On the nature of ion‐stabilized cytosine pairs in DNA i‐motifs: The importance of charge transfer processes

Kohagen Miriam; Uhlig Frank; Smiatek Jens

摘要

Abstract > Recent experimental results indicate that the stability of non‐Watson‐Crick DNA i‐motif structures can be influenced by the presence of various metal cations. Whereas Au + , Cu + , and Ag + are stabilizing agents, alkali metal ions like Na + or Li + are known to destabilize the i‐motif. In terms of reduced ion‐cytosine complexes, we rationalize the experimental observations with the help of standard and conceptual density functional theory (DFT) calculations. Our results highlight the importance of coordinating electrostatic bonds with partially covalent character for the stability of the ion‐cytosine complex. The occurrence of these bonds can be mainly attributed to charge transfer processes between two cytosines and the transition metal ions, which can be either explained by frontier molecular orbital theory in combination with a bond critical point analysis, or by the concept of chemical reactivity indices within a conceptual DFT approach. The results of our calculations establish a consistent theoretical framework to understand the experimentally observed behavior, and are also important in order to achieve more detailed insights into nucleobase pairing mechanisms in general. </abstract> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> <div class="translation abstracttxt"> <span class="zhankaihshouqi fivelineshidden" id="abstract"> <span>机译：</span><Abstract Type =“main”XML：Lang =“en”> <标题类型=“main”>抽象</ title> >最近的实验结果表明非Watson-Crick DNA I-MOTIF结构的稳定性受到各种金属阳离子的存在的影响。虽然Au + </ sup>，Cu + </ sup>，Ag + </ sup>是稳定剂，碱金属离子，如na + </ sup>或li已知 + </ sup>使I-MOTIF命名为破坏I-MOTIF。在减少离子 - 胞嘧啶复合物方面，我们在标准和概念密度泛函（DFT）计算的帮助下合理化实验观察。我们的结果突出了与部分共价特征协调静电键的重要性，以便离子 - 胞嘧啶复合物的稳定性。这些键的发生可能主要归因于两种胞嘧啶和过渡金属离子之间的电荷转移过程，其可以通过前沿分子轨道理论与债券临界点分析结合或通过化学反应性指数的概念来解释一种概念的DFT方法。我们的计算结果建立了一致的理论框架，以了解实验观察到的行为，并且对于一般来说，对于核心酶配对机构的更详细的见解也是重要的。 </ p> </ abstract> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> </div> <div class="record"> <h2 class="all_title" id="enpatent33" >著录项</h2> <ul> <li> <span class="lefttit">来源</span> <div style="width: 86%;vertical-align: text-top;display: inline-block;"> <a href='/journal-foreign-21753/'>《International Journal of Quantum Chemistry》</a> <b style="margin: 0 2px;">|</b><span>2019年第14期</span><b style="margin: 0 2px;">|</b><span>共12页</span> </div> </li> <li> <div class="author"> <span class="lefttit">作者</span> <p id="fAuthorthree" class="threelineshidden zhankaihshouqi"> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Kohagen Miriam&option=202" target="_blank" rel="nofollow">Kohagen Miriam;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Uhlig Frank&option=202" target="_blank" rel="nofollow">Uhlig Frank;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Smiatek Jens&option=202" target="_blank" rel="nofollow">Smiatek Jens;</a> </p> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zkzz" style="display: none;">展开▼</span> </div> </li> <li> <div style="display: flex;"> <span class="lefttit">作者单位</span> <div style="position: relative;margin-left: 3px;max-width: 639px;"> <div class="threelineshidden zhankaihshouqi" id="fOrgthree"> <p>Institute for Computational Physics University of StuttgartStuttgart Germany;</p> <p>Institute for Computational Physics University of StuttgartStuttgart Germany;</p> <p>Institute for Computational Physics University of StuttgartStuttgart Germany;</p> </div> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zhdw" style="display: none;">展开▼</span> </div> </div> </li> <li > <span class="lefttit">收录信息</span> <span style="width: 86%;vertical-align: text-top;display: inline-block;"></span> </li> <li> <span class="lefttit">原文格式</span> <span>PDF</span> </li> <li> <span class="lefttit">正文语种</span> <span>eng</span> </li> <li> <span class="lefttit">中图分类</span> <span><a href="https://www.zhangqiaokeyan.com/clc/1186.html" title="物理化学（理论化学）、化学物理学">物理化学（理论化学）、化学物理学;</a></span> </li> <li class="antistop"> <span class="lefttit">关键词</span> <p style="width: 86%;vertical-align: text-top;"> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=charge transfer&option=203" rel="nofollow">charge transfer;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=conceptual DFT&option=203" rel="nofollow">conceptual DFT;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=DNA&option=203" rel="nofollow">DNA;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=HSAB principle&option=203" rel="nofollow">HSAB principle;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=ions&option=203" rel="nofollow">ions;</a> </p> <div class="translation"> 机译：电荷转移;概念DFT;DNA;HSAB原则;离子; </div> </li> </ul> </div> </div> <div class="literature cardcommon"> 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methyltransferase 1 inhibitor, a method for DNA methylation inhibition, the use of the analogue in the treatment of diseases associated with deviations from normal DNA methylation</a> <b>[P]</b> . <span> 外国专利：  US9040490B2 </span> <span> . 2015-05-26</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：胞嘧啶类似物，胞嘧啶类似物的制备方法，DNA甲基转移酶1抑制剂，DNA甲基化抑制方法，该类似物在治疗与正常DNA甲基化偏离有关的疾病中的用途 </span> </p> </li> </ul> </div> </div> </div> <div class="theme cardcommon" style="overflow: auto;display:none"> <h3 class="all_title" id="enpatent55">相关主题</h3> <ul id="subject"> </ul> </div> </div> </div> </div> <div class="right rightcon"> <div class="details_img cardcommon clearfix" style="margin-bottom: 10px;display:none;" > </div> </div> </div> <div id="thesis_get_original1" class="downloadBth" style="bottom: 19px;z-index: 999;" onclick="ywcd('0704019755457','4',7,2,1,'',this,24)" 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