Katherine C. Thompson

A kinetic study of the reactions of NO3 with methyl vinyl ketone, methacrolein, acrolein, methyl acrylate and methyl methacrylate

Absolute and relative-rate techniques have been used to obtain rate coefficients for the reactions: NO3+CH3C(O)CHCH2→products (1), NO3+CH2C(CH3)CHO→products (2), NO3+CH2CHCHO→ products (3), and NO3+CH2CHC(O)OCH3→products (4). The reaction NO3+CH2C(CH3)C(O)OCH3→ products (5), has been investigated by a relative-rate method only. The rate coefficients obtained by the relative-rate method at T=296±2 K and P=760 Torr are k1=(4.7±1.7)×10-16 cm3 molecule-1 s-1, k2=(3.7±1.0)×10-15 cm3 molecule-1 s-1, k3=(1.1±0.4)×10-15 cm3 molecule-1 s-1, k4=(1.0±0.6)×10-16 cm3 molecule-1 s-1 and k5=(3.6±1.3)×10-15 cm3 molecule-1 s-1. The rate coefficients determined by the discharge-flow technique at low pressure (P=1–10 Torr) and at T=293–303 K are k1=(3.2±0.6)×10-16 cm3 molecule-1 s-1, k2=(9.6±2.0)×10-15 cm3 molecule-1 s-1, k3=(8.9±2.8)×10-15 cm3 molecule-1 s-1, k4=(1.9±0.4)×10-16 cm3 molecule-1 s-1. The discrepancy between the values obtained from the relative-rate technique and the absolute technique are discussed and explained in terms of interference in the absolute study caused by secondary chemistry and fast-reacting impurities. Product studies reveal that methyl glyoxal is a product of reactions (1) and (2) along with peroxymethacryloyl nitrate (MPAN) for reaction (2) in air. A diurnally varying boundary-layer model suggests that reaction (2) is an important loss process for methacrolein and that it can lead to the generation of OH at night.

Reaction of a Phospholipid Monolayer with Gas-Phase Ozone at the Air—Water Interface: Measurement of Surface Excess and Surface Pressure in Real Time

The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known about the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface, suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of (1)H-POPC on D(2)O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air-water interface leading to the formation of OH radicals. The highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation of oxidized lipids with shorter alkyl tails.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coefficients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic (alkane) solvent. The droplet was exposed to gas-phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha-pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic-like substances, HULIS; alpha-pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid-phase diffusion and reaction are the rate determining steps. Uptake coefficients, gamma, were found to be (1.1 +/- 0.7) x 10(-5), (1.5 +/- 0.7) x 10(-5) and (3.0-7.5) x 10(-3) for the reactions of ozone with the fumarate, benzoate and alpha-pinene containing droplets, respectively. Liquid-phase bimolecular rate coefficients for reactions of dissolved ozone molecules with fumarate, benzoate and alpha-pinene were also obtained: kfumarate = (2.7 +/- 2) x 10(5), kbenzoate = (3.5 +/- 3) x 10(5) and kalpha-pinene = (1-3) x 10(7) dm3 mol(-1) s(-1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS-proxies and for the oxidation of alpha-pinene in pentadecane. The study of the alpha-pinene/ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha-pinene suggest the formation of new species containing carbonyl groups.

Degradation and rearrangement of a lung surfactant lipid at the air-water interface during exposure to the pollutant gas ozone.

The presence of unsaturated lipids in lung surfactant is important for proper respiratory function. In this work, we have used neutron reflection and surface pressure measurements to study the reaction of the ubiquitous pollutant gas-phase ozone, O3, with pure and mixed phospholipid monolayers at the air-water interface. The results reveal that the reaction of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, with ozone leads to the rapid loss of the terminal C9 portion of the oleoyl strand of POPC from the air-water interface. The loss of the C9 portion from the interface is accompanied by an increase in the surface pressure (decrease in surface tension) of the film at the air-water interface. The results suggest that the portion of the oxidized oleoyl strand that is still attached to the lipid headgroup rapidly reverses its orientation and penetrates the air-water interface alongside the original headgroup, thus increasing the surface pressure. The reaction of POPC with ozone also leads to a loss of material from the palmitoyl strand, but the loss of palmitoyl material occurs after the loss of the terminal C9 portion from the oleoyl strand of the molecule, suggesting that the palmitoyl material is lost in a secondary reaction step. Further experiments studying the reaction of mixed monolayers composed of unsaturated lipid POPC and saturated lipid dipalmitoyl-sn-glycero-3-phosphocholine, DPPC, revealed that no loss of DPPC from the air-water interface occurs, eliminating the possibility that a reactive species such as an OH radical is formed and is able to attack nearby lipid chains. The reaction of ozone with the mixed films does cause a significant change in the surface pressure of the air-water interface. Thus, the reaction of unsaturated lipids in lung surfactant changes and impairs the physical properties of the film at the air-water interface.

