MECHANISMS OF REACTIONS OF OXYGEN WITH HEME PROTEINS

将制备血红蛋白和相关血红蛋白的模型化合物 以及它们的结构对反应动力学的影响 研究了氧气、一氧化碳和异腈。环状亚铁血红素 显示出远端副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 远端副作用的立体效应。新的邻位取代四苯基亚铁血红素 将制备衍生物及其与一氧化碳和氧气的相互作用 研究以定义血红素僵硬的新现象及其 对配体结合的影响。人工合成的血红素化合物已经证明 将用计算机研究协作性和依赖于pH的结合 建模，并通过滴定和动力学方法。血红素的闪光光解 将用FTIR方法对配合物进行研究，以获得闪光红外光谱 不稳定的中间体。闪光共振拉曼光谱的类似研究 将被用来描述发生的松弛过程 在无蛋白质的活性部位。这项研究将定义这些特征 血红素化合物及其控制变化的环境 这类血红素在血红素蛋白中的反应性。此信息将提供 理解血红蛋白和其他物质中协同作用的方法 生物分子反应，并将允许合成氧运输 供血液代用品使用的待制备材料。

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.