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Using improved HPLC analysis conditions, we report the separation of three isomers of mercapturic acid conjugates previously assigned in the literature only to 3-hydroxy-1-methylpropylmercapturic acid (HMPMA-1), a human urinary metabolite of crotonaldehyde. The new conditions, employing a biphenyl column cooled to 5 °C and eluted with a gradient of formic acid, acetonitrile, and methanol, allow the analysis of human urinary mercapturic acids derived not only from crotonaldehyde but also from its isomers methacrolein (3-hydroxy-2-methylpropyl mercapturic acid, HMPMA-2) and methyl vinyl ketone (3-hydroxy-3-methylpropyl mercapturic acid, HMPMA-3). The mercapturic acids were detected and quantified by LC-ESI-MS/MS using the corresponding stable isotope labeled mercapturic acids as internal standards. The analysis was validated for accuracy and precision and applied to urine samples collected from cigarette smokers and nonsmokers. Smokers had significantly higher levels of all three mercapturic acids than did nonsmokers. The results demonstrated that HMPMA-3 from methyl vinyl ketone comprised the major portion of the peaks previously ascribed in multiple studies to HMPMA-1. HMPMA-1 had concentrations intermediate between those of HMPMA-2 and HMPMA-3 in both smokers and nonsmokers. This study reports the first quantitation of HMPMA-2 and HMPMA-3 in human urine. The observation of higher levels of HMPMA-3 than in the other two mercapturic acids suggests a previously unrecognized potential significance of methyl vinyl ketone as a toxicant in smokers and nonsmokers.

Methacrolein (MACR) and methyl vinyl ketone (MVK) are two major intermediate products from the photochemical oxidation of isoprene, the most important biogenic volatile organic compound. In addition, MACR and MVK have primary emissions. Investigating the sources and evolution of MACR and MVK could provide helpful information for the oxidative capacity of the atmosphere. In this study, hourly measurements of isoprene, MACR, and MVK were conducted at a receptor site in the Pearl River Delta region (PRD), i.e., the Heshan site (HS), from 22 October to 20 November, 2014. The average mixing ratios of isoprene, MACR and MVK were 151 ± 17, 91 ± 6 and 79 ± 6 pptv, respectively. The daily variations and the ratios of MVK/MACR during daytime and nighttime suggested that other sources besides isoprene photooxidation influenced the MACR and MVK abundances at the HS. Positive matrix factorization was utilized to resolve the sources of MACR and MVK. Five sources were identified and quantified, including biogenic emissions, biomass burning, secondary formation, diesel, and gasoline vehicular emissions. Among them, secondary formation made the greatest contribution to observed MACR and MVK with average contributions of ~45% and ~70%, respectively. Through the yields of secondary products from the oxidation of MACR and MVK by the OH radical and the concentrations of MACR and MVK, it was found that methylglyoxal and formaldehyde were the main oxidation products of MACR and MVK at the HS site. Overall, this study evaluated the roles of primary emissions on ambient levels of MACR and MVK and advanced the understanding of photochemical oxidation of MACR and MVK in the PRD., (Copyright © 2018. Published by Elsevier B.V.)

In-cloud processing of volatile organic compounds is one of the significant routes leading to secondary organic aerosol (SOA) in the lower troposphere. In this study, we demonstrate that two atmospherically relevant α,β-unsaturated carbonyls, i.e., but-3-en-2-on (methyl vinyl ketone, MVK) and 2-methylopropenal (methacrolein, MACR), undergo sulfate radical-induced transformations in dilute aqueous systems under photochemical conditions to form organosulfates previously identified in ambient aerosols and SOA generated in smog chambers. The photooxidation was performed under sun irradiation in unbuffered aqueous solutions containing carbonyl precursors at a concentration of 0.2 mmol and peroxydisulfate as a source of sulfate radicals (SO 4 - ) at a concentration of 0.95 mmol. UV-vis analysis of solutions showed the fast decay of unsaturated carbonyl precursors in the presence of sulfate radicals. The observation confirms the capacity of sulfate radicals to transform the organic compounds into SOA components in atmospheric waters. Detailed interpretation of high-resolution negative ion electrospray ionization tandem mass spectra allowed to assign molecular structures to multiple aqueous organosulfate products, including an abundant isoprene-derived organosulfate C 4 H 8 SO 7 detected at m/z 199. The results highlight the solar aqueous-phase reactions as a potentially significant route for biogenic SOA production in clouds at locations where isoprene oxidation occurs. A recent modelling study suggests that such processes could likely contribute to 20-30 Tg year -1 production of SOA, referred to as aqSOA, which is a non-negligible addition to the still underestimated budget of atmospheric aerosol., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Highly reactive α,β-unsaturated carbonyl compounds, such as acrolein (ACR), crotonaldehyde (CA) and methyl vinyl ketone (MVK), are environmental pollutants present in high concentrations in cigarette smoke. We have previously found that these carbonyl compounds in cigarette smoke extract (CSE) react with intracellular glutathione (GSH) to produce the corresponding GSH-ACR, GSH-CA and GSH-MVK adducts via Michael addition reaction. These adducts are then further reduced to the corresponding alcohol forms by intracellular aldo-keto reductases in highly metastatic mouse melanoma (B16-BL6) cells and then excreted into the extracellular fluid. This time, we conducted a similar study using sheep erythrocytes and found analogous changes in the sheep erythrocytes after exposure to CSE as those with B16-BL6 cells. This indicates similarity of the detoxification pathways of the α,β-unsaturated carbonyl compounds in sheep blood cells and B16-BL6 cells. Also, we found that the GSH-MVK adduct was reduced by aldose reductase in a cell-free solution to generate its alcohol form, and its reduction reaction was completely suppressed by pretreatment with epalrestat, an aldose reductase inhibitor, a member of the aldo-keto reductase family. In the presence of sheep blood cells, however, reduction of the GSH-MVK adduct was partially inhibited by epalrestat. This revealed that some member of the aldo-keto reductase superfamily other than aldose reductase is involved in reduction of the GSH-MVK adduct in sheep blood. These results suggest that blood cells, mainly erythrocytes are involved in reducing the inhalation toxicity of cigarette smoke via an aldo-keto reductase pathway other than that of aldose reductase.

