Rajan Rakhi, Osterman Amy K, Gast Alexandra T, Mondragón Alfonso
From the Department of Molecular Biosciences, Northwestern University, Evanston, Illinois 60208.
From the Department of Molecular Biosciences, Northwestern University, Evanston, Illinois 60208
J Biol Chem. 2014 Oct 17;289(42):28898-909. doi: 10.1074/jbc.M114.590711. Epub 2014 Aug 18.
Topoisomerases are ubiquitous enzymes that modify the topological state of DNA inside the cell and are essential for several cellular processes. Topoisomerase V is the sole member of the type IC topoisomerase subtype. The topoisomerase domain has a unique fold among topoisomerases, and the putative active site residues show a distinct arrangement. The present study was aimed at identifying the roles of the putative active site residues in the DNA cleavage/religation process. Residues Arg-131, Arg-144, His-200, Glu-215, Lys-218, and Tyr-226 were mutated individually to a series of conservative and non-conservative amino acids, and the DNA relaxation activity at different pH values, times, and enzyme concentrations was compared with wild-type activity. The results suggest that Arg-144 is essential for protein stability because any substitution at this position was deleterious and that Arg-131 and His-200 are involved in transition state stabilization. Glu-215 reduces the DNA binding ability of topoisomerase V, especially in shorter fragments with fewer helix-hairpin-helix DNA binding motifs. Finally, Lys-218 appears to play a direct role in catalysis but not in charge stabilization of the protein-DNA intermediate complex. The results suggest that although catalytically important residues are oriented in different fashions in the active sites of type IB and type IC topoisomerases, similar amino acids play equivalent roles in both of these subtypes of enzymes, showing convergent evolution of the catalytic mechanism.
拓扑异构酶是普遍存在的酶,可改变细胞内DNA的拓扑状态,对多种细胞过程至关重要。拓扑异构酶V是IC型拓扑异构酶亚型的唯一成员。拓扑异构酶结构域在拓扑异构酶中具有独特的折叠方式,且推定的活性位点残基呈现出不同的排列。本研究旨在确定推定的活性位点残基在DNA切割/连接过程中的作用。将残基精氨酸-131、精氨酸-144、组氨酸-200、谷氨酸-215、赖氨酸-218和酪氨酸-226分别突变为一系列保守和非保守氨基酸,并将不同pH值、时间和酶浓度下的DNA松弛活性与野生型活性进行比较。结果表明,精氨酸-144对蛋白质稳定性至关重要,因为该位置的任何取代都是有害的,且精氨酸-131和组氨酸-200参与过渡态稳定。谷氨酸-215降低了拓扑异构酶V的DNA结合能力,尤其是在具有较少螺旋-发夹-螺旋DNA结合基序的较短片段中。最后,赖氨酸-218似乎在催化中起直接作用,但在蛋白质-DNA中间复合物的电荷稳定中不起作用。结果表明,尽管催化重要残基在IB型和IC型拓扑异构酶的活性位点中以不同方式排列,但相似的氨基酸在这两种酶亚型中发挥等效作用,表明催化机制的趋同进化。