Reversible oxygenation of heme bound to polyvinylpyridine and polyvinylimidazole.

Abstract

AbstractThe interaction between heme bound to poly‐4‐vinylpyridine (PVP) or poly‐N‐vinyl‐2‐methylimidazole (PVMI) and molecular oxygen (O2) was studied. In this paper, the reactions of some types of heme with O2 in organic solvents, particularly in N,N‐dimethylformamide (DMF) were discussed. The free heme not bound to an axial base was easily oxidized irreversibly to hemin in DMF with bubbled O2. The hemochromogens complexed with pyridine, imidazole, or their polymeric derivatives such as PVP and PVMI bound O2 to one of the axial coordination sites. The characteristic absorption band assignable to the resulting oxygenated heme was observed at 402 nm. This absorption band could be changed back to the characteristic band of the reduced hemochromogen at 418 nm by removing O2 dissolved in the DMF solution by a vacuum or by a stream of nitrogen. Thus, the hemochromogens bound to the synthetic polymers were found to adsorb and desorb O2 reversible in DMF.When the polymeric ligands were used, the equilibrium constants in the complexation of heme with these polymers were about 102 times as large as those of the corresponding monomeric ligands. The oxygenation rates and the capacities of O2 of the polymeric hemochromogens were larger than those of the monomeric hemochromogens. In addition, the oxygenation rate of the polymer complex was changeable owing to the conformational change of the polymeric ligand; this rate increased about ten times under the optimal condition.