Environmental Pollutant Ozone Causes Damage to Lung Surfactant Protein B (SP-B)

Lung surfactant protein B (SP-B) is an essential protein found in the surfactant fluid at the air–water interface of the lung. Exposure to the air pollutant ozone could potentially damage SP-B and lead to respiratory distress. We have studied two peptides, one consisting of the N-terminus of SP-B [SP-B(1–25)] and the other a construct of the N- and C-termini of SP-B [SP-B(1–25,63–78)], called SMB. Exposure to dilute levels of ozone (∼2 ppm) of monolayers of each peptide at the air–water interface leads to a rapid reaction, which is evident from an increase in the surface tension. Fluorescence experiments revealed that this increase in surface tension is accompanied by a loss of fluorescence from the tryptophan residue at the interface. Neutron and X-ray reflectivity experiments show that, in contrast to suggestions in the literature, the peptides are not solubilized upon oxidation but rather remain at the interface with little change in their hydration. Analysis of the product material reveals that no cleavage of the peptides occurs, but a more hydrophobic product is slowly formed together with an increased level of oligomerization. We attributed this to partial unfolding of the peptides. Experiments conducted in the presence of phospholipids reveal that the presence of the lipids does not prevent oxidation of the peptides. Our results strongly suggest that exposure to low levels of ozone gas will damage SP-B, leading to a change in its structure. The implication is that the oxidized protein will be impaired in its ability to interact at the air–water interface with negatively charged phosphoglycerol lipids, thus compromising what is thought to be its main biological function.

Evidence for a Nonbase Stacking Effect for the Environment‐sensitive Fluorescent Base Pyrrolocytosine—Comparison with 2‐Aminopurine

Pyrrolocytosine (PC), is a highly fluorescent analog of the natural nucleobase cytosine. The fluorescence of PC is quenched upon helix formation but the origin of the quenching is not known. We investigated the effects of base stacking in the aqueous phase by following the fluorescence of dinucleotides and trinucleotides containing PC. The quantum yields and lifetimes (ns) (in parenthesis) obtained at 25°C were: PC‐T, 0.026 (2.0), PC‐C, 0.033 (2.5), PC‐A, 0.032 (2.7), PC‐G, 0.021 (2.0), T‐PC‐T, 0.044 (3.0) and G‐PC‐G, 0.036 (0.65 and 2.6), compared with 0.038 (2.9) for PC and 0.028 (2.1) for the nucleoside triphosphate. The results show that base stacking does not, except in the case of guanine, quench the fluorescence of PC; indeed the increased solvent shielding can enhance the emitted fluorescence. In the case of G‐PC‐G the guanines do shield the fluorescent base from the solvent but a particular environment of PC between two guanines also appears to allow a rapid nonradiative pathway, suggested to be electron transfer to the excited PC, to depopulate the excited state leading to the shorter fluorescence lifetime.

Rate constants for the reaction of NO and HO2 with peroxy radicals formed from the reaction of OH, Cl or NO3 with alkenes, dienes and α,β-unsaturated carbonyls

Rate constants for the gas-phase reaction of NO and HO2 radicals with 33 peroxy radicals are presented. The peroxy radicals are derived from the addition of either OH, Cl, or NO3 radicals, followed by addition of O2, to a series of alkenes: tetrachloroethene, ethene, 2,3-dimethyl but-2-ene, butadiene, 2,3,4,5-tetramethyl hexa-2,4-diene, 1,1,2,3,4,4-hexachlorobutadiene, but-1-ene-3-one (methyl vinyl ketone) and 2,3-dimethylpen-2-ene-4-one. The rate constants were predicted using a correlation between the singly occupied molecular orbital (SOMO) energy of the peroxy radical and the logarithm of the rate constant for reaction with NO or HO2. A discussion of the accuracy of the method and the trends in the reactivity of the titled peroxy radicals is given. Peroxy radicals derived from halogenated alkenes have larger values of rate constants for reaction with NO relative to reaction with HO2, indicating that they are more likely to react with NO, rather than HO2, in the atmosphere. The reverse is true for peroxy radicals derived from alkylated alkenes.

