2007 Apr 13;72(8):3057-64. doi: 10.1021/jo070040m. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Ultrafast photoactivation of C─H bonds inside water-soluble nanocages. Metrics details. This reaction also causes a decrease in the overall oxidation rate, due to the fast chain-terminating reaction of HO2*with the benzylperoxyl radicals, which causes a loss of chain carriers.  |  eCollection 2019 Feb. Use the link below to share a full-text version of this article with your friends and colleagues. Nevertheless, a significant fraction of benzaldehyde is also produced in primary PhCH3 propagation, presumably via proton rather than hydrogen transfer. doi: 10.1073/pnas.1715304114. Get the latest public health information from CDC: https://www.coronavirus.gov. 27th Sep, 2019. 1995 Apr;30(4):277-90. doi: 10.1007/BF02536034. However, to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target. Mechanisms of free radical oxidation of unsaturated lipids. Proc Natl Acad Sci U S A. An equimolar amount of benzyl alcohol, together with benzoic acid, is additionally produced in the tertiary propagation of PhCHO with benzylperoxyl radicals. This site needs JavaScript to work properly. Quantitative and qualitative sensing techniques for biogenic volatile organic compounds and their oxidation products. with the benzylperoxyl radicals, which causes a loss of chain carriers. Guo S, Hu M, Peng J, Wu Z, Zamora ML, Shang D, Du Z, Zheng J, Fang X, Tang R, Wu Y, Zeng L, Shuai S, Zhang W, Wang Y, Ji Y, Li Y, Zhang AL, Wang W, Zhang F, Zhao J, Gong X, Wang C, Molina MJ, Zhang R. Proc Natl Acad Sci U S A. The OH−toluene reactions lead promptly and dominantly to cresol formation, which regulates the impacts on air quality, human health, and climate. Pronounced non-Arrhenius behaviour of hydrogen-abstractions from toluene and derivatives by phthalimide-N-oxyl radicals: a theoretical study. Ji Y, Shi Q, Li Y, An T, Zheng J, Peng J, Gao Y, Chen J, Li G, Wang Y, Zhang F, Zhang AL, Zhao J, Molina MJ, Zhang R. Proc Natl Acad Sci U S A. NLM Please enable it to take advantage of the complete set of features! The very fast benzyl peroxyl-initiated co-oxidation of benzyl alcohol generates HO2* radicals, along with benzaldehyde. Aerobic oxidation of toluene (PhCH3) is investigated by complementary experimental and theoretical methodologies. J Phys Chem A. An equimolar amount of benzyl alcohol, together with benzoic acid, is additionally produced in the tertiary propagation of PhCHO with benzylperoxyl radicals. Aerobic oxidation of toluene (PhCH3) is investigated by complementary experimental and theoretical methodologies. Herein, MgO nanosheets and single-atom Pt loaded MgO (Pt SA/MgO) nanosheets were … Mechanism of thermal toluene autoxidation. Please enable it to take advantage of the complete set of features! The authors declare no conflict of interest. Find NCBI SARS-CoV-2 literature, sequence, and clinical content: https://www.ncbi.nlm.nih.gov/sars-cov-2/. Changes in air quality and tropospheric composition due to depletion of stratospheric ozone and interactions with climate. Cite. Formation of Highly Oxidized Radicals and Multifunctional Products from the Atmospheric Oxidation of Alkylbenzenes. Keywords: 569 Accesses. Clipboard, Search History, and several other advanced features are temporarily unavailable. Proc Natl Acad Sci U S A.  |  2003 Oct 15;125(41):12655-65. doi: 10.1021/ja0350280. air pollution; aromatics; oxidation; ozone; secondary organic aerosol. Author information: (1)K.U. Environ Sci Process Impacts. Whereas the reaction of the chain‐carrying benzylperoxyl radicals with the substrate produces predominantly benzyl hydroperoxide, benzyl alcohol and benzaldehyde originate mainly from subsequent propagation of the hydroperoxide product. Find NCBI SARS-CoV-2 literature, sequence, and clinical content: https://www.ncbi.nlm.nih.gov/sars-cov-2/. 2020 Apr 16;59(16):6318-6329. doi: 10.1002/anie.201912382. 