Photosensitization of fluorofuroxans and its application to the development of visible light-triggered nitric oxide donor
Photosensitization of fluorofuroxans and its application to the development of visible light-triggered nitric oxide donor
复制标题
氟呋喃酮的光敏化及其在可见光触发一氧化氮供体开发中的应用
DOI：
10.1021/acs.joc.7b01709
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发表时间：
2017
期刊：
影响因子：
3.6
通讯作者：
Masahiko Hayashi and Ryosuke Matsubara
中科院分区：
文献类型：
--
作者：
Christopher Peter Seymour;Rei Toda;Motonari Tsubaki;Masahiko Hayashi and Ryosuke Matsubara
一氧化氮 (NO) 是一种内源性信号分子，用于多种生化过程。在时空控制下提供一氧化氮有效负载的可切换一氧化氮供体的开发具有许多医学益处。此前，基于光诱导异构化机制，4-氟呋喃酮被发现在生理条件下可作为紫外光诱导的NO供体；然而，为了进一步应用于生命系统，需要用更长波长的光进行氟呋喃异构化。在此，我们报道了在氟呋喃生的光化学异构化中使用光敏剂，从而能够利用可见光诱导异构化。在所尝试的光敏剂中，蒽醌衍生物在可见光下表现出良好的将4-氟呋喃异构化为3-氟呋喃的敏化能力。这一新现象被应用于水溶性蒽醌-氟呋喃一体分子的合成，该分子在 400-500 nm 照射下表现出良好的 NO 释放能力。通过“开”和“关”NO释放功能显示出高水平的控制，这表明光敏剂-呋喃氧杂合物将成为有价值的供体。此外，与大多数呋喃酮不同，NO 是在没有硫醇辅助因子的情况下释放的。
Nitric oxide (NO) is an endogenous signaling molecule used in multiple biochemical processes. The development of switchable NO donors that deliver an NO payload under spatiotemporal control harbors many medicinal benefits. Previously, 4-fluorofuroxans were found to function as a UV light-induced NO donor under physiological conditions based on the photoinduced isomerization mechanism; however, the isomerization of fluorofuroxans with longer wavelength light is desired for further application into living systems. Herein, we report the use of photosensitizers in the photochemical isomerization of fluorofuroxan, enabling the use of visible light to induce isomerization. Among the tried photosensitizers, anthraquinone derivatives showed a good sensitizing ability to isomerize 4-fluorofuroxan to 3-fluorofuroxan using visible light. This new phenomenon was applied to the synthesis of a water-soluble anthraquinone-fluorofuroxan all-in-one molecule, which demonstrated promising NO-releasing ability using 400–500 nm irradiation. A high level of control is displayed with “on” and “off” NO-release functionality suggesting that photosensitizer-furoxan hybrids would make valuable donors. Furthermore, unlike most furoxans, NO is released in the absence of thiol cofactor.