Reactions of dinitrogen pentoxide and nitrogen dioxide with 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine

Abstract

The reactions of gaseous dinitrogen pentoxide (N2O5) and nitrogen dioxide (NO2) with 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphocholine (POPC) coated on the inside surface of a glass reaction cell were studied at 298 K. Unsaturated phosphatidylcholines are significant components of pulmonary surfactant in the alveolar region of the lung and hence serve as a simple model to examine reactions of pulmonary surfactant with these oxidant air pollutants. Using high-performance liquid chromatography (HPLC), Fourier transform infrared and fast atom bombardment mass spectroscopy, the major products of reactions of POPC with N2O5 and NO2 were separated and identified. In the POPC-N2O5 reaction using either air or helium as a buffer gas, the nitronitrate, vinyl nitro and allylic nitro derivatives, as well as a small amount of the trans-isomer of the starting material, were obtained. The nature of the products obtained from the POPC-NO2 reaction depends on the concentration of NO2 as well as whether air is present. At low NO2 concentrations (PNO2/N2O4 less than or equal to 3.8 Torr) in air or in helium, the trans-isomer of POPC was formed almost exclusively. At higher NO2 concentrations (PNO2/N2O4 greater than or equal to 20 Torr) in helium, the dinitro, vinyl nitro and nitro alcohol derivatives were formed. In the presence of air (or 24% 18O2 in helium), a nitronitrate and a dinitronitrate were additional products. Mechanisms for the formation of the observed products and implications for the inhalation of oxides of nitrogen are discussed.

Interaction of nitrogen dioxide with human plasma Antioxidant depletion and oxidative damage

“…It is frequently suggested that NO~. toxicity involves lipid peroxidation [1, 5,6,14015,21036]. Our data are consistent with this view° in that exposure of plasma to 14 ppm NO] led to peroxidation of lipids and depletion of the lipid-soluble antioxidants ubiquinolq0 and ct-tocopherol.…”

“…Nitrogen dioxide (NO~) is a powerfully-oxidizing reactive brown gas with established pulmonary toxicity [1][2][3][4][5][6]. It can be present in homes with unrented heating sources at concentrations up to 2 ppm, in mainstream cigarette smoke (>50 ppm), in smog (up to 1 ppm) and in smoke from other burning organic materials [6][7][8].…”

Reactive uptake studies of NO3 and N2O5 on alkenoic acid, alkanoate, and polyalcohol substrates to probe nighttime aerosol chemistry

“…However, Lai and Finlayson-Pitts studied the heterogeneous reaction between N 2 O 5 and 1-palmitoyl-2-oleoyl-sn-glycero-3phosphocholine (an unsaturated organic compound) on the inside surface of a glass reaction cell, but uptake coefficients were not reported. 33 Major products identified in this previous study included molecules with nitro and nitrate functional groups. The initial step in the reaction mechanism was thought to be direct reaction of N 2 O 5 with the double bond leading to a nitronitrate which can undergo subsequent reactions.…”

Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO3 radicals

“…Recently the oxidation of condensed phase organic material by atmospheric radicals has attracted significant attention [ Arens et al , 2002; Bertram et al , 2001; Bröske et al , 2003; D'Andrea et al , 2008; Docherty and Ziemann , 2006; Eliason et al , 2004; Ellison et al , 1999; Esteve et al , 2003, 2004, 2006; George et al , 2007; Gross and Bertram , 2008; Hearn et al , 2007; Hearn and Smith , 2006; Hung et al , 2005; Inazu et al , 1997; Ishii et al , 2000; Kahan et al , 2006; Knopf et al , 2006; Lai and Finlayson‐Pitts , 1991; Lambe et al , 2007; Mak et al , 2007; McNeill et al , 2007, 2008; Moise and Rudich , 2001; Moise et al , 2002; Molina et al , 2004; Perraudin et al , 2005; Robinson et al , 1995; Rudich , 2003; Rudich et al , 2007; Vlasenko et al , 2008; Wang et al , 2000]. Field measurements suggest that this chemistry may change the composition of atmospheric particles [ Robinson et al , 2006].…”