METALLOPORPHYRINS SPIN COUPLING AND C60

本计画探讨金属卟啉的化学、自旋偶合 现象，和C60，所有的目标是发现新的基础 化学是生物学分子水平理解的基础， 药 超结构金属卟啉的生物无机化学 富勒烯将被研究，以发现新的多金属和多， 电子化学螯合铜或电子的铁卟啉 储层替代物（例如C60、二茂铁）将作为模型， 细胞色素氧化酶更多样化的金属和配体选择（例如， “膦钳卟啉”）将允许利用化学独特的 到双核配体。 将探讨自旋耦合现象， 特别是测试磁轨道正交性的概念。 过氧化物酶化合物I的模型将测试a-1-u之间的差异 和a-2-u卟啉自由基与铁的自旋偶合及其与 卟啉起皱。磁化学系列的新概念将是 探索与混合自旋铁（III）卟啉。 根本 C60的化学将被探索，以建立化学基础， 潜在的生物医学应用。所有这些研究的重点将 分析纯的确定性表征 材料的X射线晶体学和光谱学方法， 新化学的发现，以及与 金属蛋白的分子水平化学，特别是 血红素蛋白 对这一基本的生物无机化学的理解， 治疗金属蛋白紊乱的医学方法 （地中海贫血、镰状细胞贫血等）。新的配体及其金属 复合物正被用作抗关节炎药物。C60具有 在光动力疗法和作为抗病毒剂中的潜在应用。

This project explores the chemistry of metalloporphyrins, spin coupling phenomena, and C60, all with the goal of discovering fundamental new chemistry that underpins the molecular level understanding of biology and medicine. The bioinorganic chemistry of superstructured metalloporphyrins and fullerenes will be investigated to uncover new multi-metal and multi- electron chemistry. Iron porphyrins with chelated copper or electron reservoir substituents (e.g. C60, ferrocene) will serve as models for cytochrome oxidase. A more diverse selection of metals and ligands (e.g. 'phosphine pincer porphyrin') will allow exploitation of chemistry unique to binucleating ligands. Spin coupling phenomena will be explored, particularly to test concepts of orthogonality of magnetic orbitals. Models for peroxidase Compound I will test the difference between a-1-u and a-2-u porphyrin radical spin coupling to iron and its relationship to porphyrin ruffling. The novel concept of a Magnetochemical Series will be explored with admixed spin iron(III) porphyrins. The fundamental chemistry of C60 will be explored to establish a chemical basis for potential biomedical applications. Emphasis in all of these studies will be placed on the definitive characterization of analytically pure materials by X-ray crystallography and spectroscopic methods, on the discovery of new chemistry, and on the demonstration of relationships to the molecular level chemistry of metalloproteins, particularly hemoproteins. An understanding of this fundamental bioinorganic chemistry must underlie medical approaches to the therapy of metalloprotein disorders (thalassemias, sickle cell anemia, etc.). New ligands and their metal complexes are finding applications as anti-arthritic drugs. C60 has potential applications in photodynamic therapy and as an anti-viral agent.