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Oxoferryl porphyrin π-cation radical active sites of compound I intermediates which are found in enzymes such as peroxidases and catalases have been extensively modeled by oxidized synthetic metalloporphyrins. The electronic symmetry states of these compounds were initially assigned on the basis of electronic absorption data. In recent years new experimental and theoretical results have become available which have led to a re-evaluation and modification of the original assignments. A historical perspective of these developments is provided in the context of recent NMR, resonance Raman, and other spectroscopic data and theoretical calculations for the synthetic models and enzymatic systems.
This mini-review focuses on the biosynthesis pathways leading to naturally occurring porphyrins. ALA, protoporphyrin IX, chlorophylls and their derivatives are increasingly used in medicine, sensing, or chemical biology applications. Knowledge of their biosynthesis and unique functions in living organisms is a prerequisite before involving these molecules in drugs or processes.