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Second‐coordination sphere effects can have varying roles in enzymatic reaction mechanisms and drive the reaction to alternative pathways. In this review, based on extensive computational studies on heme and nonheme iron dioxygenases, several main second‐coordination sphere effects are identified that determine substrate activation and product distribution. These range from substrate and oxidant positioning...
Mononuclear iron‐containing enzymes are highly versatile oxidants that often react stereospecifically and/or regioselectively with substrates. Combined experimental and computational studies on heme monooxygenases, nonheme iron dioxygenases and halogenases have revealed the intricate details of the second‐coordination sphere, which determine this specificity and selectivity. These second‐coordination...
Iron‐containing metalloenzymes are found throughout the natural world and are vital catalysts in many crucial metabolic and biosynthetic biological pathways. In nature, the major classes of metallo‐heme‐proteins are the monooxygenases, containing a protoporphyrin IX center, the catalases and the peroxidases. The cytochromes P450 (P450s) are a superfamily of heme‐containing, structurally and functionally...
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