FORMALDEHYDE AS A PROBE OF DNA STRUCTURE .2. REACTION WITH ENDOCYCLIC IMINO GROUPS OF DNA BASES
FORMALDEHYDE AS A PROBE OF DNA STRUCTURE .2. REACTION WITH ENDOCYCLIC IMINO GROUPS OF DNA BASES
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DOI：
10.1021/bi00677a030
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发表时间：
1975-01-01
期刊：
影响因子：
2.9
通讯作者：
HIPPEL, PHV
中科院分区：
文献类型：
--
作者：
MCGHEE, JD;HIPPEL, PHV
James D.作者声明：Peter H. von Hippel* 摘要：本文描述了甲醛与胸腺嘧啶、尿嘧啶、一系列卤代尿嘧啶衍生物以及聚尿苷酸和聚肌苷酸的内环亚氨基反应的平衡和动力学。主要结果是：（i）所有化合物形成羟甲基加合物的平衡常数均为2 -2.5（/-1），与它们的pK无关;（ii）在pH约为4-9的范围内，5 ′-TMP的正向和反向反应速率常数均为特定的碱催化速率;（iii）测定了反应速率常数对温度和几种溶剂添加剂的响应;（iv）在中性pH值下，嘧啶系列化合物的自由能与反应速率的对数成线性关系。正向和反向速率常数和去质子化的pK;（v）
James D. McGhee and Peter H. von Hippel* abstract: We describe the equilibrium and kinetic as-pects of the formaldehyde reaction with the endocyclic imino groups of derivatives of thymine, uracil, and a series of halogenated uracils, as well as poly (uridylic acid) and poly (inosinic acid). The main results are:(i) the equilibri-um constants for forming a hydroxymethyl adduct remain quite constant at about2-2.5 (/-1) for all the compounds studied, independent of their pK;(ii) both forward and reverse rate constants with 5'-TMP are specific base cata-lyzed in the pH range of about 4-9;(iii) the response of the rate constants to temperature andto several solvent addi-tives are measured;(iv) at neutral pH, for the series of py-rimidine compounds, a linear free energy relation is observed between the logarithm of both the. forward and the reverse rate constant and the pK for deprotonation;(v) the