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The isomerization of cytosine: Intramolecular hydrogen atom transfer mediated through formic acid

机译：胞嘧啶的异构化：通过甲酸介导的分子内氢原子转移

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Abstract > The catalytic ability of H <sub>2</sub> O and HCOOH to facilitate the tautomerism of KA to KIt isomer has been studied. It is shown that the direct tautomerism (path A) is unlikely because of the high activation free energy, whereas the presence of H <sub>2</sub> O and HCOOH (paths B and C) significantly contributes to decreasing the activation free energy. Meanwhile, the conventional transition state theory followed by Wigner tunneling correction is applied to estimate the rate constants. The rate constant with Wigner tunneling correction for direct tautomerization is obviously smaller than that of HCOOH‐mediated tautomerization, which is the most plausible mechanism. Finally, another important finding is that the ratio of reaction rates between direct tautomerism reaction and catalyst‐induced tautomerism increases with the increase of the catalyst concentration at a given temperature. The results of the present study demonstrate the feasibility of acid catalysis for DNA bases isomerization reaction that would otherwise be forbidden. </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”>摘要</标题> > H <sub> 2 </ sub> O和HCOOH的催化能力，便于研究了KA对套件异构体的互变异物。结果表明，由于高活化能量高，因此不太可能是不太可能的，而H <sub> 2 </ sub> O和HCOOH（路径b和c）的存在显着促成可自由的激活活力。同时，应用了传统的转换状态理论，然后应用Wigner隧道校正来估计速率常数。具有直接互联化的Wigner隧道校正的速率常数明显小于HCOOH介导的互联化的互联化，这是最合理的机制。最后，另一个重要的发现是直接互变异物反应和催化剂诱导的互变异构体之间的反应速率与给定温度下的催化剂浓度的增加增加。本研究结果表明，酸性催化的可行性将被禁止的DNA碱基异构化反应。 </ 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-35546/'>《Journal of Physical Organic Chemistry》</a> <b style="margin: 0 2px;">|</b><span>2018年第7期</span><b style="margin: 0 2px;">|</b><span>共8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=Jin Lingxia&option=202" target="_blank" rel="nofollow">Jin Lingxia;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Song Xiaoling&option=202" target="_blank" rel="nofollow">Song Xiaoling;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Cao Zhe&option=202" target="_blank" rel="nofollow">Cao Zhe;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Luo LiYang&option=202" target="_blank" rel="nofollow">Luo LiYang;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Zhao Caibin&option=202" target="_blank" rel="nofollow">Zhao Caibin;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Lu Jiufu&option=202" target="_blank" rel="nofollow">Lu Jiufu;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Zhang Qiang&option=202" target="_blank" rel="nofollow">Zhang Qiang;</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>Shaanxi Key Laboratory of Catalysis School of Chemical &</p> <p>Environment ScienceShaanxi University of TechnologyHanzhong China;</p> <p>Shaanxi Key Laboratory of Catalysis School of Chemical &</p> <p>Environment ScienceShaanxi University of TechnologyHanzhong China;</p> <p>Shaanxi Key Laboratory of Catalysis School of Chemical &</p> <p>Environment ScienceShaanxi University of TechnologyHanzhong China;</p> <p>Shaanxi Key Laboratory of Catalysis School of Chemical &</p> <p>Environment ScienceShaanxi University of TechnologyHanzhong China;</p> <p>Shaanxi Key Laboratory of Catalysis School of Chemical &</p> <p>Environment ScienceShaanxi University of TechnologyHanzhong China;</p> <p>Shaanxi Key Laboratory of Catalysis School of Chemical &</p> <p>Environment ScienceShaanxi University of TechnologyHanzhong China;</p> <p>Shaanxi Key Laboratory of Catalysis School of Chemical &</p> <p>Environment ScienceShaanxi University of TechnologyHanzhong China;</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/4796.html" title="有机化学一般性问题">有机化学一般性问题;</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=cytosine&option=203" rel="nofollow">cytosine;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=formic acid&option=203" rel="nofollow">formic acid;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=intramolecular hydrogen atom transfer&option=203" rel="nofollow">intramolecular hydrogen atom transfer;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=isomerization&option=203" rel="nofollow">isomerization;</a> </p> <div class="translation"> 机译：胞嘧啶;甲酸;分子内氢原子转移;异构化; 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</div> </li> <li> <div> <b>6. </b><a class="enjiyixqcontent" href="/academic-conference-cn_meeting-29680_thesis/020222244918.html">苯甲酰苯胺衍生物分子内电荷转移与质子转移的取代基效应</a> <b>[C]</b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=张煊&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 张煊</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=张晗&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,张晗</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=郭琳&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,郭琳</a> <span> <a href="/conference-cn-29680/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 第八届中国化学会分析化学年会暨第八届全国原子光谱学术会议 </a> <span> <span> . 