SYNTHETIC MODELS OF IRON SITES IN BIOLOGICAL SYSTEMS

该研究计划的主题是开发系统和 铁簇或聚集体的合成策略， 定义为通过简单阴离子配体桥连的多个铁离子 氧化物，氢氧化物。 这些聚集体将作为结构性的、电子的 以及生物系统中非血红素铁中心的功能模型， 一般的铁氧聚集过程，为了更好地了解 铁在自然界中的重要作用 铁在分子氧和 电子转移反应以及许多酶促过程，因此， 了解这些铁中心的形成和功能， 铁的储存对健康至关重要。 破坏有效使用 铁的各种作用导致许多疾病。 等药物 例如，阿司匹林与铁酶位点相互作用， 完全理解铁的配位化学和反应性 在设计这种药物时会说。 对化学这一探索性领域的系统方法包括 首先，分离和表征各种Fe（II）单核 和多核配合物;它们与 二氧形成多核铁（III）氧聚集体。 这种相互作用 与双氧模型的一些重要的生物功能-作为不同的 作为可逆的分子氧传输，到底物氧化（烃 氧化）和自由基生成（DNA合成）。 逐步形成 这些聚集体随后被确定尽可能详细， 为了达到控制金属聚集体的原则， 阵 铁贮存蛋白内的铁聚集过程 铁蛋白是特别令人关注的， 方向，聚集体，其中仅涉及单氧桥， 其中双齿羧酸根和磷酸根基团起结构性作用的那些 作用 表征新材料所依赖的物理化学技术 是X射线晶体学，1H NMR，EPR，UV-Vis光谱和穆斯堡尔谱 和磁性。 了解这些特性以及 定义的模型化合物大大加快了物理解释 金属蛋白的性质。

The governing theme of this research program is to develop systematic and reational strategies for the synthesis of iron clusters or aggregates, defined as multiple iron ions bridged by simple anionic ligands such as oxide, hydroxide. These aggregates are to serve as structural, electronic and functional models of non-heme iron centers in biological systems and of general iron-oxo aggregation processes, in order to better understand the critical role of iron in Nature. Iron plays a crucial role in dioxygen and electron transfer reactions as well as many enzymic processes, thus an understanding of the formation and function of these iron centers and the storage of iron is essential for health. Disruption of the efficient usage of iron in all its diverse roles leads to a number of diseases. Drugs such as aspirin, for example, interact with iron enzymatic sites and a more complete understanding of the coordination chemistry and reactivity of iron with oxygen will said in the design of such drugs. The systematic approach to this exploratory area of chemistry involves first the isolation and characterization of a variety of Fe(II) mononuclear and multinuclear complexes; their interconversions and interactions with dioxygen to form multinuclear iron(III) oxo aggregates. This interaction with dioxygen models a number of crucial biological functions - as diverse as reversible dioxygen transport, to substrate oxidation (hydrocarbon oxidation) and radical generation (DNA synthesis). The stepwise formation of these aggregates is subsequently determined in as much detail as possible in order to arrive at principles which govern metal aggregate formation. The iron aggregation processes within the iron storage protein ferritin are of particular concern and are being approached from two directions, aggregates where only single oxygen bridges are involved and those in which bidentate carboxylate and phosphate groups play a structural role. Physicochemical techniques relied upon to characterize new materials are X-ray crystallography, 1H NMR, EPR, UV-Vis spectroscopies and Mossbauer and magnetic properties. Understanding the properties of these well defined model compounds greatly accelerates the interpretation of physical properties of metalloproteins.