Mukhopadhyay R, Shi J, Rosen B P
Department of Biochemistry, Wayne State University, School of Medicine, Detroit, Michigan 48201, USA.
J Biol Chem. 2000 Jul 14;275(28):21149-57. doi: 10.1074/jbc.M910401199.
In Saccharomyces cerevisiae, expression of the ACR2 and ACR3 genes confers arsenical resistance. Acr2p is the first identified eukaryotic arsenate reductase. It reduces arsenate to arsenite, which is then extruded from cells by Acr3p. In this study, we demonstrate that ACR2 complemented the arsenate-sensitive phenotype of an arsC deletion in Escherichia coli. ACR2 was cloned into a bacterial expression vector and expressed in E. coli as a C-terminally histidine-tagged protein that was purified by sequential metal chelate affinity and gel filtration chromatography. Acr2p purified as a homodimer of 34 kDa. The purified protein was shown to catalyze the reduction of arsenate to arsenite. Enzymatic activity as a function of arsenate concentration exhibited an apparent positive cooperativity with an apparent Hill coefficient of 2.7. Activity required GSH and glutaredoxin as the source of reducing equivalents. Thioredoxin was unable to support arsenate reduction. However, glutaredoxins from both S. cerevisiae and E. coli were able to serve as reductants. Analysis of grx mutants lacking one or both cysteine residues in the Cys-Pro-Tyr-Cys active site demonstrated that only the N-terminal cysteine residue is essential for arsenate reductase activity. This suggests that during the catalytic cycle, Acr2p forms a mixed disulfide with GSH before being reduced by glutaredoxin to regenerate the active Acr2p reductase.
在酿酒酵母中,ACR2和ACR3基因的表达赋予了对砷的抗性。Acr2p是首个被鉴定出的真核生物砷酸盐还原酶。它将砷酸盐还原为亚砷酸盐,然后由Acr3p将其排出细胞。在本研究中,我们证明ACR2弥补了大肠杆菌中arsC缺失导致的砷酸盐敏感表型。ACR2被克隆到细菌表达载体中,并在大肠杆菌中作为C端带有组氨酸标签的蛋白表达,该蛋白通过连续的金属螯合亲和层析和凝胶过滤层析进行纯化。纯化后的Acr2p为34 kDa的同二聚体。纯化后的蛋白显示出催化砷酸盐还原为亚砷酸盐的能力。酶活性作为砷酸盐浓度的函数表现出明显的正协同性,表观希尔系数为2.7。活性需要谷胱甘肽(GSH)和谷氧还蛋白作为还原当量的来源。硫氧还蛋白无法支持砷酸盐还原。然而,来自酿酒酵母和大肠杆菌的谷氧还蛋白都能够作为还原剂。对在Cys-Pro-Tyr-Cys活性位点缺少一个或两个半胱氨酸残基的谷氧还蛋白突变体的分析表明,只有N端半胱氨酸残基对于砷酸盐还原酶活性是必不可少的。这表明在催化循环过程中,Acr2p在被谷氧还蛋白还原以再生活性Acr2p还原酶之前,先与GSH形成混合二硫键。