双链 DNA 中胞嘧啶 NH 基团的缓慢旋转动力学。
Slow Rotational Dynamics of Cytosine NH Groups in Double-Stranded DNA.
机构信息
Department of Biochemistry & Molecular Biology, Sealy Center for Structural Biology & Molecular Biophysics, University of Texas Medical Branch, Galveston, Texas 77555-1068, United States.
出版信息
Biochemistry. 2022 Jul 19;61(14):1415-1418. doi: 10.1021/acs.biochem.2c00299. Epub 2022 Jun 27.
Abstract
Aromatic NH groups are essential as hydrogen-bond donors in secondary structures of DNA and RNA. Although rapid rotations of NH groups of adenine and guanine bases were previously characterized, there has been a lack of quantitative information about slow rotations of cytosine NH groups in Watson-Crick base pairs. In this study, using an NMR method we had recently developed, we determined the kinetic rate constants and energy barriers for cytosine NH rotations in a 15-base-pair DNA duplex. Our data show that the rotational dynamics of cytosine NH groups depend on local environments. Qualitative correlation between the ranges of N chemical shifts and rotational time scales for various NH groups of nucleic acids and proteins illuminates a relationship between the partial double-bond character of the C-N bond and the time scale for NH rotations.
摘要
芳香族的 NH 基团是 DNA 和 RNA 二级结构中氢键供体所必需的。尽管腺嘌呤和鸟嘌呤碱基的 NH 基团的快速旋转此前已有特征描述，但沃森-克里克碱基对中胞嘧啶 NH 基团的缓慢旋转还缺乏定量信息。在这项研究中，我们使用最近开发的 NMR 方法，确定了 15 个碱基对 DNA 双螺旋中胞嘧啶 NH 旋转的动力学速率常数和能量势垒。我们的数据表明，胞嘧啶 NH 基团的旋转动力学取决于局部环境。各种核酸和蛋白质的 NH 基团的 N 化学位移范围和旋转时间尺度之间的定性相关性，阐明了 C-N 键的部分双键性质与 NH 旋转时间尺度之间的关系。
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