globalchange  > 气候变化与战略
DOI: 10.1073/pnas.1912235117
论文题名:
Carbenium ion-mediated oligomerization of methylglyoxal for secondary organic aerosol formation
作者: Ji Y.; Shi Q.; Li Y.; An T.; Zheng J.; Peng J.; Gao Y.; Chen J.; Li G.; Wang Y.; Zhang F.; Zhang A.L.; Zhao J.; Molina M.J.; Zhang R.
刊名: Proceedings of the National Academy of Sciences of the United States of America
ISSN: 0027-8424
出版年: 2020
卷: 117, 期:24
起始页码: 13294
结束页码: 13299
语种: 英语
英文关键词: Aqueous ; Brown carbon ; Cationic ; Oligomerization ; Secondary organic aerosol
Scopus关键词: carbenium ion ; diol ; ion ; methylglyoxal ; organic compound ; tetrol ; unclassified drug ; aqueous solution ; Article ; controlled study ; hydration ; kinetics ; oligomerization ; priority journal ; protonation ; quantum chemistry ; secondary organic aerosol ; thermodynamics
英文摘要: Secondary organic aerosol (SOA) represents a major constituent of tropospheric fine particulate matter, with profound implications for human health and climate. However, the chemical mechanisms leading to SOA formation remain uncertain, and atmospheric models consistently underpredict the global SOA budget. Small α-dicarbonyls, such as methylglyoxal, are ubiquitous in the atmosphere because of their significant production from photooxidation of aromatic hydrocarbons from traffic and industrial sources as well as from biogenic isoprene. Current experimental and theoretical results on the roles of methylglyoxal in SOA formation are conflicting. Using quantum chemical calculations, we show cationic oligomerization of methylglyoxal in aqueous media. Initial protonation and hydration of methylglyoxal lead to formation of diols/tetrol, and subsequent protonation and dehydration of diols/tetrol yield carbenium ions, which represent the key intermediates for formation and propagation of oligomerization. On the other hand, our results reveal that the previously proposed oligomerization via hydration for methylglyoxal is kinetically and thermodynamically implausible. The carbenium ion-mediated mechanism occurs barrierlessly on weakly acidic aerosols and cloud/fog droplets and likely provides a key pathway for SOA formation from biogenic and anthropogenic emissions. © 2020 National Academy of Sciences. All rights reserved.
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资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/164162
Appears in Collections:气候变化与战略

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作者单位: Ji, Y., Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China, Guangzhou Key Laboratory Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, 510006, China, Department of Atmospheric Sciences, Texas A & M University, College Station, TX 77843, United States, Department of Chemistry, Texas A & M University, College Station, TX 77843, United States; Shi, Q., Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China, Guangzhou Key Laboratory Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, 510006, China; Li, Y., Department of Atmospheric Sciences, Texas A & M University, College Station, TX 77843, United States, Department of Chemistry, Texas A & M University, College Station, TX 77843, United States; An, T., Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China, Guangzhou Key Laboratory Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, 510006, China; Zheng, J., Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Nanjing University of Information Science and Technology, Nanjing, 210044, China; Peng, J., Department of Atmospheric Sciences, Texas A & M University, College Station, TX 77843, United States, Department of Chemistry, Texas A & M University, College Station, TX 77843, United States; Gao, Y., Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China, Guangzhou Key Laboratory Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, 510006, China; Chen, J., Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China, Guangzhou Key Laboratory Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, 510006, China; Li, G., Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China, Guangzhou Key Laboratory Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou, 510006, China; Wang, Y., Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, United States; Zhang, F., Department of Atmospheric Sciences, Texas A & M University, College Station, TX 77843, United States, Department of Chemistry, Texas A & M University, College Station, TX 77843, United States, State Key Laboratory of Earth Surface Processes and Resource Ecology, College of Global Change and Earth System Science, Beijing Normal University, Beijing, 100875, China; Zhang, A.L., Department of Chemistry, College of Natural Sciences, University of Texas at Austin, Austin, TX 78712, United States; Zhao, J., Department of Atmospheric Sciences, Texas A & M University, College Station, TX 77843, United States, Department of Chemistry, Texas A & M University, College Station, TX 77843, United States; Molina, M.J., Department of Chemistry and Biochemistry, University of California San Diego, San Diego, CA 92093, United States; Zhang, R., Department of Atmospheric Sciences, Texas A & M University, College Station, TX 77843, United States, Department of Chemistry, Texas A & M University, College Station, TX 77843, United States

Recommended Citation:
Ji Y.,Shi Q.,Li Y.,et al. Carbenium ion-mediated oligomerization of methylglyoxal for secondary organic aerosol formation[J]. Proceedings of the National Academy of Sciences of the United States of America,2020-01-01,117(24)
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