Excited-state tautomerization of cytidine in water solution when exposed to UVC light

IF 1.9 4区化学 Q2 CHEMISTRY, ORGANIC

Journal of Physical Organic Chemistry Pub Date : 2023-10-24 DOI:10.1002/poc.4576

Tsvetina D. Cherneva, Mina M. Todorova, Rumyana I. Bakalska, Ivan G. Shterev, Ernst Horkel, Vassil B. Delchev

引用次数: 0

Abstract

The irradiation of water solution of cytidine with UVC light showed that the compound participates in a tautomerism following the kinetics of a first-order reaction. The PIDA mechanism showed that the proton detachments in the tautomers of cytidine occur through the repulsive ¹πσ* excited states and lead to conical intersections S₀/S₁, whose structures were optimized. More probable is the IRC mechanism, which proceeds along ¹nπ* excited state reaction paths. This mechanism includes a water molecule as a catalyst, which assists the phototransformation of amino-oxo tautomer of cytidine into imino-hydroxy one.

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水溶液中胞苷在紫外线照射下的激发态同分异构现象

用紫外线照射胞苷的水溶液表明，该化合物按照一阶反应动力学参与了同分异构反应。PIDA 机制表明，胞苷的同分异构体中质子的分离是通过具有排斥性的 1πσ* 激发态发生的，并导致锥形交叉 S0/S1，其结构已被优化。更有可能的是沿着 1nπ* 激发态反应路径进行的 IRC 机制。该机制包括一个水分子作为催化剂，帮助胞苷的氨基-氧代同系物向亚氨基-羟基同系物进行光转化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Physical Organic Chemistry 化学-物理化学

CiteScore

3.60

自引率

11.10%

发文量

161

审稿时长

2.3 months

期刊介绍： The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.