Stoichiometry dependent modifications in synthetic heme peroxo reactivity with nitrosonium: a new paradigm for understanding heme mediated nitration chemistry

2026-03-01

PRE

Samith B. Jayawardana

Collin B. Gabel

Arya A Bhosale

Aruzhan Abdikaiym

Gbolagade Olajide

Shanuk Rajapakse

Tibor Szilvási *

Brad S. Pierce

Gayan B. Wijeratne *

DOI：10.1039/d6dt00522e

Original

Original request for help

Save

Abstract

En 中文

Reactivity studies of synthetic heme-peroxo complexes with excess NO+ uncover an unprecedented reaction pathway that diverges sharply from the canonical nitric oxide dioxygenase (NOD) chemistry observed with 1 equiv. of NO+. When exposed to excess NO+, heme-peroxo adducts generate two stoichiometric equivalents of (NO2)-N-center dot radicals and concurrently yield naked ferric heme products. Comprehensive spectroscopic and computational analyses support this distinctive interconversion, and the resulting (NO2)-N-center dot radicals are shown to drive the nitration and oxidation of a series of bioinspired substrates. This stoichiometry-dependent reactivity shift highlights a long-proposed, but experimentally elusive principle governing interactions between heme-oxygen intermediates and nitrogen oxides, providing new mechanistic insight into nitrosative stress pathways relevant to analogous biological systems.

Keywords:

NITRIC-OXIDE

NITROGEN-DIOXIDE

S-NITROSOTHIOLS

PEROXYNITRITE

NITROSYLATION

MECHANISMS

COMPLEX

IRON

Stoichiometry dependent modifications in synthetic heme peroxo reactivity with nitrosonium: a new paradigm for understanding heme mediated nitration chemistry

Abstract

Journal

Organization

Cited Papers

Citing Papers