2008
DOI: 10.1021/bi801015c
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Abstract: The nitrite anion is known to oxidize and degrade hemoglobin (Hb). Recent literature reports suggest a nitrite reductase activity for Hb, converting nitrite into nitric oxide. Surprisingly, no structural information about Hb-nitrite interactions has been reported. We have determined the crystal structure of the ferric Hb-nitrite complex at 1.80 A resolution. The nitrite ligand adopts the uncommon O-nitrito binding mode. In addition, the nitrito conformations in the alpha and beta subunits are different, reflec… Show more

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Cited by 77 publications
(116 citation statements)
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“…The five-coordinate heme can now bind to external ligands such as nitrite. As evidenced in recent reports (45,46) by experimental and density functional theoretical studies, nitrite may bind to the heme in either N-nitro-or O-nitrito-conformations (Scheme 1, second step). We cannot conclude from our results if either binding mode is preferred, and given the differences in the heme pocket of Ngb, as compared with Mb (supplemental Fig.…”
Section: Discussionmentioning
confidence: 76%
“…The five-coordinate heme can now bind to external ligands such as nitrite. As evidenced in recent reports (45,46) by experimental and density functional theoretical studies, nitrite may bind to the heme in either N-nitro-or O-nitrito-conformations (Scheme 1, second step). We cannot conclude from our results if either binding mode is preferred, and given the differences in the heme pocket of Ngb, as compared with Mb (supplemental Fig.…”
Section: Discussionmentioning
confidence: 76%
“…The same laboratory was able to prepare nitrite ion complexes of metHb in a similar fashion. However, for this protein, the ferriheme centers in the ␣-and ␤-subunits show significant differences in their coordination of nitrite ion [62]. For each subunit, the nitrite ligand is coordinated as the nitrito isomer, but the crystal structures show considerable differences in the mode of coordination.…”
Section: The Coordination Chemistry Of Nitritementioning
confidence: 90%
“…Regardless of the global importance of nitrite processing in RBCs, the mechanism proposed in Scheme 5 is quite interesting, especially given the reports described above that complexes of metMb and of metHb are both nitrito (Fe-ONO) isomers [61,62]. Although the structure of the nitrite ion complex of Fe III (TPPS) in aqueous solution is unknown, analogous ferriheme models are nitro isomers, so the same would be expected for Fe III (TPPS)(H 2 O)(NO 2 ).…”
Section: Nitrite Catalysis Of Reductive Nitrosylationmentioning
confidence: 99%
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“…The lower binding affinity of nitrite for ferric heme relative to that of NO (85,86) raised questions as to the validity of this temporal sequence. Subsequent simulation studies (60) indicated that N 2 O 3 could be formed with either NO binding first, followed by nitrite reacting with ferric bound NO, or through the initially proposed sequence in which nitrite binds first (31,59,87).…”
Section: Issue Of Mechanistic Sequence Nitrite Followed By Nomentioning
confidence: 99%