Chemiluminescent aldehyde and beta-diketone reactions promoted by peroxynitrite.
Peroxynitrite is shown here to promote the aerobic oxidation of isobutanal (IBAL) and 3-methyl-2,4-pentanedione (MP) in a pH 7.2 phosphate buffer into acetone plus formate and biacetyl plus acetate, respectively. These products are expected from dioxetane intermediates, whose thermolysis is known to be chemiluminescent (CL). Accordingly, the extent of total oxygen uptake by IBAL at different concentrations parallels the corresponding CL maximum intensities. The pH profile based on oxygen uptake data for the MP reaction matches the titration curve of peroxynitrous acid (pK(a) approximately 7), indicating that peroxynitrite anion is the oxidizing agent. Energy transfer studies with IBAL and the 9, 10-dibromoanthracene-2-sulfonate ion, a triplet carbonyl detector, indicates that triplet acetone (tau = 19 micros) is the energy donor. It is postulated that IBAL- or MP-generated triplet carbonyls are produced by the thermolysis of dioxetane intermediates, which are formed by the cyclization of alpha-hydroperoxide intermediates produced by insertion of dioxygen into the IBAL or MP enolyl radicals, followed by their reduction. Accordingly, EPR spin-trapping studies with 3,5-dibromo-4-nitrosobenzenesulfonic acid (DBNBS) and 2-methyl-2-nitrosopropane (MNP) revealed the intermediacy of carbon-centered radicals, as expected for one-electron abstraction from the enol forms of IBAL or MP by peroxynitrite. The EPR data obtained with IBAL also reveal formation of the isopropyl radical produced by competitive nucleophilic addition of ONOO(-) to IBAL, followed by homolytic cleavage of this adduct and beta-scission of the resulting Me(2)CHCH(O(-))O(*). Superstoichiometric formation of fragmentation products from IBAL or MP attests to the prevalence of an autoxidation chain reaction, here proposed to be initiated by one-electron abstraction by ONOO(-) from the substrate. This work reveals the potential role of peroxynitrite as a generator of electronically excited species that may contribute to deleterious and pathological processes associated with excessive nitric oxide and aldehyde production.
Knudsen
F S
FS
Departamento de Bioquímica and Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, CP 26077, 05599-970 São Paulo, SP, Brazil.
Penatti
C A
CA
Royer
L O
LO
Bidart
K A
KA
Christoff
M
M
Ouchi
D
D
Bechara
E J
EJ
D000447:Aldehydes / Q000737:chemistry*; D008163:Luminescent Measurements; D009566:Nitrates / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010420:Pentanes / Q000737:chemistry*; D019097:Spin Trapping
C410285:3-methyl-2,4-pentanedione; D000447:Aldehydes; D009566:Nitrates; D016877:Oxidants; D010420:Pentanes; C039642:peroxynitric acid; C017439:isobutyraldehyde