SYNTHETIC MODELS OF IRON SITES IN BIOLOGICAL SYSTEMS

这一研究计划的主导主题是开发系统化和 用于合成铁簇合物或聚集体的反应策略， 定义为由简单阴离子配体桥联的多个铁离子，如 氧化物，氢氧化物。这些聚集体将作为结构的、电子的 和生物系统中非血红素铁中心的功能模型 一般铁氧聚合过程，以便更好地了解 铁在自然界中的关键作用。铁在氧气中起着至关重要的作用 电子转移反应以及许多酶过程，因此 对这些铁中心的形成和功能以及 铁的储存对健康是必不可少的。对高效使用的破坏 铁的所有不同作用都会导致许多疾病。毒品，如 例如，阿司匹林与铁酶和更多的 对铁的配位化学和反应性有全面的了解 在设计这类药物时会说有氧气。 对化学这一探索性领域的系统方法包括 第一，多种铁(II)单核化合物的分离和鉴定 和多核配合物；它们的相互转化和相互作用 氧形成多核铁(III)氧聚集体。这种互动 通过氧气模型，许多关键的生物功能--同样多样化 作为可逆的氧气运输，向底物氧化(碳氢化合物 氧化)和自由基生成(DNA合成)。阶梯式队形 随后详细地确定了这些集合体的 可能是为了得出管理金属集合体的原则 队形。铁储存蛋白中的铁聚集过程 铁蛋白尤其令人担忧，目前有两家公司正在与其接洽 方向，聚集体，其中只涉及单一的氧桥和 双齿羧酸盐和磷酸基团起结构作用的那些 角色。物理化学技术被用来表征新材料 是X射线结晶学、~1H核磁共振、电子顺磁共振、紫外可见光谱和穆斯堡尔谱 和磁性。了解这些井的性质 定义的模型化合物极大地加快了物理解释的速度 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.