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Photochemical and photophysical investigations of dye derivatized iron sulfur nitrosyl compounds: Photochemical production of nitric oxide via single and two photon excitation.

机译:染料衍生的铁硫亚硝酰基化合物的光化学和光物理研究:通过单和两个光子激发光化学生产一氧化氮。

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摘要

Nitric Oxide (NO) is a ubiquitous biological messenger which is involved in a plethora of roles in mammalian biology including vasodilation, immune response, and neurotransmission. NO has also been demonstrated to be a gamma-radiation sensitizer, and as such, maybe used to improve the therapeutic effects of radiation treatment in the fight against certain cancers. These properties have provided attractive promise for the use of NO in the treatment of disease, but the deleterious effects of NO on vascular biology have limited their use as thermal NO delivery systems. One strategy to circumvent the undesired side effects of thermally delivered NO drugs is to develop thermally stable, NO containing precursors that can be photochemically triggered to release nitric oxide. In this regard, our group is concerned with the development of metal-nitrosyl complexes that photochemically produce nitric oxide on demand. A characteristic of particular importance to photochemical delivery drugs is the ability to absorb light at wavelengths between 800--1100 run where light penetration through tissue is maximized. Therefore the current focus is on designing compounds that can absorb light (by single or two photon excitation) in the NIR, undergo energy transfer to the metal center, and then result in the photochemical labilization of NO. A second advantage of using two photon excitation (TPE) for pro-drug activation is the enhanced spatial selectivity gained due to the intensity squared dependence of a two photon process.; In these contexts, the primary focus of this dissertation has been on the development, photochemical and photophysical investigations of dye derivatized iron sulfur nitrosyl compounds (known as the Roussin's red salt esters, RSE) for use as photochemical NO delivery agents via single and two photon excitation. One compound developed for these purposes was Fluor-RSE (Bis-[(mu-S, mu-S')-fluorescein-thioethylester]-tetranitrosyl diiron), which contains two fluorescein moieties as the light absorbing antenna. The photochemistry and photophysics of Fluor-RSE were investigated under single photon excitation (SPE) with UV-vis light and two photon excitation with near infrared (NIR) light, and have demonstrated that Fluor-RSE photochemically produces NO via single and two photon excitation.
机译:一氧化氮(NO)是一种普遍存在的生物信使,它在哺乳动物生物学中具有多种作用,包括血管舒张,免疫反应和神经传递。还已经证明NO是伽马射线辐射敏化剂,因此,可以用于改善放射线对抗某些癌症的治疗效果。这些性质为将NO用于治疗疾病提供了诱人的希望,但是NO对血管生物学的有害作用限制了它们作为热NO输送系统的用途。规避热传递NO药物不良副作用的一种策略是开发热稳定的,含NO的前体,这些前体可以通过光化学作用释放出一氧化氮。在这方面,我们小组关注开发可根据需要以光化学方式生产一氧化氮的金属-亚硝酰基配合物。对光化学传递药物特别重要的一个特征是能够吸收800--1100nm波长的光,其中最大程度地穿透组织。因此,当前的重点是设计能够吸收NIR中的光(通过单光子激发或两个光子激发),经历能量转移到金属中心,然后导致NO的光化学标记的化合物。使用两个光子激发(TPE)进行前药激活的第二个优点是由于两个光子过程的强度平方相关性而获得的增强的空间选择性。在这些情况下,本论文的主要重点是染料衍生的铁硫亚硝酰基化合物(称为鲁辛红盐酯,RSE)的开发,光化学和光物理研究,该化合物可通过单光子和两个光子用作光化学NO传递剂。激发。为此目的开发的一种化合物是Fluor-RSE(Bis-[[(mu-S,mu-S')-荧光素-硫代乙酯]-四亚硝酰基二铁),其中包含两个荧光素部分作为吸光天线。在紫外可见光的单光子激发(SPE)和近红外(NIR)的两个光子激发下,对Fluor-RSE的光化学和光物理进行了研究,并证明Fluor-RSE通过单和两个光子激发以光化学方式产生NO。 。

著录项

  • 作者

    Wecksler, Stephen Robert.;

  • 作者单位

    University of California, Santa Barbara.;

  • 授予单位 University of California, Santa Barbara.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2006
  • 页码 322 p.
  • 总页数 322
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;
  • 关键词

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