MODELING MANGANESE PEROXIDASE--A REACTIVITY STUDY

这一建议的主要目的是了解新的Fe/III(血红素)-X-Mn/II络合物[X=桥羟基(OH)-或氧代(O2)]的反应性和配位化学是锰过氧化物酶(MNP)的功能模型。建议的络合物包含生物相关的金属，铁和锰，这是MNP氧化降解木质素所需的。建议的络合物包含生物相关的金属，铁和锰，这是MNP氧化降解木质素所需的。将采取完善的合成策略和严格的提纯技术，以获得最终的Fe/III(血红素)-X-Mn/II产品。所提出的化合物与过氧化氢的反应活性应该产生桥式过氧基(O2/2)-络合物，甚至可能产生类似于化合物II的(卟啉)Fe/IV=O中间体。为了测试氧化降解催化的可能性，将在氧化中间体中引入与生物相关的底物(即木质素模型化合物)。一系列光谱方法[X-射线氧化降解催化的可能性。将使用一系列光谱方法[X射线结晶学、电顺磁共振、磁学、顺磁位移核磁共振、红外、磁性圆二色、电子吸收、共振拉曼]来探测所建议化合物的几何结构和电子结构，以及活性中间体。

The main objective of this proposal is to understand the reactivity and coordination chemistry of new Fe/III(heme)-X-Mn/II complexes [X=bridging hydroxo (Oh)- or oxo (O2)] is functional models of manganese peroxidase (MnP). The proposed complexes contain the biologically relevant metals, Fe and Mn, that MnP requires for oxidative degradation of lignin. The proposed complexes contain the biologically relevant metals, Fe and Mn, that MnP requires for oxidative degradation of lignin. Well developed synthetic strategies and rigorous purification techniques will be carried out in order to obtain the final Fe/III(heme)-X- Mn/II product. The reactivity of the proposed compounds with peroxide should generate bridging peroxo (O2/2)-complex or possibly even a (porphyrin)Fe/IV=O intermediate similar to compound II. Biologically relevant substrates (i.e. lignin model compounds) will be introduced to the oxidized intermediates in order to test the possibility of oxidative degradation catalysis. An array of spectroscopic methods [X-ray possibility of oxidative degradation catalysis. An array of spectroscopic methods [X-ray crystallography, electroparamagnetic resonance, magnetism, paramagnetic shifted nuclear magnetic resonance, infrared, magnetic circular dichroism, electron absorption, resonance Raman] will be used to probe the geometric and electronic structure of the proposed compounds, as well as the reactive intermediates.