2003</span> </span> </div> </li> <li> <div> <b>7. </b><a class="enjiyixqcontent" href="/academic-degree-domestic_mphd_thesis/020311544010.html">对二甲氨基苯甲酸多酯在自簇集体中的分子内电荷转移</a> <b>[A] </b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=温珍昌&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 温珍昌</a> <span> . 2001</span> </span> </div> </li> </ul> <ul style="display: none;"> <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/patent-detail/06120105185032.html">通过由电的在分子和电极之间的分子间或分子内电荷转移而发生电子转换的物质组合物</a> <b>[P]</b> . <span> 中国专利： CN1985331A </span> <span> . 2007-06-20</span> </div> </li> <li> <div> <b>2. </b><a class="enjiyixqcontent" href="/patent-detail/061203124559.html">目标物保护的哑铃分子探针介导的级联滚环扩增策略用于DNA甲基转移酶活性的灵敏检测</a> <b>[P]</b> . <span> 中国专利： CN105349683B </span> <span> . 2018.12.18</span> </div> </li> <li> <div> <b>3. </b><a class="enjiyixqcontent" href="/patent-detail/06130485005557.html">METHOD FOR PREPARING COMPLEX ETHERS OF SULPHOXIDE 7-ACYLAMINO-3-acyclic cime-DZ-CEFALOSPORIN1 The invention relates to an improved method for the production of cephalosporin derivatives, which can be used in the pharmaceutical industry. CO formulas where R is an acyl group; X is hydrogen or a nucleophilic group; R 'is hydrogen, a silyl group or an alkyl or aralkyl having from 1 to 20 carbon atoms, which means that the corresponding 7-acylamido-A ^ (or A ^ ) -cephalosporin It is recommended to oxidize with peracid or hydrogen peroxide in the presence of acid, and then isolate the products in a known manner. According to the present invention, to simplify the process, it was proposed to carry out the functionalization of the exocyclic oximethyl group at position 3 of the sulfoxide 10157-acylaminodemethyl cephalosporin without associating isomerization of the double bond with a ceraflosporomer cephalosporin-type antibiotics. Described method for preparing 7-acylamino-3-hydroxymethyl-A2-ce</a> <b>[P]</b> . <span> 外国专利：  SU422161A3 </span> <span> . 1974-03-30</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：制备硫化物7-酰基氨基-3-无环肟-DZ-CEFALOSPORIN1的复杂醚的方法本发明涉及生产头孢菌素衍生物的改进方法，其可用于制药工业。其中R为酰基的CO式; X是氢或亲核基团; R′是氢，甲硅烷基或具有1至20个碳原子的烷基或芳烷基，这意味着相应的7-酰基酰胺基-A ^（或A ^）-头孢菌素。建议用过酸或过氧化氢氧化。酸的存在，然后以已知方式分离产物。根据本发明，为简化方法，提出了在亚砜10157-酰基氨基脱甲基头孢菌素的3位上进行环外氧甲基的官能化，而无需使双键的异构化与头孢菌素头孢菌素型抗生素相关联。所述的制备7-酰基氨基-3-羟甲基-A2-ce的方法 </span> </p> </li> <li> <div> <b>4. </b><a class="enjiyixqcontent" href="/patent-detail/06130452460977.html">PROCEDURE FOR THE OBTAINING OF HYDROGEN PEROXIDE COMPLEXES, MONOPERCARBOXILIC ACIDS WITH 1 TO 4 ATOMS OF CARBON, AND DIPERCARBOXILIC ACIDS WITH 4 TO 18 ATOMS OF CARBON IN A FLUIDIZED BED PROCEDURE.</a> <b>[P]</b> . <span> 外国专利：  ES2129800T3 </span> <span> . 1999-06-16</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：在流化床程序中获取过氧化氢复合物，具有1至4个碳原子的单过碳酸和具有4至18个碳原子的双高碳酸的步骤。 </span> </p> </li> <li> <div> <b>5. </b><a class="enjiyixqcontent" href="/patent-detail/06130409494755.html">method for obtaining a pulsed neutron-induced gamma ray response that is substantially free of sensitivity to the hydrogen index of a formation and related to the atom density / electron density weighted in the inelastic cross section of the formation for formation evaluation, and apparatus to obtain a pulsed neutron-induced gamma ray response that is substantially free of sensitivity to the hydrogen index of a formation and related to the inelastic cross-section weighted atom density / electron density for formation evaluation</a> <b>[P]</b> . <span> 外国专利：  BR112013015185A2 </span> <span> . 2017-09-19</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：获得基本上不对地层的氢指数敏感并且与在地层的非弹性截面中加权的原子密度/电子密度有关的，对地层的氢指数不敏感的脉冲中子诱发伽马射线响应的方法，以及获得该装置的设备脉冲中子诱发的伽马射线响应，该响应基本上对地层的氢指数不敏感，并且与非弹性截面加权原子密度/电子密度有关，用于地层评估 </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('0704025793817','4',7,2,1,'',this,24)" class="delivery" prompt="010401" title="通过人工服务将文献原文发送至邮箱" >获取原文</div> <div class="journalsub-pop-up" style="display: none"> <div class="journal-sub"> <h2>期刊订阅</h2> <img src="https://cdn.zhangqiaokeyan.com/img/loginclose.png" alt="" 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