Sekiguchi J, Shuman S
Molecular Biology Program, Sloan-Kettering Institute, 1275 York Avenue, New York, NY 10021, USA.
Nucleic Acids Res. 1997 Sep 15;25(18):3649-56. doi: 10.1093/nar/25.18.3649.
Vaccinia DNA topoisomerase catalyzes the cleavage and re-joining of DNA strands through a DNA-(3'-phosphotyrosyl)-enzyme intermediate formed at a specific target sequence, 5'-(C/T)CCTT downward arrow. The 314 aa protein consists of three protease-resistant structural domains demarcated by protease-sensitive interdomain segments referred to as the bridge and the hinge. The bridge is defined by trypsin-accessible sites at Arg80, Lys83 and Arg84. Photocrosslinking and proteolytic footprinting experiments suggest that residues near the interdomain bridge interact with DNA. To assess the contributions of specific amino acids to DNA binding and transesterification chemistry, we introduced alanine substitutions at 16 positions within a 24 aa segment from residues 63 to 86(DSKGRRQYFYGKMHVQNRNAKRDR). Assays of the rates of DNA relaxation under conditions optimal for the wild-type topoisomerase revealed significant mutational effects at six positions; Arg67, Tyr70, Tyr72, Arg80, Arg84 and Asp85. The mutated proteins displayed normal or near-normal rates of single-turnover transesterification to DNA. The effects of amino acid substitutions on DNA binding were evinced by inhibition of covalent adduct formation in the presence of salt and magnesium. The mutant enzymes also displayed diminished affinity for a subset of cleavage sites in pUC19 DNA. Tyr70 and Tyr72 were subjected to further analysis by replacement with Phe, His, Gln and Arg. At both positions, the aromatic moiety was important for DNA binding.
痘苗病毒DNA拓扑异构酶通过在特定靶序列5'-(C/T)CCTT向下箭头处形成的DNA-(3'-磷酸酪氨酸)-酶中间体催化DNA链的切割和重新连接。这个314个氨基酸的蛋白质由三个抗蛋白酶的结构域组成,这些结构域由被称为桥和铰链的蛋白酶敏感的结构域间片段分隔开。桥由位于Arg80、Lys83和Arg84处的胰蛋白酶可及位点定义。光交联和蛋白水解足迹实验表明,结构域间桥附近的残基与DNA相互作用。为了评估特定氨基酸对DNA结合和酯交换化学的贡献,我们在63至86位残基(DSKGRRQYFYGKMHVQNRNAKRDR)的24个氨基酸片段内的16个位置引入了丙氨酸替代。在野生型拓扑异构酶最适宜的条件下对DNA松弛速率进行测定,结果显示在六个位置有显著的突变效应;Arg67、Tyr70、Tyr72、Arg80、Arg84和Asp85。突变后的蛋白质对DNA的单周转酯交换反应速率显示正常或接近正常。在有盐和镁存在的情况下,共价加合物形成受到抑制,这表明氨基酸替代对DNA结合有影响。突变酶对pUC19 DNA中一部分切割位点的亲和力也有所降低。通过用Phe、His、Gln和Arg替代对Tyr70和Tyr72进行了进一步分析。在这两个位置,芳香基团对DNA结合都很重要。