2007 Sep 6;111(35):8663-76. doi: 10.1021/jp068640x. Enter your email address below and we will send you your username, If the address matches an existing account you will receive an email with instructions to retrieve your username, I have read and accept the Wiley Online Library Terms and Conditions of Use, http://www.wiley‐vch.de/contents/jc_2267/2007/f700563_s.pdf. 2017 Sep 19;114(38):E7856-E7857. USA.gov. Hermans I(1), Peeters J, Vereecken L, Jacobs PA. Epub 2017 Sep 7. University for Development Studies. Abstract. No induction periods are observed. ChemSusChem. Whereas the reaction of … The phenolic pathway yields HO. Oxidation Mechanisms of Toluene and Benzene An expanded and improved version of a previously published benzene oxidation mechanism is presented and shown to model published experimental data fairly successfully. Get the latest research from NIH: https://www.nih.gov/coronavirus. Environ Sci Technol. USA.gov. The aromatic ring and other covalent bonds (C═O, C–O, and O–H) are detected during photocatalytic oxidation. Get the latest research from NIH: https://www.nih.gov/coronavirus. Oxidation mechanism of aromatic peroxy and bicyclic radicals from OH-toluene reactions. doi: 10.1073/pnas.1713835114. Tang X, Wilson SR, Solomon KR, Shao M, Madronich S. Photochem Photobiol Sci. 2019 Apr 30;116(18):8657-8666. doi: 10.1073/pnas.1900125116. The very fast benzyl peroxyl‐initiated co‐oxidation of benzyl alcohol generates HO2. Leuven, Department of Chemistry, Celestijnenlaan 200F, B‐3001 Heverlee, Belgium. View the article PDF and any associated supplements and figures for a period of 48 hours. COVID-19 is an emerging, rapidly evolving situation. Angew Chem Int Ed Engl.  |  Remarkable nucleation and growth of ultrafine particles from vehicular exhaust. See this image and copyright information in PMC. National Center for Biotechnology Information, Unable to load your collection due to an error, Unable to load your delegates due to an error. ( A ) Addition to the…, Toluene oxidation and urban photochemical…, Toluene oxidation and urban photochemical smog. Epub 2007 Mar 16. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. Correction for Ji et al., Reassessing the atmospheric oxidation mechanism of toluene. Severe haze in northern China: A synergy of anthropogenic emissions and atmospheric processes. 2008 Feb 28;10(8):1125-32. doi: 10.1039/b716932a. Unlimited viewing of the article PDF and any associated supplements and figures. Leuven, Centre for Surface Science and Catalysis, Kasteelpark Arenberg 23, B‐3001 Heverlee, Belgium, ETH Zürich, Institute for Chemical and Bioengineering, Wolfgang‐Pauli Strasse 10, Hönggerberg, HCI, CH‐8093 Zurich, Switzerland, Fax: (+41) 44‐6321163, K.U. Phys Chem Chem Phys. The "hot" oxy radicals generated in this step can also abstract aromatic hydrogen atoms from PhCH3, and this results in production of cresols, known inhibitors of radical-chain reactions. Molecule-Induced Radical Formation (MIRF) Reactions-A Reappraisal. HHS Elucidating the fate of the OH-adduct in toluene oxidation under tropospheric boundary layer conditions. Epub 2017 Jul 18. (, Potential energy surfaces of the OH−toluene reaction. Catalytic oxidation of toluene over active MnO x catalyst prepared via an alkali-promoted redox precipitation method. Supporting information for this article is available on the WWW under http://www.wiley‐vch.de/contents/jc_2267/2007/f700563_s.pdf or from the author. This drastically changes the autoxidation mechanism and, among other things, causes a sharp decrease in the hydroperoxide yield. ( A )…, Potential energy surfaces of the OH−toluene reaction. Lipids. Carbenium ion-mediated oligomerization of methylglyoxal for secondary organic aerosol formation. If you have previously obtained access with your personal account, please log in. Learn about our remote access options, K.U. Clipboard, Search History, and several other advanced features are temporarily unavailable. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Moreover, due to the fast equilibrium PhCH2OOH+HO2.⇌PhCH2OO.+H2O2, and the much lower reactivity of H2O2 compared to PhCH2OOH, the fast co‐oxidation of the alcohol means that HO2.