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NITROSYL AND NITROSO COMPLEXES OF METALLOPORPHYRINS

金属卟啉的亚硝基和亚硝基配合物

基本信息

批准号：
6181311
负责人：
George Bannerman Richter-Addo
金额：
$ 7.32万
依托单位：
UNIVERSITY OF OKLAHOMA
依托单位国家：
美国
项目类别：
财政年份：
1996
资助国家：
美国
起止时间：
1996-08-01 至 2002-07-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/6181311
关键词：
X ray crystallography active sites chemical bond chemical synthesis chlorin iron metalloporphyrins nitric oxide nitrites nitrosamines nitroso compounds ruthenium

项目摘要

Our efforts in the area of bioinorganic chemistry of nitric oxide (NO) are directed towards understanding how this small paramagnetic molecule functions in the chemistry of mammalian systems. The growth in interest in NO chemistry can be attributed to the discovery within the last several years that this remarkable small molecule is responsible for a host of biological phenomena such as the maintenance of normal blood pressure, neurotransmission, and DNA damage. Research in our laboratory involves the study of the fundamental chemistry of metal-NO linkages in biomolecules. No such studies have been done previously. Thus, the preparation of a series of NO complexes of metalloporphyrins (of varying electron-donating ability) and metallochlorins of some late first-row transition metals (Mn, Fe, Co) will be pursued. These metals are biologically active in a variety of ligand environments, and the NO complexes of metalloporphyrins/chlorins are potential models for heme-NO and cytochrome-NO interactions. The fundamental chemistry of the resulting product species with electrophilic and nucleophilic reagents to produce new sulfur-nitrogen, carbon-nitrogen, and nitrogen-nitrogen bonds will be investigated. The interaction of nitrosamines and thionitrites with the metalloporphyrins/chlorins will also be studied. Although nitrosamines are of environmental consequence and can be found in food and cigarette smoke, no studies have been conducted on how these carcinogenic molecules bind to metal complexes that may be present in the human body. Thus, the study of how the atoms in the nitrosamines bind to the metal centers in porphyrin-type compounds, and how these interactions control the eventual decomposition and/or activation pathways of the resulting biochemical species will be pivotal to developing new chemical routes for the deactivation of these carcinogens.

我们在一氧化氮(NO)生物无机化学领域的努力旨在理解这种顺磁小分子是如何哺乳动物系统的化学功能。利息的增长在任何化学中都不能归因于上一次的发现几年来，这种非凡的小分子负责一系列生物现象，如维持正常血液压力、神经传递和DNA损伤。我们实验室的研究涉及研究金属的基本化学--无键生物分子。此前还没有人做过这样的研究。因此，不同金属卟啉系列NO络合物的制备电子供体能力)和某晚第一排的金绿素过渡金属(锰、铁、钴)将受到追捧。这些金属是在各种配基环境中具有生物活性，而NO 金属卟啉/氯化物络合物是血红素-NO的潜在模型和细胞色素-无相互作用。生物化学的基本原理使用亲电试剂和亲核试剂生成的产品种类生产新的硫氮、碳氮和氮素债券将受到调查。亚硝胺和亚硝胺的相互作用还将研究含有金属卟啉/氯的硫硝酸盐。尽管亚硝胺会对环境造成后果，而且在食物和香烟烟雾中，还没有研究表明这些物质是如何致癌分子与金属络合物结合，这些金属络合物可能存在于人体。因此，研究亚硝胺中的原子如何与卟啉类化合物中的金属中心结合，以及这些相互作用控制着最终的分解和/或激活由此产生的生化物种的途径将是关键开发新的化学途径来灭活这些致癌物质。