein activity by targeting protein-protein interactions.
疱疹病毒依赖同源二聚体蛋白酶进行病毒衣壳成熟。一种小分子化合物 DD2 先前被证明可以通过捕获无活性的单体构象来破坏卡波西肉瘤相关疱疹病毒蛋白酶(KSHV Pr)的二聚化,并且通过羧酸生物等排替换生成的两种类似物(化合物 2 和 3)被证明可以抑制所有三种人类疱疹病毒(HHV)亚科(α、β和γ)的相关蛋白酶。抑制数据表明,化合物 2 对测试蛋白酶的活性与 DD2 相当,甚至优于 DD2。核磁共振波谱和张和波曼(Zhang 和 Poorman)开发的动力学分析的新应用[Zhang,Z.Y.,Poorman,R.A.,等人。(1991)J. Biol. Chem. 266,15591-15594]表明,DD2、化合物 2 和化合物 3 通过二聚体破坏抑制 HHV 蛋白酶。这三种化合物都以类似于 DD2 与 KSHV 蛋白酶结合的方式结合其他 HHV 蛋白酶的二聚体界面。与 KSHV Pr 单体的两种类似物的共结晶结构的测定和分析验证并详细阐述了这种化学支架的结合模式,解释了一个新观察到的关键结构-活性关系。这些结果揭示了广谱变构抑制人类疱疹病毒蛋白酶的典型化学支架,以及一种通过靶向蛋白质-蛋白质相互作用来变构调节蛋白质活性的小分子的识别方法。