Mazzarelli J, Scholtissek S, McLaughlin L W
Department of Chemistry, Boston College, Chestnut Hill, Massachusetts 02167.
Biochemistry. 1989 May 30;28(11):4616-22. doi: 10.1021/bi00437a016.
Oligodeoxynucleotides have been prepared which contain changes in the functional group pattern present in the EcoRV recognition site d(GATATC). These modifications involve the deletion of specific functional groups or the reversal of the relative positions of functional groups within the canonical six base pair recognition site. The duplex stability of these modified oligodeoxynucleotides has been assessed by determining the thermodynamic parameters characterizing helix formation. Steady-state kinetic parameters have been used to characterize the interaction of the modified oligodeoxynucleotides with the EcoRV endonuclease. The enzyme is very sensitive to the deletion of either of the adenine amino or thymine methyl groups, or the reversal of the relative positions of the adenine amino group and thymine carboxy group which form an interstrand hydrogen bond in the major groove of the B-DNA helix. Conversely, deletion of the guanine amino group had only minimal effects upon the measured kinetic parameters. Deletion of the exocyclic amino group from the "inner" dA-dT base pair resulted in the fragment which interacted with the enzyme on the basis of observed inhibition experiments but was not cleaved. The results suggest that the endonuclease interacts with its recognition sequence via contacts in the major groove of the B-DNA helix and that both hydrogen bonding to the adenine amino groups and also hydrophobic interactions with the thymine methyl groups are involved.
已制备出含有EcoRV识别位点d(GATATC)中官能团模式变化的寡脱氧核苷酸。这些修饰包括特定官能团的缺失或在标准六碱基对识别位点内官能团相对位置的颠倒。通过确定表征螺旋形成的热力学参数,评估了这些修饰的寡脱氧核苷酸的双链稳定性。稳态动力学参数已用于表征修饰的寡脱氧核苷酸与EcoRV核酸内切酶的相互作用。该酶对腺嘌呤氨基或胸腺嘧啶甲基的任何一个缺失,或对在B-DNA螺旋大沟中形成链间氢键的腺嘌呤氨基和胸腺嘧啶羧基相对位置的颠倒非常敏感。相反,鸟嘌呤氨基的缺失对所测动力学参数的影响最小。从“内部”dA-dT碱基对中缺失环外氨基,产生了在观察到的抑制实验基础上与酶相互作用但未被切割的片段。结果表明,核酸内切酶通过与B-DNA螺旋大沟中的接触与其识别序列相互作用,并且涉及与腺嘌呤氨基的氢键结合以及与胸腺嘧啶甲基的疏水相互作用。