Study Of CADO Enzyme And Manganese Nitride Complex By Theoretical Calculation

In this paper,the method of density functional theory(DFT)was used to study the reaction mechanism of cyanobacteria aldehyde deformylation oxygenase(cADO)catalyzed the conversion of long-chain aliphatic aldehydes to alkanes.We proposed a reaction route that is thermodynamically more favorable and consistent with the isotope labeling experiments.The calculated results predicted that the electrons from the reduction system out-sphere plays a key role in the process of catalytic reaction by cADO enzyme,which gives an important theoretical guidance for further understanding of the catalytic reaction mechanism of cADO enzyme.The second work of this paper is to study the control of the electronic properties for manganese nitrogen complexes by the ancillary ligand.By using a series of ligand with different substituents of the ancillary ligand of manganese nitrogen complexes,it was found two kinds of oxidation structures,the radical occupied on the metal or the ring ligand.The relationship of oxidation structure of ligand substituents was summarized.This paper consists of five chapters.Chapter 1 briefly introduces the iron enzymes and transition metal nitride;Chapter 2 describes the background knowledge of the computational chemistry and transition state theory and briefly introduces the calculation software(ORCA);Chapter 3 depicts the mechanism of long chain fatty aldehyde deformylation reaction catalyzed by cADO enzyme;Chapter 4 illustrates the control of the electronic properties for manganese nitrogen complexes by substituents of the ancillary ligand;Chapter 5 is the summary and conclusion of this paper.