MODELING MANGANESE PEROXIDASE--A REACTIVITY STUDY

本提案的主要目的是了解新的Fe/III（血红素）-X-Mn/II复合物[X=桥接羟基（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。所提出的复合物含有生物相关的金属，铁和锰，锰锰过氧化物酶需要氧化降解木质素。所提出的复合物含有生物相关的金属，铁和锰，锰锰过氧化物酶需要氧化降解木质素。为了获得最终的Fe/III（血红素）-X-Mn/II产物，将实施良好的合成策略和严格的纯化技术。所提出的化合物与过氧化物的反应性应产生桥接过氧（O2/2）-络合物或甚至可能产生类似于化合物II的（卟啉）Fe/IV=O中间体。将生物相关底物（即木质素模型化合物）引入氧化中间体，以测试氧化降解催化的可能性。一系列的光谱方法[X射线氧化降解催化的可能性。将使用一系列光谱方法[X射线晶体学、电顺磁共振、磁性、顺磁位移核磁共振、红外、磁性圆二色性、电子吸收、共振拉曼]来探测拟定化合物以及活性中间体的几何和电子结构。

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.