Resonance Raman detection of the myoglobin nitrito heme Fe–O–NO/2-nitrovinyl species: implications for helix E-helix F interactions
Literature Information
Alexandra Lambrou, Eftychia Pinakoulaki
The description of biological activity in heme proteins responsible for activating small molecules requires identification of ligand movement into the metal and non-metal binding sites. Mechanisms of nitrite reductase activity in globins are difficult to verify without the structures of the bound ligand, but we now have such information from resonance Raman spectroscopy on the myoglobin nitrito heme Fe–O–NO/2-nitrovinyl species in their natural environment rather than in crystals. Our results indicate that the formation of the nitrito heme Fe–O–NO/2-nitrovinyl species is pH-dependent. The conditions under which the nitrito heme Fe–O–NO/2-nitrovinyl species is generated strongly suggest that this form corresponds to an acid induced transformation. We propose that the movement of helices E and F at low pH results in the protonation of nitrito heme Fe–O–NO by His64 Nε–H(E) to form the nitrous heme Fe–O(H)–NO species.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












![2-Methyl-2-propanyl 4-oxo-3,9-diazabicyclo[4.2.1]nonane-9-carboxylate structure 2-Methyl-2-propanyl 4-oxo-3,9-diazabicyclo[4.2.1]nonane-9-carboxylate structure](https://static.chemtradehub.com/structs/131/1312456-05-5-9a15.webp)

