Theoretical investigation of the ring opening process of verdoheme to biliverdin in the presence of dioxygen.
The conversion of ferrous verdoheme to ferric biliverdin in the presence of O(2) was investigated using the B3LYP method. Both 6-31G and 6-31G (d) basis sets were employed for geometry optimization calculation as well as energy stabilization estimation. Three possible pathways for the conversion of iron verdoheme to iron biliverdin were considered. In the first route oxygen and reducing electron were employed. In this path formation of ferrous verdoheme-O(2) complex was followed by the addition of one electron to the ferrous-oxycomplex to produce ferric peroxide intermediate. The ferric peroxide intermediate experienced an intramolecular nucleophilic attack to the most positive position at 5-oxo carbons on the ring to form a closed ring biliverdin. Subsequently the ring opening process took place and the iron (III) biliverdin complex was formed. Closed ring iron biliverdin intermediate and open ring iron biliverdin formed as a product of verdoheme cleavage were respectively 13.20 and 32.70 kcal mol(-1) more stable than ferric peroxide intermediate. Barrier energy for conversion of ferric peroxide to closed ring Fe (III) biliverdin and from the latter to Fe (III) biliverdin were respectively 8.67 and 3.35 kcal mol(-1). In this path spin ground states are doublet except for iron (III) biliverdin in which spin state is quartet. In the second path a ferrous-O(2) complex was formed and, without going to a one electron reduction process, nucleophilic attack of iron superoxide complex took place followed by the formation of iron (III) biliverdin. This path is thermodynamically and kinetically less favorable than the first one. In addition, iron hydro peroxy complex or direct attack of O(2) to macrocycle to form an isoporphyrin type intermediate have shown energy surfaces less favorable than aforementioned routes.
Department of Chemistry, Faculty of Sciences, Shahid Beheshti University, G. C., Evin, Tehran, Iran.
Mahin
M
Gheidi
Nasser
N
Safari
Mansour
M
Zahedi
D001664:Biliverdine / Q000737:chemistry*; D004583:Electrons; D006418:Heme / Q000031:analogs & derivatives* / Q000737:chemistry; D007093:Imidazoles / Q000737:chemistry; D007501:Iron / Q000737:chemistry; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D011522:Protons; D012997:Solvents; D013499:Surface Properties; D013816:Thermodynamics
D007093:Imidazoles; D011522:Protons; D012997:Solvents; C099547:verdoheme; D006418:Heme; D007501:Iron; D001664:Biliverdine; D010100:Oxygen