{"title":"硝基取代的非天然核酸碱基的光物理学。","authors":"Adithya Krishnan Pradeep Kumar, Supriyo Santra, Debashree Ghosh","doi":"10.1021/acs.jpca.4c03948","DOIUrl":null,"url":null,"abstract":"<p><p>The unnatural nucleic acid base (uNAB), 6-amino-3-methyl-5-nitropyridin-2(1H)one, often referred to as <i>Z</i> can form a base pair with the uNAB 2-aminoimidazo[1,2-<i>a</i>]-1,3,5-triazin-4(8H)-one (referred to as P) and is analogous to a guanine-cytosine (G-C) pair. However, it is well-known that the nonradiative decay pathway of the P-Z pair is significantly different from that of the G-C pair (Cui et al., <i>Front. Chem.</i> <b>2020</b>, <i>8</i>, 605117-605125). In this work, we study the excited state processes in <i>Z</i> using state-of-the-art multireference methods and dynamical techniques to ascertain the predominant nonradiative channels. We find that unlike in the natural NABs, the excited state processes in <i>Z</i> are driven primarily by the -NO<sub>2</sub> group rotation. The electron-withdrawing effect of the -NO<sub>2</sub> substituent plays a crucial role. We further ascertained that ultrafast deactivation channels are possible in <i>Z</i> and identified the stationary point geometries that are responsible for these channels.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"9551-9558"},"PeriodicalIF":2.7000,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photophysics of Nitro-Substituted Unnatural Nucleic Acid Base.\",\"authors\":\"Adithya Krishnan Pradeep Kumar, Supriyo Santra, Debashree Ghosh\",\"doi\":\"10.1021/acs.jpca.4c03948\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The unnatural nucleic acid base (uNAB), 6-amino-3-methyl-5-nitropyridin-2(1H)one, often referred to as <i>Z</i> can form a base pair with the uNAB 2-aminoimidazo[1,2-<i>a</i>]-1,3,5-triazin-4(8H)-one (referred to as P) and is analogous to a guanine-cytosine (G-C) pair. However, it is well-known that the nonradiative decay pathway of the P-Z pair is significantly different from that of the G-C pair (Cui et al., <i>Front. Chem.</i> <b>2020</b>, <i>8</i>, 605117-605125). In this work, we study the excited state processes in <i>Z</i> using state-of-the-art multireference methods and dynamical techniques to ascertain the predominant nonradiative channels. We find that unlike in the natural NABs, the excited state processes in <i>Z</i> are driven primarily by the -NO<sub>2</sub> group rotation. The electron-withdrawing effect of the -NO<sub>2</sub> substituent plays a crucial role. We further ascertained that ultrafast deactivation channels are possible in <i>Z</i> and identified the stationary point geometries that are responsible for these channels.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\" \",\"pages\":\"9551-9558\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-11-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpca.4c03948\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/10/29 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.4c03948","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/29 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
非天然核酸碱基(uNAB)--6-氨基-3-甲基-5-硝基吡啶-2(1H)-酮(通常称为 Z)可与 uNAB 2-氨基咪唑并[1,2-a]-1,3,5-三嗪-4(8H)-酮(称为 P)形成碱基对,类似于鸟嘌呤-胞嘧啶(G-C)对。然而,众所周知,P-Z 对的非辐射衰变途径与 G-C 对有很大不同(Cui 等,Front.)在这项工作中,我们利用最先进的多参量方法和动力学技术研究了 Z 的激发态过程,以确定主要的非辐射通道。我们发现,与天然 NABs 不同,Z 中的激发态过程主要由 -NO2 基团旋转驱动。-NO2取代基的抽电子效应起着至关重要的作用。我们进一步确定了 Z 中可能存在超快失活通道,并确定了造成这些通道的静止点几何结构。
Photophysics of Nitro-Substituted Unnatural Nucleic Acid Base.
The unnatural nucleic acid base (uNAB), 6-amino-3-methyl-5-nitropyridin-2(1H)one, often referred to as Z can form a base pair with the uNAB 2-aminoimidazo[1,2-a]-1,3,5-triazin-4(8H)-one (referred to as P) and is analogous to a guanine-cytosine (G-C) pair. However, it is well-known that the nonradiative decay pathway of the P-Z pair is significantly different from that of the G-C pair (Cui et al., Front. Chem.2020, 8, 605117-605125). In this work, we study the excited state processes in Z using state-of-the-art multireference methods and dynamical techniques to ascertain the predominant nonradiative channels. We find that unlike in the natural NABs, the excited state processes in Z are driven primarily by the -NO2 group rotation. The electron-withdrawing effect of the -NO2 substituent plays a crucial role. We further ascertained that ultrafast deactivation channels are possible in Z and identified the stationary point geometries that are responsible for these channels.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.