Tanner N K, Cech T R
Department of Chemistry and Biochemistry, University of Colorado, Boulder 80309-0215.
Biochemistry. 1987 Jun 16;26(12):3330-40. doi: 10.1021/bi00386a013.
We have converted the intramolecular cyclization reaction of the self-splicing intervening sequence (IVS) ribonucleic acid (RNA) from Tetrahymena thermophila into an intermolecular guanosine addition reaction. This was accomplished by selectively removing the 3'-terminal nucleotide by oxidation and beta-elimination; the beta-eliminated IVS thereby is no longer capable of reacting with itself. However, under cyclization conditions, a free guanosine molecule can make a nucleophilic attack at the normal cyclization site. We have used this guanosine addition reaction as a model system for a Michaelis-Menten kinetic analysis of the guanosine binding site involved in cyclization. The results indicate that functional groups on the guanine that are used in a G-C Watson-Crick base pair are important for the cyclization reaction. This is the same result that was obtained for the guanosine binding site involved in splicing [Bass, B. L., & Cech, T. R. (1984) Nature (London) 308, 820-826]. Unlike splicing, however, certain additional nucleotides 5' to the guanosine moiety make significant binding contributions. We conclude that the guanosine binding site in cyclization is similar to, but not identical with, the guanosine binding site in splicing. The same binding interactions used in cyclization could help align the 3' splice site of the rRNA precursor for exon ligation. We also report that the phosphodiester bond at the cyclization site is susceptible to a pH-dependent hydrolysis reaction; the phosphodiester bond is somehow activated toward attack by the 3'hydroxyl of a guanosine molecule or by a hydroxyl ion.
我们已将嗜热栖热菌的自我剪接间隔序列(IVS)核糖核酸(RNA)的分子内环化反应转化为分子间鸟苷加成反应。这是通过氧化和β-消除选择性去除3'-末端核苷酸来实现的;经β-消除的IVS因此不再能够自身反应。然而,在环化条件下,游离的鸟苷分子可在正常环化位点进行亲核攻击。我们已将此鸟苷加成反应用作对环化过程中涉及的鸟苷结合位点进行米氏动力学分析的模型系统。结果表明,用于G-C沃森-克里克碱基对的鸟嘌呤上的官能团对环化反应很重要。这与剪接过程中涉及的鸟苷结合位点所得到的结果相同[巴斯,B.L.,& 切赫,T.R.(1984年)《自然》(伦敦)308,820 - 826]。然而,与剪接不同的是,鸟苷部分5'端的某些额外核苷酸对结合有显著贡献。我们得出结论,环化中的鸟苷结合位点与剪接中的鸟苷结合位点相似但不相同。环化中使用的相同结合相互作用可能有助于使rRNA前体的3'剪接位点对齐以便外显子连接。我们还报告说,环化位点的磷酸二酯键易受pH依赖性水解反应的影响;磷酸二酯键以某种方式被激活,易于受到鸟苷分子的3'羟基或羟基离子的攻击。