Synthesis and Photophysics of Water-Soluble Psoralens with Red-Shifted Absorption,Photochemistry and Photobiology

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Synthesis and Photophysics of Water-Soluble Psoralens with Red-Shifted Absorption
Photochemistry and Photobiology ( IF 2.6 ) Pub Date : 2021-06-28 , DOI: 10.1111/php.13480
Janina Bertling ₁ , Kristoffer A Thom ₁ , Sarah Geenen ₂ , Hannah Jeuken ₁ , Lysander Presser ₂ , Thomas J J Müller ₂ , Peter Gilch ₁

Affiliation

8-Methoxypsoralen (8-MOP) serves as a PUVA (psoralen + UV-A) agent in the treatment of certain skin diseases. Derivatives of 8-MOP with cationic aromatic substituents at the five positions were synthesized and characterized by steady-state, femtosecond and nanosecond spectroscopy as well as cyclic voltammetry. The aromatic substituents' positive charge increases the water solubility and the affinity toward intercalation into DNA. The aromatic substituents were supposed to lower the psoralen S₁ energy and thereby suppress a photo-induced electron transfer (PET) with guanine-bearing DNA. Such a suppression of this PET is expected to increase the propensity of psoralens to photo-addition to DNA. For derivatives bearing methylpyridinium residues, femtosecond spectroscopy revealed an intramolecular PET occurring on the picosecond time scale. This PET precludes the population of the triplet state. As triplet states are the precursor state for the photo-addition to DNA, their intermolecular PET renders these derivatives ineffective in terms of PUVA. For two derivatives bearing trimethylphenylammonium moieties, such an intramolecular PET does not occur and the triplet state is populated. Surprisingly, these compounds also exhibit no PUVA activity. Based on these findings, implications for further optimization of PUVA agents are discussed.

中文翻译：

红移吸收水溶性补骨脂素的合成及光物理

8-甲氧基补骨脂素 (8-MOP) 用作治疗某些皮肤病的 PUVA（补骨脂素 + UV-A）剂。合成了 8-MOP 在五个位置上具有阳离子芳族取代基的衍生物，并通过稳态、飞秒和纳秒光谱以及循环伏安法对其进行了表征。芳族取代基的正电荷增加了水溶性和对嵌入 DNA 的亲和力。芳香族取代基应该降低补骨脂素 S ₁能量，从而抑制带有鸟嘌呤的 DNA 的光诱导电子转移 (PET)。预计这种 PET 的这种抑制会增加补骨脂素对 DNA 的光加成倾向。对于带有甲基吡啶鎓残基的衍生物，飞秒光谱揭示了在皮秒时间尺度上发生的分子内 PET。该 PET 排除了三重态的人口。由于三重态是光加成 DNA 的前体状态，它们的分子间 PET 使这些衍生物在 PUVA 方面无效。对于带有三甲基苯基铵部分的两种衍生物，不会出现这样的分子内 PET 并且填充了三重态。令人惊讶的是，这些化合物也没有表现出 PUVA 活性。基于这些发现，讨论了进一步优化 PUVA 剂的意义。

更新日期：2021-06-28

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