MOLECULAR MECHANISMS OF BIOLOGICAL REDOX REACTIONS

使用各种光谱、物理和动力学方法， 表征重要生物学中的电子转移机制 系统. 重点放在酶复合物的线粒体 电子传递链和金属黄素蛋白上的黄嘌呤氧化酶。 主要的长期目标是确定结构和动态 线粒体复合体的属性足够详细， 能量守恒机制的假设可以被严格地 评估。 主要技术有光学、磁性圆二色性和电子 顺磁共振光谱，将采用在两个平衡 核磁共振和拉曼光谱 也将被利用。 需要处理的主要问题包括： (a)细胞色素组分的结构和动力学性质 氧化酶和氧中间体的性质。 (b)酵母复合物III的电子转移机制及其应用 Q循环的有效性。 (c)络合物III中血红素中心的配体。 (d)络合物II和III中铁硫中心的性质。 (e)配合物II的电子转移机理。 (f)酶的稳态动力学基本原理分析 每个底物的非相互作用反应位点。

A variety of spectroscopic, physical and kinetic methods are used to characterize the mechanism of electron transfer in important biological systems. Emphasis is placed on the enzyme complexes of the mitochondrial electron transfer chain and on the metalloflavoprotein, xanthine oxidase. Principal long-term objectives are to define the structural and dynamic attributes of the mitochondrial complexes in sufficient detail that hypotheses for the mechanisms of energy conservation can be rigorously evaluated. The principal techniques, optical, magnetic circular dichroism and electron paramagnetic resonance spectroscopy, will be employed in both equilibrium and kinetic experiments; nuclear magnetic resonance and Raman spectroscopy will also be utilized. Major issues to be addressed include: (a) The structural and kinetic properties of the components of cytochrome oxidase and the nature of the oxygen intermediates. (b) The mechanism of electron transfer in yeast Complex III and the validity of the Q-cycle. (c) Ligands of the heme centers in Complex III. (d) The nature of the iron-sulfur centers in Complexes II and III. (e) The mechanism of electron transfer in Complex II. (f) Analyses of the fundamentals of steady state kinetics in enzymes with non-interacting reaction sites for each substrate.