Protonation Weakens the Influence of Ribose on Triplet Decay of 2-Thiocytidine

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters Pub Date : 2024-11-20 DOI:10.1021/acs.jpclett.4c02575

Shuyi Yan, Wenwen Guo, Jialong Jie, Qian Zhou, Di Song, Dongyu Li, Hongmei Su

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Abstract

Long-lived triplet states are critical intermediates of thiobases for their applications in photodynamic therapy and as photoprobes for DNA/RNA–protein interactions, where thiobases are embedded in DNA/RNA and exist as thionucleosides. However, sugar moieties accelerate triplet decay rates, which is a common issue that must be resolved for thionucleosides. Here, we explore whether protonation of 2-thiocytosine (2tCyt) and 2-thiocytidine (2tCyd) under acidic pH can alter their triplet decays. Femtosecond spectroscopy demonstrates that 2tCytH⁺ and 2tCydH⁺ exhibit similar triplet lifetimes (3.1 ns), suggesting protonation diminishes the influence of ribose on triplet decay. Notably, the triplet lifetime of 2tCydH⁺ is 2-fold prolonged compared to 2tCyd. Further calculations reveal protonation effectively weakens the influence of ribose by altering electronic structures of triplet states and inhibiting the photoisomerization leading to rapid decay. These findings point to a new avenue of using protonation to modulate triplet decay dynamics of thionucleosides and develop pH-responsive strategy in photochemical applications.

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质子化削弱核糖对 2-硫胞苷三重分解的影响

长寿命三重态是硫代核苷酸应用于光动力疗法和 DNA/RNA 蛋白相互作用光探测的关键中间体，硫代核苷酸嵌入 DNA/RNA 中，并以硫代核苷的形式存在。然而，糖分子会加快三重态衰变速率，这是硫代核苷必须解决的一个常见问题。在此，我们探讨了 2-硫胞嘧啶（2tCyt）和 2-硫胞苷（2tCyd）在酸性 pH 下的质子化是否会改变它们的三重态衰变。飞秒光谱显示，2tCytH+ 和 2tCydH+ 的三重态寿命（3.1 ns）相似，这表明质子化会减弱核糖对三重态衰变的影响。值得注意的是，与 2tCyd 相比，2tCydH+ 的三重态寿命延长了 2 倍。进一步的计算显示，质子化通过改变三重态的电子结构和抑制导致快速衰变的光异构化，有效地削弱了核糖的影响。这些发现为利用质子化来调节硫代核苷的三重态衰变动力学以及在光化学应用中开发 pH 响应策略提供了一条新途径。

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

The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

9.60

自引率

7.00%

发文量

1519

审稿时长

1.6 months

期刊介绍： The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.