蝶呤-胸苷加合物:从它们的光化学合成到它们的光敏性。

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
The Journal of Physical Chemistry B Pub Date : 2025-04-03 Epub Date: 2025-03-25 DOI:10.1021/acs.jpcb.5c00185
Gricelda Godoy-Ortega, Gemma M Rodríguez-Muñiz, Virginie Lhiaubet-Vallet, Carolina Lorente, Andrés H Thomas
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引用次数: 0

摘要

Pterin (Ptr)是芳香pterins的模型化合物,它是存在于人体皮肤中的有效光敏剂,能够在UVA照射下氧化生物分子。光敏化涉及由于另一种化学物质(光敏剂)最初吸收辐射而引起的生物分子的化学改变。在厌氧条件下,Ptr与胸腺嘧啶(T)反应形成光加合物(T-Ptr)。本文提出了以2′-脱氧胸腺嘧啶5′-单磷酸(dTMP)和单链寡核苷酸5′-d(TTTTT)-3′(dT5)制备和纯化T-Ptr加合物的方法,并研究了它们的光敏性。有趣的是,Ptr部分,当连接到T时,保留其光物理性质。加合物dTMP-Ptr在激发后形成单线态和三重态激发态,后者能够将能量传递给溶解的O2并产生单线态氧,其效率与Ptr相似。在空气平衡溶液中,dTMP-Ptr和dT5-Ptr加合物都能使色氨酸和2'-脱氧鸟苷5'-单磷酸的氧化光敏,这是生物系统中光敏的两个主要目标,其效率接近于游离Ptr。参与生物分子氧化的机制可以是I型(电子转移)或II型(单线态氧)。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Pterin-Thymidine Adducts: From Their Photochemical Synthesis to Their Photosensitizing Properties.

Pterin (Ptr) is the model compound of aromatic pterins, which are efficient photosensitizers present in human skin and are able to oxidize biomolecules upon UVA irradiation. Photosensitization involves chemical alteration of a biomolecule as a result of the initial absorption of radiation by another chemical species, the photosensitizer. Under anaerobic conditions, Ptr reacts with thymine (T) to form photoadducts (T-Ptr). In this work, we present a method to prepare and purify T-Ptr adducts, using 2'-deoxythymidine 5'-monophosphate (dTMP) and single stranded oligonucleotide 5'-d(TTTTT)-3' (dT5), and investigate their photosensitizing properties. Interestingly, the Ptr moiety, when attached to T, retains its photophysical properties. The adduct dTMP-Ptr, upon excitation, forms singlet and triplet excited states, the latter being capable of transferring energy to dissolved O2 and generating singlet oxygen, with an efficiency similar to Ptr. In air-equilibrated solutions, both dTMP-Ptr and dT5-Ptr adducts can photosensitize the oxidation of tryptophan and 2'-deoxyguanosine 5'-monophosphate, two of the main targets of photosensitization in biological systems, with efficiencies close to that of free Ptr. The mechanisms involved in the oxidation of biomolecules can be either type I (electron transfer) or type II (singlet oxygen).

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来源期刊
CiteScore
5.80
自引率
9.10%
发文量
965
审稿时长
1.6 months
期刊介绍: An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.
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