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Development of new caged-NO molecules having aromatic nitro compound as a basic framework and their NO-release abilities

以芳香硝基化合物为基本骨架的新型笼状NO分子的研制及其NO释放能力

基本信息

批准号：
20750035
负责人：
INUI Hiroshi
金额：
$ 2.75万
依托单位：
Kitasato University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Young Scientists (B)
财政年份：
2008
资助国家：
日本
起止时间：
2008 至 2010
项目状态：
已结题

项目摘要

Photochemical nitric oxide (NO) donors, which make it possible to release NO at the desired time and space, are useful to study various physiological processes in detail. In this work, a variety of 9-nitroanthracene derivatives having a substituent at 10-position was designed and synthesized as NO donor candidates, and the mechanism and ability on the photochemical NO release from the compounds were investigated using matrix-isolation technique and product analyses in solutions. Upon irradiation in matrices at 10 K, it was established that most of the nitroanthracenes with visible light gives NO and the oxyradical-forms via the nitrite-forms, and that the oxyradical + NO and the nitrite can be converted photochemically each other. And also, it was found that 9,10-dinitroanthracene afford NO and anthraquinone without giving the intermediates such as the nitrite and oxyradical. While the irradiation of nitroanthrancenes in solutions at room temperature afforded mainly bianthrone-forms, anthraquinoe, and anthracenedione oxyme accompanied with NO generation. On the basis of the results from the trapping of NO with Griess reagent and the measurements of absolute quantum yield for the photodecomposition of substrates, it was confirmed that the ability of photochemical NO generation increases according to increasing the electron-withdrawing properties of a substituent introduced to 10-position of 9-nitroanthracene. This result can be interpreted as a consequence of accelerating the transformation from nitro-forms to nitrite-forms by increasing the torsion angle between nitro group and anthracene-sp^2 plane.

光化学一氧化氮 (NO) 供体可以在所需的时间和空间释放 NO，有助于详细研究各种生理过程。在这项工作中，设计并合成了多种在10位具有取代基的9-硝基蒽衍生物作为NO供体候选物，并利用基质分离技术和溶液中的产物分析研究了这些化合物光化学释放NO的机制和能力。在 10 K 的基质中照射后，发现大多数硝基蒽在可见光下会通过亚硝酸盐形式生成 NO 和氧自由基形式，并且氧自由基 + NO 和亚硝酸盐可以通过光化学方式相互转化。并且还发现9,10-二硝基蒽可以生成NO和蒽醌，而不生成亚硝酸盐和氧自由基等中间体。而硝基蒽在室温下的溶液中的辐照主要产生联蒽酮形式、蒽醌和蒽二酮肟，并伴有NO生成。根据格里斯试剂捕获NO的结果以及底物光分解绝对量子产率的测量结果，证实了光化学NO生成能力随着引入到9-硝基蒽10位的取代基的吸电子性能的增加而增加。这一结果可以解释为通过增加硝基与蒽-sp^2平面之间的扭转角加速从硝基形式向亚硝酸盐形式转变的结果。