The reactions of atomic chlorine with acrolein, methacrolein and methyl vinyl ketone

An investigation into the reactions between Cl atoms and acrolein (1), methacrolein (2) and methyl vinyl ketone (3) is presented. Values of the rate constants for the reactions have been determined by an absolute technique for the first time. At a pressure of 1.6 Torr, the rate constants obtained were: k1 = 1.1 ± 0.2, k2 = 3.3 ± 0.6 and k3 = 0.99 ± 0.20 in units of 10−10 cm3 molecule−1 s−1. k1 was also determined at atmospheric pressure using a relative-rate technique. The rate constant obtained was (2.2 ± 0.3) × 10−10 cm3 molecule−1 s−1; the larger value compared with that for 1.6 Torr is thought to reflect a true dependence of the reaction rate on pressure. The final products of the reactions performed under an atmosphere of synthetic air were investigated using FTIR spectroscopy. The only chlorinated organic species identified as products of the reactions were chloroacetaldehyde in the case of reaction of Cl atoms with acrolein; chloroacetone with methacrolein; and chloroacetaldehyde with methyl vinyl ketone. Branching ratios for abstraction (the fraction of reactions occurring by abstraction relative to the sum of addition and abstraction processes) were found to be 0.22 ± 0.13 for acrolein, 0.18 ± 0.02 for methacrolein and <0.03 for methyl vinyl ketone. The reaction of Cl atoms with methacrolein proceeds ia a mechanism that involves the decomposition of the methyl vinyl radical. The decomposition of this radical in synthetic air, and in the absence of NO, appears to lead to the formation of significantly more CO than previously thought. This observation is in agreement with the work of J. J. Orlando, S. E. Paulson and G. S. Tyndall, Geophys. Res. Lett., 1999, 26, 2191 (ref. 1), who studied the decomposition of the radical under different conditions.

An experimental study of the gas-phase reactions of the NO3 radical with three sesquiterpenes: isolongifolene, alloisolongifolene, and α-neoclovene

Isolongifolene, alloisolongifolene, and α-neoclovene are sesquiterpenes, hydrocarbons of general formula C15H24; these sesquiterpenes contain a single carbon–carbon double bond. They are emitted to the atmosphere by plants during the night and the day. Rate coefficients for the reactions between the night-time atmospheric oxidant, the NO3 radical, and isolongifolene (k1), alloisolongifolene (k2), and α-neoclovene (k3) have been determined at T=298±2 K and P=760±10 Torr by the relative-rate method. The values of the rate constants measured were k1=(3.9±1.6)×10-12 cm3 molecule-1 s-1, k2=(1.4±0.7)×10-12 cm3 molecule-1 s-1 and k3=(8.2±4.6)×10-12 cm3 molecule-1 s-1. The reference reaction for determining k1 and k3 was the reaction between NO3 and α-pinene (k9), and the reference reaction for determining k2 was the reaction between NO3 and cyclohexa-1,4-diene (k10). The values used for the rate constants for the reference reactions are k9=6.2×10-12 cm3 molecule-1 s-1 and k10=6.6×10-13 cm3 molecule-1 s-1, with likely errors of 30% on each. Error limits quoted on our measured rate constants (k1–k3) include these potential errors on k9 or k10. The chemical atmospheric lifetimes of these sesquiterpenes are considered. They are short, and are dominated by the reaction with the NO3 radical by night; OH and O3 both make significant contributions by day.

Hydrogen bonded complexes between nitrogen dioxide, nitric acid, nitrous acid and water with SiH3OH and Si(OH)4

The inter-conversion of nitrogen oxides and oxy acids on silica surfaces is of major atmospheric importance. As a preliminary step towards rationalising experimental observations, and understanding the mechanisms behind such reactions we have looked at the binding energies of NO2, N2O4, HNO3, HONO and H2O with simple proxies of a silica surface, namely SiH3OH and Si(OH)4 units. The geometries of these molecular clusters were optimised at both HF/6-311+G(d) and B3LYP/6-311+G(d) level of theory. The SCF energies of the species were determined at the HF/6-311++G(3df,2pd) and B3LYP/6-311++G(3df,2pd) level. The values indicate that nitric acid is by far the most strongly bound species, in agreement with experimental observations. It was also found that the dimer N2O4 is significantly more strongly bound to the Si(OH)4 and SiH3OH units than NO2 itself. The vibrational frequencies calculated for the hydrogen-bonded complexes are compared to the experimentally observed frequencies of the adsorbed species where possible.