Lawley P D, Warren W
Chem Biol Interact. 1976 Feb;12(2):211-20. doi: 10.1016/0009-2797(76)90100-9.
Persistence of methylpurines in DNA methylated in vitro and in vivo in Escherichia coli WP2 cells, by dimethyl sulphate (DMS) was studied, with particular reference to the minor products 7-methyladenine and 3-methylguanine, not previously investigated in this respect, but known to be removed from DNA in vitro by spontaneous hydrolysis at neutral pH. The half-life of 7-methyladenine in vivo was relatively short (2.6 +/- 0.2 h) but not significantly shorter than in vitro at pH 7.2, 37 degrees C. The half-life of 3-methylguanine was 3.6 +/- 0.3 h in vivo, markedly shorter than in vitro, where its stability was somewhat greater than that of 7-methylguanine. Enzymatic excision of 3-methylguanine was therefore indicated to occur in E. coli. Previous findings that 7-methylguanine is probably not enzymatically excised from DNA in vivo, whereas 3-methyladenine is rapidly removed, were confirmed, and additional support for the concept of enzymatic removal of 3-methyladenine was obtained by showing extensive inhibition of its removal from cells treated with iodoacetamide prior to methylation. It is suggested that methylations of adenine or guanine in DNA at N-3 constitute blocks to template activity of DNA and stimulate a "repair" response of enzymatic removal of 3-methylpurines. Possible valence bond structures for 3-methylpurine residues in DNA are discussed, leading to the suggestion that ionized forms with positively charged amino groups may be the most effective blocks to template activity.
研究了硫酸二甲酯(DMS)在体外和体内对大肠杆菌WP2细胞DNA甲基化中甲基嘌呤的持久性,特别关注次要产物7-甲基腺嘌呤和3-甲基鸟嘌呤,此前尚未在这方面进行过研究,但已知在中性pH下可通过体外自发水解从DNA中去除。7-甲基腺嘌呤在体内的半衰期相对较短(2.6±0.2小时),但在37℃、pH 7.2时并不比体外显著短。3-甲基鸟嘌呤在体内的半衰期为3.6±0.3小时,明显短于体外,其稳定性略高于7-甲基鸟嘌呤。因此表明3-甲基鸟嘌呤在大肠杆菌中会发生酶促切除。先前的研究结果得到证实,即7-甲基鸟嘌呤在体内可能不会从DNA中被酶促切除,而3-甲基腺嘌呤会被迅速去除,并且通过显示对甲基化前用碘乙酰胺处理的细胞中3-甲基腺嘌呤去除的广泛抑制,获得了对3-甲基腺嘌呤酶促去除概念的额外支持。有人提出,DNA中腺嘌呤或鸟嘌呤在N-3位的甲基化构成了对DNA模板活性的阻碍,并刺激了对3-甲基嘌呤进行酶促去除的“修复”反应。讨论了DNA中3-甲基嘌呤残基可能的价键结构,结果表明带有带正电荷氨基的离子形式可能是对模板活性最有效的阻碍。