Incorporation of molybdenum in rubredoxin: models for mononuclear molybdenum enzymes
Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry(2015)
摘要
Molybdenum is found in the active site of enzymes usually coordinated by one or two pyranopterin molecules. Here, we mimic an enzyme with a mononuclear molybdenum- bis pyranopterin center by incorporating molybdenum in rubredoxin. In the molybdenum-substituted rubredoxin, the metal ion is coordinated by four sulfurs from conserved cysteine residues of the apo-rubredoxin and two other exogenous ligands, oxygen and thiol, forming a Mo (VI) -(S-Cys) 4 (O)(X) complex, where X represents –OH or –SR. The rubredoxin molybdenum center is stabilized in a Mo(VI) oxidation state, but can be reduced to Mo(IV) via Mo(V) by dithionite, being a suitable model for the spectroscopic properties of resting and reduced forms of molybdenum- bis pyranopterin-containing enzymes. Preliminary experiments indicate that the molybdenum site built in rubredoxin can promote oxo transfer reactions, as exemplified with the oxidation of arsenite to arsenate.
更多查看译文
关键词
Metal-substituted rubredoxin,Models of molybdenum-containing enzymes,Resonance Raman,19F-NMR,DMSO reductase family
AI 理解论文
溯源树
样例
生成溯源树,研究论文发展脉络
Chat Paper
正在生成论文摘要