Hargrove Tatiana Y, Friggeri Laura, Wawrzak Zdzislaw, Sivakumaran Suneethi, Yazlovitskaya Eugenia M, Hiebert Scott W, Guengerich F Peter, Waterman Michael R, Lepesheva Galina I
Department of Biochemistry, Vanderbilt University School of Medicine, Nashville, TN 37232.
Synchrotron Research Center, Life Science Collaborative Access Team, Northwestern University, Argonne, IL.
J Lipid Res. 2016 Aug;57(8):1552-63. doi: 10.1194/jlr.M069229. Epub 2016 Jun 16.
Rapidly multiplying cancer cells synthesize greater amounts of cholesterol to build their membranes. Cholesterol-lowering drugs (statins) are currently in clinical trials for anticancer chemotherapy. However, given at higher doses, statins cause serious side effects by inhibiting the formation of other biologically important molecules derived from mevalonate. Sterol 14α-demethylase (CYP51), which acts 10 steps downstream, is potentially a more specific drug target because this portion of the pathway is fully committed to cholesterol production. However, screening a variety of commercial and experimental inhibitors of microbial CYP51 orthologs revealed that most of them (including all clinical antifungals) weakly inhibit human CYP51 activity, even if they display high apparent spectral binding affinity. Only one relatively potent compound, (R)-N-(1-(3,4'-difluorobiphenyl-4-yl)-2-(1H-imidazol-1-yl)ethyl)-4-(5-phenyl-1,3,4-oxadiazol-2-yl)benzamide (VFV), was identified. VFV has been further tested in cellular experiments and found to decrease proliferation of different cancer cell types. The crystal structures of human CYP51-VFV complexes (2.0 and 2.5 Å) both display a 2:1 inhibitor/enzyme stoichiometry, provide molecular insights regarding a broader substrate profile, faster catalysis, and weaker susceptibility of human CYP51 to inhibition, and outline directions for the development of more potent inhibitors.
快速增殖的癌细胞会合成更多的胆固醇来构建细胞膜。降胆固醇药物(他汀类药物)目前正处于抗癌化疗的临床试验阶段。然而,高剂量使用时,他汀类药物会通过抑制由甲羟戊酸衍生的其他生物重要分子的形成而导致严重的副作用。作用于下游10步的甾醇14α-去甲基酶(CYP51)可能是一个更具特异性的药物靶点,因为该途径的这一部分完全致力于胆固醇的产生。然而,对多种微生物CYP51直系同源物的商业和实验抑制剂进行筛选后发现,即使它们表现出高表观光谱结合亲和力,其中大多数(包括所有临床抗真菌药物)对人CYP51活性的抑制作用较弱。仅鉴定出一种相对有效的化合物,即(R)-N-(1-(3,4'-二氟联苯-4-基)-2-(1H-咪唑-1-基)乙基)-4-(5-苯基-1,3,4-恶二唑-2-基)苯甲酰胺(VFV)。VFV已在细胞实验中进一步测试,并发现可降低不同癌细胞类型的增殖。人CYP51-VFV复合物的晶体结构(2.0和2.5 Å)均显示出2:1的抑制剂/酶化学计量比,提供了关于更广泛底物谱、更快催化以及人CYP51对抑制作用较弱敏感性的分子见解,并概述了开发更有效抑制剂的方向。