Chemistry of Metal Nitrosyls with Photolabile NO

金属亚硝基化合物与光不稳定 NO 的化学

• 批准号: 0553405
• 负责人: Pradip Mascharak
• 金额: $ 43.2万
• 依托单位: University of California-Santa Cruz
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-07-01 至 2011-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0553405&HistoricalAwards=false
• 关键词: Chemistry; Metal; Nitrosyls; Photolabile; NO

The award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Pradip K. Mascharak at the University of California at Santa Cruz to synthesize new non-heme iron, ruthenium and manganese nitrosyls that will release NO upon illumination at various wavelengths of light. The spectroscopic and electronic properties of these complexes will be explored in order to determine what factor(s) promote the photolability of NO and their structures will be determined. A set of guiding principles and a series of ligands designed after the metal-binding domain of the enzyme nitrile hydratase, which is photoregulated through NO binding, will be utilized in the syntheses of these metal nitrosyls. In addition, redox and magnetic measurements will be performed on both photoactive and inactive metal nitrosyls to elucidate the origin of the photolability of NO bound at these metal centers in different oxidation states. Theoretical calculations will also be performed to gather further insight into this process. The mechanisms of the light-induced NO release will be explored and the capacities of the nitrosyl complexes to transfer NO to various biologically relevant substrates, such as glutathione and proteins, will be measured. This research aims at identifying the chemical architectures and the associated electronic features that provide for the photolability of NO. Such nitrosyl complexes will provide the biochemists with a tool to study the kinetics of NO binding (and inhibition) to heme and non-heme proteins by optical spectroscopy. The results of this research work will provide valuable chemical insights toward syntheses of inorganic NO donors as photochemotherapeutics. This research also provides an opportunity for graduate and undergraduate students to participate in systematic goal-oriented research at the interface of chemistry and biology.

无机，生物无机和有机化学计划的奖项支持Pradip K教授的研究。位于圣克鲁斯的加州大学的Mascharak合成了新的非血红素铁、钌和锰亚硝基化合物，这些化合物在各种波长的光照射下都会释放出NO。 将探索这些复合物的光谱和电子性质，以确定哪些因素促进NO的光化性，并确定它们的结构。 一套指导原则和一系列的配体后，设计的酶腈水合酶，这是通过NO结合光调节的金属结合域，将被用于这些金属亚硝基的合成。此外，氧化还原和磁性测量将进行光活性和非活性的金属亚硝基，以阐明在这些金属中心在不同的氧化态的光敏性NO绑定的起源。 还将进行理论计算，以进一步了解这一过程。光诱导的NO释放的机制将被探索和亚硝酰基复合物转移NO到各种生物相关的底物，如谷胱甘肽和蛋白质的能力，将被测量。这项研究的目的是确定的化学结构和相关的电子功能，提供了光的NO。这样的亚硝酰基配合物将提供一个工具，研究动力学的NO结合（和抑制）血红素和非血红素蛋白的光学光谱。 本研究的结果将为无机NO供体的光化学治疗提供有价值的化学见解。这项研究也为研究生和本科生提供了一个机会，在化学和生物学的接口参与系统的目标导向的研究。