Protein Cross-Linking and Oligomerization through Dityrosine Formation upon Exposure to Ozone

Air pollution is a potential driver for the increasing prevalence of allergic disease, and post-translational modification by air pollutants can enhance the allergenic potential of proteins. Here, the kinetics and mechanism of protein oligomerization upon ozone (O₃) exposure were studied in coated-wall flow tube experiments at environmentally relevant O₃ concentrations, relative humidities and protein phase states (amorphous solid, semisolid, and liquid). We observed the formation of protein dimers, trimers, and higher oligomers, and attribute the cross-linking to the formation of covalent intermolecular dityrosine species. The oligomerization proceeds fast on the surface of protein films. In the bulk material, reaction rates are limited by diffusion depending on phase state and humidity. From the experimental data, we derive a chemical mechanism and rate equations for a kinetic multilayer model of surface and bulk reaction enabling the prediction of oligomer formation. Increasing levels of tropospheric O₃ in the Anthropocene may promote the formation of protein oligomers with enhanced allergenicity and may thus contribute to the increasing prevalence of allergies

Computational Study of the Effect of Glyoxal–Sulfate Clustering on the Henry’s Law Coefficient of Glyoxal

We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported (Kampf, C. J.; Environ. Sci. Technol. 2013, 47, 4236−4244) strong dependence of the Henry’s law coefficient of glyoxal (C₂O₂H₂) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C₂O₃H₄ and C₂O₄H₆) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic aerosol formation, especially in regions with high sulfate concentrations. We used our computed equilibrium constants for the complexation reactions to assess the magnitude of the Henry’s law coefficient enhancement and found it to be in reasonable agreement with experimental results. This indicates that the complexation of glyoxal hydrates with sulfate can explain the observed uptake enhancement

Novel Tracer Method To Measure Isotopic Labeled Gas-Phase Nitrous Acid (HO¹⁵NO) in Biogeochemical Studies

Gaseous nitrous acid (HONO), the protonated form of nitrite, contributes up to ∼60% to the primary formation of hydroxyl radical (OH), which is a key oxidant in the degradation of most air pollutants. Field measurements and modeling studies indicate a large unknown source of HONO during daytime. Here, we developed a new tracer method based on gas-phase stripping-derivatization coupled to liquid chromatography–mass spectrometry (LC-MS) to measure the ¹⁵N relative exceedance, ψ­(¹⁵N), of HONO in the gas-phase. Gaseous HONO is quantitatively collected and transferred to an azo dye, purified by solid phase extraction (SPE), and analyzed using high performance liquid chromatography coupled to mass spectrometry (HPLC-MS). In the optimal working range of ψ­(¹⁵N) = 0.2–0.5, the relative standard deviation of ψ­(¹⁵N) is <4%. The optimum pH and solvents for extraction by SPE and potential interferences are discussed. The method was applied to measure HO¹⁵NO emissions from soil in a dynamic chamber with and without spiking ¹⁵N labeled urea. The identification of HO¹⁵NO from soil with ¹⁵N urea addition confirmed biogenic emissions of HONO from soil. The method enables a new approach of studying the formation pathways of HONO and its role for atmospheric chemistry (e.g., ozone formation) and environmental tracer studies on the formation and conversion of gaseous HONO or aqueous NO₂^– as part of the biogeochemical nitrogen cycle, e.g., in the investigation of fertilization effects on soil HONO emissions and microbiological conversion of NO₂^– in the hydrosphere