Generation and Solution Reactivity of Nitroxyl (HNO)

硝酰基 (HNO) 的生成和溶液反应性

• 批准号: 0518406
• 负责人: John Toscano
• 金额: $ 53.1万
• 依托单位: Johns Hopkins University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-05-15 至 2009-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0518406&HistoricalAwards=false
• 关键词: Generation; Solution; Reactivity; Nitroxyl; HNO

With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor John Toscano of the Chemistry Department at Johns Hopkins University. The research will extend the PI's studies of reactive intermediates to research involving the generation and solution reactivity of nitroxyl (HNO). The research will address two main goals: (1) to develop a variety of new photochemical and thermal precursors to HNO and (2) to use these precursors (as well as existing ones) to elucidate the fundamental solution-phase chemistry of HNO. Photochemical precursors to HNO that will be examined include HNO-diene Diels-Alder adducts, hydroxynitrene (HON) precursors, and photosensitive O-substituted sulfohydroxamic acid derivatives. The project will involve the use of nanosecond time-resolved infrared (TRIR) spectroscopy, as well as more standard experimental and computational tools. The direct detection of HNO by TRIR spectroscopy in both aqueous and organic solvents will be attempted. The reactivity of HNO with various species of both fundamental and biological interest will also be examined by TRIR spectroscopy.The biochemistry of the nitroxyl system has recently received significant attention, especially as a potential alternative to current treatments of cardiac failure. Although unique biological responses have been attributed to nitroxyl, very little is known about the fundamental solution chemistry of this deceptively simple system. The mechanistic information concerning nitroxyl, which impacts upon the physiology of many organisms, will be extremely valuable to the biomedical community. This research will afford broad training for students who will acquire a wide range of skills. Undergraduate participation in the proposed research will be emphasized with students from Johns Hopkins University and nearby Towson University involved.

有了这个更新奖，有机和高分子化学计划继续支持约翰霍普金斯大学化学系教授约翰托斯卡诺的工作。 这项研究将扩大PI的研究涉及硝酰基（HNO）的生成和溶液反应性的反应性中间体的研究。 该研究将解决两个主要目标：（1）开发各种新的光化学和热前体HNO和（2）使用这些前体（以及现有的）阐明HNO的基本溶液相化学。 将被检查的HNO的光化学前体包括HNO-二烯Diels-Alder加合物、羟基氮烯（HON）前体和光敏O-取代的磺基异羟肟酸衍生物。该项目将涉及使用纳秒时间分辨红外（TRIR）光谱，以及更多的标准实验和计算工具。尝试在水溶液和有机溶剂中用TRIR光谱法直接检测HNO。HNO与各种物质的基本和生物学利益的反应性也将被检查TRIR spectroscopy.的nitroxyl系统的生物化学最近受到了极大的关注，特别是作为一个潜在的替代目前的治疗心力衰竭。虽然独特的生物反应已归因于硝酰基，很少有人知道这个看似简单的系统的基本溶液化学。 硝酰基对许多生物体的生理有影响，其机制信息对生物医学界将是极其有价值的。 这项研究将为学生提供广泛的培训，他们将获得广泛的技能。 本科生参与拟议的研究将强调与学生从约翰霍普金斯大学和附近的陶森大学参与。