Ma Jing, Lim Chaemin, Sacher Joshua R, Van Houten Bennett, Qian Wei, Wipf Peter
Department of Pharmacology and Chemical Biology, University of Pittsburgh, and Hillman Cancer Center, University of Pittsburgh Cancer Institute, 5117 Centre Avenue, Pittsburgh, PA 15213, United States; Department of Respiratory and Critical Care Medicine, Tongji Hospital, Tongji Medical College of HuaZhong University of Science and Technology, Wuhan 430030, China.
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260, United States; Accelerated Chemical Discovery Center, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260, United States.
Bioorg Med Chem Lett. 2015 Nov 1;25(21):4828-4833. doi: 10.1016/j.bmcl.2015.06.073. Epub 2015 Jun 26.
Mitochondria play important roles in tumor cell physiology and survival by providing energy and metabolites for proliferation and metastasis. As part of their oncogenic status, cancer cells frequently produce increased levels of mitochondrial-generated reactive oxygen species (ROS). However, extensive stimulation of ROS generation in mitochondria has been shown to be able to induce cancer cell death, and is one of the major mechanisms of action of many anticancer agents. We hypothesized that enhancing mitochondrial ROS generation through direct targeting of a ROS generator into mitochondria will exhibit tumor cell selectivity, as well as high efficacy in inducing cancer cell death. We thus synthesized a mitochondrial targeted version of β-lapachone (XJB-Lapachone) based on our XJB mitochondrial targeting platform. We found that the mitochondrial targeted β-lapachone is more efficient in inducing apoptosis compared to unconjugated β-lapachone, and the tumor cell selectivity is maintained. XJB-Lapachone also induced extensive cellular vacuolization and autophagy at a concentration not observed with unconjugated β-lapachone. Through characterization of mitochondrial function we revealed that XJB-Lapachone is indeed more capable of stimulating ROS generation in mitochondria, which led to a dramatic mitochondrial uncoupling and autophagic degradation of mitochondria. Taken together, we have demonstrated that targeting β-lapachone accomplishes higher efficacy through inducing ROS generation directly in mitochondria, resulting in extensive mitochondrial and cellular damage. XJB-Lapachone will thus help to establish a novel platform for the design of next generation mitochondrial targeted ROS generators for cancer therapy.
线粒体通过为肿瘤细胞的增殖和转移提供能量及代谢物,在肿瘤细胞生理功能及存活过程中发挥着重要作用。作为其致癌状态的一部分,癌细胞中线粒体产生的活性氧(ROS)水平通常会升高。然而,线粒体中ROS生成的过度刺激已被证明能够诱导癌细胞死亡,并且是许多抗癌药物的主要作用机制之一。我们推测,通过将ROS生成剂直接靶向线粒体来增强线粒体ROS生成,将表现出肿瘤细胞选择性,以及在诱导癌细胞死亡方面的高效性。因此,我们基于XJB线粒体靶向平台合成了一种线粒体靶向型β-拉帕醌(XJB-拉帕醌)。我们发现,与未偶联的β-拉帕醌相比,线粒体靶向型β-拉帕醌在诱导细胞凋亡方面更有效,并且保持了肿瘤细胞选择性。XJB-拉帕醌还在未偶联的β-拉帕醌未观察到的浓度下诱导了广泛的细胞空泡化和自噬。通过对线粒体功能的表征,我们揭示XJB-拉帕醌确实更能够刺激线粒体中的ROS生成,这导致了显著的线粒体解偶联和线粒体的自噬降解。综上所述,我们证明了靶向β-拉帕醌通过直接在线粒体中诱导ROS生成实现了更高的疗效,从而导致广泛的线粒体和细胞损伤。因此,XJB-拉帕醌将有助于建立一个用于设计下一代线粒体靶向ROS生成剂用于癌症治疗的新平台。