The unsaturated carbonyl compounds are known as the environmental pollutants. Acrolein (ACR) and methyl vinyl ketone (MVK) are representative unsaturated carbonyl compounds. ACR is contained in smoke, automobile exhaust, industrial waste, and several foods. MVK is widely used as the industrial chemical. Although ACR and MVK are highly toxic, the molecular mechanism for their cytotoxicity has been unclear. We have previously reported that ACR and MVK are major cytotoxic compounds in the gas phase of cigarette smoke, and protein kinase C (PKC) inhibitor and NADPH oxidases inhibitor partially rescued cells from ACR- or MVK-induced cell death (Noya et al., Toxicology, 314, 1-10, 2013). PKC translocation, which is hallmark for PKC activation, and cell damage were induced by treatment of cultured cells with ACR or MVK. Intracellular Ca 2+ chelator completely suppressed ACR- or MVK-induced PKC translocation to the cell membrane and cell damage, while extracellular Ca 2+ chelator had no effects on ACR- and MVK-induced cytotoxicity. These results suggest that intracellular Ca 2+ is an essential factor for cell damage caused by both PKC-dependent and PKC-independent pathways, and mobilization of Ca 2+ from intracellular Ca 2+ stores is induced by ACR or MVK., (Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.)

The heterogeneous reactions of methacrolein (MAC) and methyl vinyl ketone (MVK) on α-Al(2)O(3) surfaces have been studied in a flow reactor using transmission-Fourier Transform Infrared (T-FTIR) spectroscopy to monitor the reaction progress. Unlike SiO(2) particles where MAC and MVK are weakly physisorbed, the results in this work demonstrate that on c-AlO3 particles MAC and MVK are irreversibly adsorbed and can rapidly react on the surface to form various products such as aldehydes, organic acids, hydrogen peroxide, and even higher molecular weight compounds. The initial uptake rates and initial uptake coefficients for MAC and MVK on α-Al(2)O(3) under dry conditions were determined to explore the reactivity of the particles. Furthermore, the effect of water vapor on the heterogeneous reactions was also investigated as a function of relative humidity. Both the heterogeneous uptake and transformation of MAC and MVK on α-Al(2)O(3) were largely suppressed under humid conditions due to the depletion of surface active sites by water molecules. On the basis of experimental results, atmospheric implications of heterogeneous reactions of MAC and MVK were discussed. Our work suggests that heterogeneous reactions on α-Al(2)O(3) can be important sinks for MAC and MVK as well as possible contributors to atmospheric organic aerosol.

High-level electronic structure calculations were carried out for the study of the reaction pathways in the OH-initiated oxidations of methyl vinyl ketone (MVK) and methacrolein (MACR). For the two conformers of MVK (called synperiplanar and antiperiplanar), the addition channels of OH to the terminal and central carbon atom of the double bond dominate the overall rate constant, whereas the abstraction of the methyl hydrogen atoms has no significant kinetic role. In the case of MACR, only the antiperiplanar conformer is important in its reactivity. In addition, the lower Gibbs free energy barrier for MACR corresponds to the aldehydic hydrogen abstraction reaction, which will be somewhat more favorable than the addition processes. The subtle balance between the different pathways (additions versus abstractions) serves to give an understanding of the pressure dependence of the rate constants of these tropospheric oxidation processes.

The experimental simulation was employed to study the aqueous-phase ozonolysis reactions of methacrolein (MAC) and methyl vinyl ketone (MVK) in the atmosphere, at the 25.0 degrees C +/- 0.1 degree C temperature and 1.0 x 10(5) Pa pressure of air. In both MAC and MVK ozonolysis reactions in water, formaldehyde, methylglyoxal, hydrogen peroxides (H2O2) and hydroxymethyl hydroperoxides (HMHP) were found; and their yields (%) were determined: 49.9 +/- 2.9, 26.6 +/- 3.9, 4.6 +/- 0.4 and 10.0 +/- 0.8 respectively for MAC; 40.8+/- 2.2, 40.7 +/- 3.5, 6.8 +/- 0.5 and 10.4 +/- 0.8 respectively for MVK. Finally, the reaction mechanisms are deduced to explain the formation of products observed.