Merck Frosst Centre for Therapeutic Research, Kirkland, Quebec, Canada.
J Biol Chem. 2011 Aug 26;286(34):29575-83. doi: 10.1074/jbc.M111.268235. Epub 2011 Jul 7.
The rapid emergence and the prevalence of resistance mutations in HIV-1 reverse transcriptase (RT) underscore the need to identify RT inhibitors with novel binding modes and mechanisms of inhibition. Recently, two structurally distinct inhibitors, phosphonoformic acid (foscarnet) and INDOPY-1 were shown to disrupt the translocational equilibrium of RT during polymerization through trapping of the enzyme in the pre- and the post-translocation states, respectively. Here, we show that foscarnet and INDOPY-1 additionally display a shared novel inhibitory preference with respect to substrate primer identity. In RT-catalyzed reactions using RNA-primed substrates, translocation inhibitors were markedly less potent at blocking DNA polymerization than in equivalent DNA-primed assays; i.e. the inverse pattern observed with marketed non-nucleoside inhibitors that bind the allosteric pocket of RT. This potency profile was shown to correspond with reduced binding on RNA·DNA primer/template substrates versus DNA·DNA substrates. Furthermore, using site-specific footprinting with chimeric RNA·DNA primers, we demonstrate that the negative impact of the RNA primer on translocation inhibitor potency is overcome after 18 deoxyribonucleotide incorporations, where RT transitions primarily into polymerization-competent binding mode. In addition to providing a simple means to identify similarly acting translocation inhibitors, these findings suggest a broader role for the primer-influenced binding mode on RT translocation equilibrium and inhibitor sensitivity.
HIV-1 逆转录酶(RT)的快速出现和耐药突变的流行强调了识别具有新型结合模式和抑制机制的 RT 抑制剂的必要性。最近,两种结构上不同的抑制剂膦甲酸(磷甲酸)和 INDOPY-1 被证明分别通过将酶分别捕获在易位前和易位后状态来破坏 RT 在聚合过程中的易位平衡。在这里,我们表明,膦甲酸和 INDOPY-1 还表现出与底物引物身份相关的共同新型抑制偏好。在使用 RNA 起始底物的 RT 催化反应中,与等效的 DNA 起始测定相比,易位抑制剂在阻止 DNA 聚合方面的效力明显降低;即与结合 RT 变构口袋的市售非核苷抑制剂观察到的相反模式。该效价谱与 RNA·DNA 引物/模板底物与 DNA·DNA 底物相比,结合减少相对应。此外,使用具有嵌合 RNA·DNA 引物的定点足迹法,我们证明在 18 个脱氧核苷酸掺入后,RNA 引物对易位抑制剂效力的负面影响被克服,此时 RT 主要过渡到聚合能力结合模式。除了提供一种识别具有类似作用的易位抑制剂的简单方法外,这些发现还表明引物影响的结合模式对 RT 易位平衡和抑制剂敏感性具有更广泛的作用。