Bailey Lauren D, Kalyana Sundaram Ramalingam Venkat, Li Huiyuan, Duffy Caitlin, Aneja Rachna, Rosemary Bastian Arangassery, Holmes Andrew P, Kamanna Kantharaju, Rashad Adel A, Chaiken Irwin
Department of Biochemistry and Molecular Biology, Drexel University College of Medicine , Philadelphia, Pennsylvania 19102, United States.
School of Biomedical Engineering, Science and Health Systems, Drexel University , Philadelphia, Pennsylvania 19104, United States.
ACS Chem Biol. 2015 Dec 18;10(12):2861-73. doi: 10.1021/acschembio.5b00381. Epub 2015 Oct 22.
We investigated the mode of action underlying lytic inactivation of HIV-1 virions by peptide triazole thiol (PTT), in particular the relationship between gp120 disulfides and the C-terminal cysteine-SH required for virolysis. Obligate PTT dimer obtained by PTT SH cross-linking and PTTs with serially truncated linkers between pharmacophore isoleucine-ferrocenyltriazole-proline-tryptophan and cysteine-SH were synthesized. PTT variants showed loss of lytic activity but not binding and infection inhibition upon SH blockade. A disproportionate loss of lysis activity vs binding and infection inhibition was observed upon linker truncation. Molecular docking of PTT onto gp120 argued that, with sufficient linker length, the peptide SH could approach and disrupt several alternative gp120 disulfides. Inhibition of lysis by gp120 mAb 2G12, which binds at the base of the V3 loop, as well as disulfide mutational effects, argued that PTT-induced disruption of the gp120 disulfide cluster at the base of the V3 loop is an important step in lytic inactivation of HIV-1. Further, PTT-induced lysis was enhanced after treating virus with reducing agents dithiothreitol and tris (2-carboxyethyl)phosphine. Overall, the results are consistent with the view that the binding of PTT positions the peptide SH group to interfere with conserved disulfides clustered proximal to the CD4 binding site in gp120, leading to disulfide exchange in gp120 and possibly gp41, rearrangement of the Env spike, and ultimately disruption of the viral membrane. The dependence of lysis activity on thiol-disulfide interaction may be related to intrinsic disulfide exchange susceptibility in gp120 that has been reported previously to play a role in HIV-1 cell infection.
我们研究了肽三唑硫醇(PTT)对HIV-1病毒粒子进行裂解失活的作用模式,特别是糖蛋白120(gp120)二硫键与病毒裂解所需的C端半胱氨酸巯基之间的关系。合成了通过PTT巯基交联获得的专性PTT二聚体以及在药效基团异亮氨酸-二茂铁基三唑-脯氨酸-色氨酸和半胱氨酸巯基之间带有串联截短接头的PTT。PTT变体在巯基被封闭后表现出裂解活性丧失,但结合和感染抑制活性未丧失。接头截短后观察到裂解活性与结合和感染抑制活性不成比例地丧失。PTT与gp120的分子对接表明,在接头长度足够时,肽的巯基可以接近并破坏几种不同的gp120二硫键。在V3环基部结合的gp120单克隆抗体2G12对裂解的抑制作用以及二硫键突变效应表明,PTT诱导V3环基部的gp120二硫键簇的破坏是HIV-1裂解失活的重要步骤。此外,在用还原剂二硫苏糖醇和三(2-羧乙基)膦处理病毒后,PTT诱导的裂解作用增强。总体而言,这些结果与以下观点一致:PTT的结合使肽的巯基定位,以干扰gp120中靠近CD4结合位点聚集的保守二硫键,导致gp120以及可能的gp41中的二硫键交换、Env刺突重排,并最终破坏病毒膜。裂解活性对硫醇-二硫键相互作用的依赖性可能与先前报道的在HIV-1细胞感染中起作用的gp120内在二硫键交换敏感性有关。