COPPER AND IRON DIOXYGEN REACTIVITY IN MODEL COMPLEXES

描述：(改编自申请者的摘要)独特的生物运动 对合成小分子的催化反应性，而令人敬畏的 挑战，是一项非常耐人寻味和信息量很大的努力，提供了 对原生反应性的批判性见解。宏大而长远的目标 这项研究的重点是阐明化合物的结构和电子性质。 生物单核、双核和三核中形成的CuO2形态 铜中心及其氧化反应性的后续表征。这个 方法学是合成类比方法来研究活性中心。 金属生物分子，由此合成低分子络合物，并 在小分子细节水平上进行检查，以揭示 金属络合物不受蛋白质基质的影响。这个 前提是生物体的形成和随后的反应性 在以下情况下，中间体在小型合成络合物中应该是可重现的 设计了适当的连接环境，如果是有害的 避免了反应性中间体的双分子反应。创建 光谱上一致的功能模型是最终目标，因此 建议的生物机制的具体方面可在 小分子级别的细节。具体目标是：结构性的， [Cu(I)LDAL(MeCN)]1+-O2的光谱和反应活性表征 产品使用简单的全烷基二胺配体(LDA)提供化学 可能的生物中间体和光谱基准的优先顺序 这些中间体可以通过它来识别。反应性表征 新的中间体可能导致新的生物启发氧化催化剂。定义 催化功能半乳糖氧化酶的机理关系 将复合体模型复制到本机系统。更高抗氧化性的研究进展 模型络合物将有助于机理和动力学的研究。集成 组氨酸终止的多肽进入配基框架将提供更多 半乳糖氧化酶的生物学相关功能模型。功能性 单核三配位铜原子与铜原子的反应性 调查促进氧气活化的环境类型、类型 铜-氧中间体的形成及酚基氧化机理 修饰，单核铜酶的一个新兴主题。开发一种 单核铁酶脂氧合酶与血管紧张素转换酶的作用机制 显示与CH最一致的氧化行为的单核铁模型 氢原子抽象。

DESCRIPTION: (adapted from applicant's abstract) Movement of unique biological catalytic reactivity to small synthetic molecules, while a formidable challenge, is an extremely intriguing and informative endeavor providing critical insights into the native reactivity. The broad and long-term objective of this research is elucidation of the structural and electronic properties of Cu-O2 species formed in biological mononuclear, binuclear and trinuclear Cu-sites and subsequent characterization of their oxidative reactivity. The methodology is that of the synthetic analog approach to the active sites of metallobiomolecules, whereby low molecular weight complexes are synthesized and examined at a small molecule level of detail to reveal intrinsic properties of the metal complexes uncoupled from the influences of the protein matrix. The premise is that the formation and subsequent reactivity of biological intermediates should be reproducible in small synthetic complexes if appropriate ligation environments are engineered, and if deleterious bimolecular reactions of the reactive intermediates are avoided. Creation of spectroscopically congruent, functional models is the ultimate goal so that specific aspects of proposed biological mechanisms may be investigated at a small molecule level of detail. The specific aims are as follows: Structural, spectroscopic and reactivity characterization of [Cu(I)LDAL(MeCN)]1+-O2 products using simple peralkylated diamines ligands (LDA) to provide chemical precedence for possible biological intermediates and spectroscopic benchmarks by which such intermediates may be identified. Reactivity characterization of new intermediates may lead to new bio-inspired oxidation catalysts. Defining the mechanistic relationship of catalytically functional galactose oxidase model complexes to the native system. Development of more oxidatively resistant model complexes will aid in the mechanistic and kinetic studies. Integration of histidine terminated peptides into the ligand framework will provide more biologically relevant functional models of galactose oxidase. Functional modeling of the reactivity of mononuclear trigonally-ligated copper sites to investigate the type of environments that promote O2 activation, the type of Cu-O2 intermediates formed, and the mechanism of phenolate group oxidative modification, an emerging theme in mononuclear copper enzymes. Development of a mechanistic relationship between lipoxygenase, a mononuclear iron enzyme, and mononuclear iron models that exhibit oxidation behavior most consistent with CH hydrogen atom abstraction.