Couto Sheila G, Nonato M Cristina, Costa-Filho Antonio J
Grupo de Biofísica Molecular Sérgio Mascarenhas, Instituto de Física de São Carlos, Universidade de São Paulo, 13560-970, São Carlos, SP, Brazil.
Biophys J. 2008 Mar 1;94(5):1746-53. doi: 10.1529/biophysj.107.120055. Epub 2007 Nov 9.
Dihydroorotate dehydrogenase (DHODH) catalyzes the oxidation of dihydroorotate to orotate during the fourth step of the de novo pyrimidine synthesis pathway. In rapidly proliferating mammalian cells, pyrimidine salvage pathway is insufficient to overcome deficiencies in that pathway for nucleotide synthesis. Moreover, as certain parasites lack salvage enzymes, relying solely on the de novo pathway, DHODH inhibition has turned out as an efficient way to block pyrimidine biosynthesis. Escherichia coli DHODH (EcDHODH) is a class 2 DHODH, found associated to cytosolic membranes through an N-terminal extension. We used electronic spin resonance (ESR) to study the interaction of EcDHODH with vesicles of 1,2-dioleoyl-sn-glycero-phosphatidylcholine/detergent. Changes in vesicle dynamic structure induced by the enzyme were monitored via spin labels located at different positions of phospholipid derivatives. Two-component ESR spectra are obtained for labels 5- and 10-phosphatidylcholine in presence of EcDHODH, whereas other probes show a single-component spectrum. The appearance of an additional spectral component with features related to fast-motion regime of the probe is attributed to the formation of a defect-like structure in the membrane hydrophobic region. This is probably the mechanism used by the protein to capture quinones used as electron acceptors during catalysis. The use of specific spectral simulation routines allows us to characterize the ESR spectra in terms of changes in polarity and mobility around the spin-labeled phospholipids. We believe this is the first report of direct evidences concerning the binding of class 2 DHODH to membrane systems.
二氢乳清酸脱氢酶(DHODH)在从头嘧啶合成途径的第四步催化二氢乳清酸氧化为乳清酸。在快速增殖的哺乳动物细胞中,嘧啶补救途径不足以克服该途径中核苷酸合成的缺陷。此外,由于某些寄生虫缺乏补救酶,仅依赖从头途径,抑制DHODH已成为阻断嘧啶生物合成的有效方法。大肠杆菌DHODH(EcDHODH)是2类DHODH,通过N端延伸与胞质膜相关联。我们使用电子自旋共振(ESR)研究EcDHODH与1,2-二油酰基-sn-甘油-磷脂酰胆碱/去污剂囊泡的相互作用。通过位于磷脂衍生物不同位置的自旋标记监测酶诱导的囊泡动态结构变化。在EcDHODH存在下,5-和10-磷脂酰胆碱标记获得双组分ESR光谱,而其他探针显示单组分光谱。出现与探针快速运动状态相关特征的额外光谱成分归因于膜疏水区域中形成缺陷样结构。这可能是蛋白质在催化过程中捕获用作电子受体的醌的机制。使用特定的光谱模拟程序使我们能够根据自旋标记磷脂周围的极性和流动性变化来表征ESR光谱。我们相信这是关于2类DHODH与膜系统结合的直接证据的首次报道。