title: Calculated Mechanism of Cyanobacterial Aldehyde-Deformylating Oxygenase: Asymmetric Aldehyde Activation by a Symmetric Diiron Cofactor.
abstract: Cyanobacterial aldehyde-deformylating oxygenase (cADO) is a nonheme diiron enzyme that catalyzes the conversion of aldehyde to alk(a/e)ne, an important transformation in biofuel research. In this work, we report a highly desired computational study for probing the mechanism of cADO. By combining our QM/MM results with the available57Fe Mössbauer spectroscopic data, the gained detailed structural information suggests construction of asymmetry from the symmetric diiron cofactor in an aldehyde substrate and O2activation. His160, one of the two iron-coordinate histidine residues in cADO, plays a pivotal role in this asymmetric aldehyde activation process by unprecedented reversible dissociation from the diiron cofactor, a behavior unknown in any other nonheme dinuclear or mononuclear enzymes. The revealed intrinsically asymmetric interactions of the substrate/O2with the symmetric cofactor in cADO are inspirational for exploring diiron subsite resolution in other nonheme diiron enzymes.
authors: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.|University of Chinese Academy of Sciences , Beijing 100049, People's Republic of China.
authors: Chao
authors: C
authors: Wang
authors: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.|University of Chinese Academy of Sciences , Beijing 100049, People's Republic of China.
authors: Chongyang
authors: C
authors: Zhao
authors: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.|University of Chinese Academy of Sciences , Beijing 100049, People's Republic of China.
authors: Lianrui
authors: L
authors: Hu
authors: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.
authors: Hui
authors: H
authors: Chen
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D000458:Cyanobacteria / Q000737:chemistry*; D010084:Oxidation-Reduction; D010105:Oxygenases / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D010105:Oxygenases