Nitric oxide coupling to generate N2O promoted by a single-heme system as examined by density functional theory

作者：Yi, Jun^*; Campbell, Adam L. O.; Richter-Addo, George B.^*

来源：Nitric Oxide-Biology and Chemistry, 2016, 60: 69-75.

DOI：10.1016/j.niox.2016.09.004

• Nitric oxide coupling
• Hyponitrite
• Density functional theory
• Iron porphine
• Nitrous oxide

Bacteria utilize a heme/non-heme enzyme system to detoxify nitric oxide (NO) to N2O. In order to probe the capacity of a single-heme system to mediate this NO-to-N2O transformation, various scenarios for addition of electrons, protons, and a second NO molecule to a heme nitrosyl to generate N2O were explored by density functional theory calculations. We describe, utilizing this single-heme system, several stepwise intermediates along pathways that enable the critical N-N bond formation step yielding the desired Fe-N2O product. We also report a hitherto unreported directional second protonation that results in either productive N2O formation with loss of water, or formation of a non-productive hypo nitrous acid adduct Fe{HON=NOH}.

• 出版日期2016-11-30
• 单位南京理工大学