MECHANISMS OF REACTIONS OF OXYGEN WITH HEME PROTEINS

将制备血红蛋白和相关血红素蛋白的模型化合物 以及它们的结构对反应动力学的影响 分子氧、一氧化碳和异腈。 环蕃血红素 显示远侧空间效应的化合物将通过 结构，光谱和动力学方法，以确定性质 远侧空间效应的影响。 新的邻位取代四苯基血红素 将制备衍生物，并研究它们与CO和分子氧的相互作用 研究，以确定血红素刚性的新现象及其 对配体结合的影响。 合成血红素化合物已经证明， 显示协同性和pH依赖性结合将通过计算机进行研究 模拟和滴定和动力学方法。 血红素的闪光光解 络合物将通过FTIR方法进行研究，以获得 不稳定的中间体 闪光共振拉曼光谱的类似研究 将进行，以描述松弛过程发生 在无蛋白质的活性部位。 本研究将确定这些特征 血红素化合物和它们的环境，控制着各种 血红素在血红素蛋白中的反应性。 这些信息将提供 了解血红蛋白和其他蛋白协同性的方法 生物分子反应，并将允许合成氧运输 作为血液替代品使用的材料。

Model compounds for hemoglobin and related hemoproteins will be prepared and the effect of their structure on the dynamics of reaction with dioxygen, carbon monoxide, and isonitriles studied. Cyclophane heme compounds displaying distal side steric effect will be studied by structural, spectroscopic and kinetic methods in order to define the nature of the distal side steric effect. New ortho-substituted tetraphenylheme derivatives will be prepared and their interaction with CO and dioxygen studied in order to define the new phenomenon of heme rigidity and its effect on ligand binding. Synthetic heme compounds already demonstrated to show cooperativity and pH-dependent binding will be studied by computer modeling and by titration and kinetic methods. Flash photolysis of heme complexes will be studied by FTIR methods to obtain flash IR spectra of unstable intermediates. Similar studies by flash resonance Raman spectra will be undertaken in order to describe the relaxation processes occurring in protein-free active sites. This study will define those characteristics of heme compounds and their environment which control the varied reactivities of such hemes in hemoproteins. This information will provide the means of understanding the cooperativity in hemoglobin and other biomolecular reactions and will allow synthetic oxygentransporting materials, for use as blood substitutes, to be prepared.