Thermal and Photochemical Reactions of Transition Metal Complexes of the Nitrogen Oxides

氮氧化物过渡金属配合物的热反应和光化学反应

• 批准号: 0352650
• 负责人: Peter Ford
• 金额: $ 71.9万
• 依托单位: University of California-Santa Barbara
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-03-01 至 2009-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0352650&HistoricalAwards=false
• 关键词: Thermal; Photochemical; Reactions; Transition; Metal

This award supports research by Professor Peter C. Ford at the University of California at Santa Barbara to pursue investigations of the photochemical and thermal reactions of transition metal complexes of nitric oxide (NO) and other nitrogen oxide ligands (NOx). One goal is to develop precursors that can be photochemically activated for NO delivery to biological targets. Another goal is to characterize interactions of NO and other NOx such as nitrite ion, NO2, N2O3, the nitroxyl anion NO- and HNO, with metal centers and the influence of such interactions on the reactivities of these species. Modern kinetics instrumentation will be used to elucidate the pathways by which these compounds react, either spontaneously or under photochemical stimulation. These methods include time-resolved optical and infrared spectroscopy of reactive intermediates generated by laser flash photolysis or by rapid mixing. Computational techniques will be employed to investigate the relative energies and spectra of known and unknown compounds (using density functional theory) and to simulate the kinetics behavior observed or expected for complex reaction systems. Studies will explore the reaction mechanisms for the basic chemical transformations such as the formation and breaking of metal-ligand bonds and the atom and electron transfer reactions that constitute the chemistry of these "simple" species. Although fundamental in nature, the proposed studies have potential relevance to the design of materials displaying desirable photochemical properties for biomedical applications and for the reinterpretation of the mechanism(s) by which a prospective vasodilator is formed in the hemoglobin of red blood cells. The research also serves as a platform for the education and training of members of underrepresented groups at the graduate, undergraduate and postdoctoral levels.

该奖项支持Peter C教授的研究。圣巴巴拉的加州大学的福特博士研究了一氧化氮（NO）和其他氮氧化物配体（NOx）的过渡金属络合物的光化学和热反应。 一个目标是开发可以被光化学激活以将NO递送到生物靶标的前体。 另一个目标是表征NO和其他NOx如亚硝酸根离子、NO2、N2 O3、硝酰基阴离子NO-和HNO与金属中心的相互作用以及这种相互作用对这些物质的反应性的影响。 现代动力学仪器将被用来阐明这些化合物的反应，无论是自发或光化学刺激下的途径。 这些方法包括激光闪光光解或快速混合产生的活性中间体的时间分辨光学和红外光谱。 计算技术将用于研究已知和未知化合物的相对能量和光谱（使用密度泛函理论），并模拟复杂反应系统观察到或预期的动力学行为。 研究将探索基本化学转化的反应机制，如金属-配体键的形成和断裂，以及构成这些“简单”物质化学的原子和电子转移反应。 虽然本质上是基础性的，但所提出的研究与显示生物医学应用所需的光化学性质的材料的设计以及对红细胞血红蛋白中形成预期血管扩张剂的机制的重新解释具有潜在的相关性。 这项研究还为在研究生、本科生和博士后一级教育和培训代表性不足群体的成员提供了一个平台。