Abstract

Nitrogen dioxide is one of the most ubiquitous and damaging of the world's pollutants.
Our aim i s to provide data that rationalize and predict the reactions of NO2 with the types of molecules that are potential targets when animals breath NO2-containing polluted air. In this proposal we describe 7 specific research projects. (1) We will continue our study of the products formed when cyclohexene (a simplified model of a cis-unsaturated fatty acid) reacts with NO2. We have reported a complete product analysis in organic solvents. We now propose a study of cyclohexene in an aqueous micellular system and ask: What is the effect of an aqueous solvent on the product mixture? We also ask: What is the fraction of NO2/N2O4 that reacts with water, dismutating to form nitrite and nitrate ions, and what fraction reacts with cyclohexene? (2) We will study the reaction of NO2 with unsaturated fatty acid esters in organic solvents to determine the fraction of the NO2 that reacts by addition to the double bond versus the fraction that abstracts an allylic hydrogen atom. (3) We will determine the structure of all of the products formed when methyl oleate reacts with NO2 in organic solvents. Analysis will use state-of-the-art GC-MS. (4) We will use kinetic methods to ask: What fraction of NO2 reacts with polyunsaturated fatty acids (PUFA) in an aqueous micellar system and what fraction reacts with water? (5) In the same system used in section 4, we will ask: What fraction of the NO2 reacts with PUFA by addition versus hydrogen-atom abstraction? (6) We will use stopped-flow kinetics to measure the absolute rate constants for reaction of PUFA, tocopherol and other antioxidants, thiols, and amino acids with NO2. (7) We will use stopped-flow kinetics to determine the absolute rate constants for the reaction of NO2 with polynuclear aromatic hydrocarbons (PAH). We have already reported a study of the relative rates of these reactions, but mechanistic complexities require the knowledge of absolute rate constants.

  Funding Agency

Agency
National Institute of Health (NIH)
Institute
National Heart, Lung, and Blood Institute (NHLBI)
Type
Method to Extend Research in Time (MERIT) Award (R37)
Project #
5R37HL016029-20
Application #
2214934
Study Section
Special Emphasis Panel (NSS)
Project Start
1977-09-01
Project End
1995-11-30
Budget Start
1993-12-01
Budget End
1995-11-30
Support Year
20
Fiscal Year
1994
Total Cost
Indirect Cost

  Institution

Name
Louisiana State University A&M Col Baton Rouge
Department
Miscellaneous
Type
Schools of Arts and Sciences
DUNS #
075050765
City
Baton Rouge
State
LA
Country
United States
Zip Code
70803

  Publications

Gallon, A A; Pryor, W A (1994) The reaction of low levels of nitrogen dioxide with methyl linoleate in the presence and absence of oxygen. Lipids 29:171-6
Pryor, W A (1994) Mechanisms of radical formation from reactions of ozone with target molecules in the lung. Free Radic Biol Med 17:451-65
Gallon, A A; Pryor, W A (1993) The identification of the allylic nitrite and nitro derivatives of methyl linoleate and methyl linolenate by negative chemical ionization mass spectroscopy. Lipids 28:125-33
Wang, K; Bermudez, E; Pryor, W A (1993) The ozonation of cholesterol: separation and identification of 2,4-dinitrophenylhydrazine derivatization products of 3 beta-hydroxy-5-oxo-5,6-secocholestan-6-al. Steroids 58:225-9
Squadrito, G L; Uppu, R M; Cueto, R et al. (1992) Production of the Criegee ozonide during the ozonation of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine liposomes. Lipids 27:955-8
Pryor, W A (1992) How far does ozone penetrate into the pulmonary air/tissue boundary before it reacts? Free Radic Biol Med 12:83-8
Squadrito, G L; Shane, B S; Fronczek, F R et al. (1990) 1H NMR studies on mutagenic nitrofluoranthenes and exposure risk assessment. Chem Res Toxicol 3:231-5
Ewing, J C; Cosgrove, J P; Giamalva, D H et al. (1989) Autoxidation of methyl linoleate initiated by the ozonide of allylbenzene. Lipids 24:609-15
Lachocki, T M; Nuggehalli, S K; Scherer, K V et al. (1989) The smoke produced from the oxidative pyrolysis of perfluoro polymers: an ESR spin-trapping study. Chem Res Toxicol 2:174-80
Yoshikawa, T; Giamalva, D H; Flory, W et al. (1988) Toxicity of aromatic hydrocarbons. VII. Hepatotoxicity of 9-nitrophenanthrene, and protection against it by beta-naphthoflavone. Biochem Int 16:935-40

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