Singlet oxygen generation by the reaction of acrolein with peroxynitrite via a 2-hydroxyvinyl radical intermediate

Author(s)

Goncalves, Leticia C. P. ^[1] ; Massari, Julio ^[1] ; Licciardi, Saymon ^{[2, 1]} ; Prado, Fernanda M. ^[3] ; Linares, Edlaine ^[3] ; Klassen, Aline ^[1] ; Tavares, Marina F. M. ^[1] ; Augusto, Ohara ^[3] ; Di Mascio, Paolo ^[3] ; Bechara, Etelvino J. H. ^{[2, 1]}

Affiliation

^[1] Univ Sao Paulo, Dept Quim Fundamental, Inst Quim, Av Prof Lineu Presses 748, BR-05508000 Sao Paulo, SP - Brazil

^[2] Univ Fed Sao Paulo, Inst Ciencias Ambientais Quim & Farmaceut, Dept Ciencias Exatas & Terra, Diadema, SP - Brazil

^[3] Univ Sao Paulo, Inst Quim, Dept Bioquim, Sao Paulo, SP - Brazil

• Document type: Journal article
• Source: Free Radical Biology and Medicine; v. 152, p. 83-90, MAY 20 2020.
• Web of Science Citations: 0

Abstract

Acrolein (2-propenal) is an environmental pollutant, food contaminant, and endogenous toxic by-product formed in the thermal decomposition and peroxidation of lipids, proteins, and carbohydrates. Like other alpha,beta-unsaturated aldehydes, acrolein undergoes Michael addition of nucleophiles such as basic amino acids residues of proteins and nucleobases, triggering aging associated disorders. Here, we show that acrolein is also a potential target of the potent biological oxidant, nitrosating and nitrating agent peroxynitrite. In vitro studies revealed the occurrence of 1,4-addition of peroxynitrite (k(2) = 6 x 10(3) M-1 s(-1), pH 7.2, 25 degrees C) to acrolein in air-equilibrated phosphate buffer. This is attested by acrolein concentration-dependent oxygen uptake, peroxynitrite consumption, and generation of formaldehyde and glyoxal as final products. These products are predicted to be originated from the Russell termination of (OOCH)-O-center dot=CH(OH) radical which also includes molecular oxygen at the singlet delta state (O-2 (1)Delta g). Accordingly, EPR spin trapping studies with the 2,6-nitrosobenzene-4-sulfonate ion (DBNBS) revealed a 6-line spectrum attributable to the 2-hydroxyvinyl radical adduct. Singlet oxygen was identified by its characteristic monomolecular IR emission at 1,270 nm in deuterated buffer, which was expectedly quenched upon addition of water and sodium azide. These data represent the first report on singlet oxygen creation from a vinylperoxyl radical, previously reported for alkyl- and formylperoxyl radicals, and may contribute to better understand the adverse acrolein behavior in vivo. (AU)

• FAPESP's process: 18/25842-8 - Sources, Targets and Biological Responses of Triplet Species and Singlet Oxygen: Pathogenicity and Quenching.
• Grantee: Leticia Christina Pires Gonçalves
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 12/12663-1 - Singlet molecular oxygen and peroxides in chemical biology
• Grantee: Paolo Di Mascio
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 13/07937-8 - Redoxome - Redox Processes in Biomedicine
• Grantee: Ohara Augusto
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 17/27059-6 - Expanding the metabolic coverage using ion chromatography-mass spectrometry in metabolomics studies of immunosuppressive therapies in renal transplantation
• Grantee: Marina Franco Maggi Tavares
• Support Opportunities: Regular Research Grants
• FAPESP's process: 17/22501-2 - Electronic chemiexcitation in biological systems: bioluminescence and photochemistry in the dark
• Grantee: Etelvino José Henriques Bechara
• Support Opportunities: Research Projects - Thematic Grants