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@ARTICLE{Mentel:202148,
      author       = {Mentel, T. F. and Springer, M. and Ehn, M. and Kleist, E.
                      and Pullinen, I. and Kurtén, T. and Rissanen, M. and
                      Wahner, A. and Wildt, J.},
      title        = {{F}ormation of highly oxidized multifunctional compounds:
                      autoxidation of peroxy radicals formed in the ozonolysis of
                      alkenes – deduced from structure–product relationships},
      journal      = {Atmospheric chemistry and physics},
      volume       = {15},
      number       = {12},
      issn         = {1680-7324},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2015-04437},
      pages        = {6745 - 6765},
      year         = {2015},
      abstract     = {It has been postulated that secondary organic particulate
                      matter plays a pivotal role in the early growth of newly
                      formed particles in forest areas. The recently detected
                      class of extremely low volatile organic compounds (ELVOC)
                      provides the missing organic vapors and possibly contributes
                      a significant fraction to atmospheric SOA (secondary organic
                      aerosol). The sequential rearrangement of peroxy radicals
                      and subsequent O2 addition results in ELVOC which are highly
                      oxidized multifunctional molecules (HOM). Key for efficiency
                      of such HOM in early particle growth is that their formation
                      is induced by one attack of the oxidant (here O3), followed
                      by an autoxidation process involving molecular oxygen.
                      Similar mechanisms were recently observed and predicted by
                      quantum mechanical calculations e.g., for isoprene. To
                      assess the atmospheric importance and therewith the
                      potential generality, it is crucial to understand the
                      formation pathway of HOM.To elucidate the formation path of
                      HOM as well as necessary and sufficient structural
                      prerequisites of their formation we studied homologous
                      series of cycloalkenes in comparison to two monoterpenes. We
                      were able to directly observe highly oxidized
                      multifunctional peroxy radicals with 8 or 10 O atoms by an
                      Atmospheric Pressure interface High Resolution Time of
                      Flight Mass Spectrometer (APi-TOF-MS) equipped with a
                      NO3−-chemical ionization (CI) source. In the case of O3
                      acting as an oxidant, the starting peroxy radical is formed
                      on the so-called vinylhydroperoxide path. HOM peroxy
                      radicals and their termination reactions with other peroxy
                      radicals, including dimerization, allowed for analyzing the
                      observed mass spectra and narrowing down the likely
                      formation path. As consequence, we propose that HOM are
                      multifunctional percarboxylic acids, with carbonyl,
                      hydroperoxy, or hydroxy groups arising from the termination
                      steps. We figured that aldehyde groups facilitate the
                      initial rearrangement steps. In simple molecules like
                      cycloalkenes, autoxidation was limited to both terminal C
                      atoms and two further C atoms in the respective α
                      positions. In more complex molecules containing tertiary H
                      atoms or small, constrained rings, even higher oxidation
                      degrees were possible, either by simple H shift of the
                      tertiary H atom or by initialization of complex ring-opening
                      reactions.},
      cin          = {IEK-8 / IBG-2},
      ddc          = {550},
      cid          = {I:(DE-Juel1)IEK-8-20101013 / I:(DE-Juel1)IBG-2-20101118},
      pnm          = {243 - Tropospheric trace substances and their
                      transformation processes (POF3-243) / HITEC - Helmholtz
                      Interdisciplinary Doctoral Training in Energy and Climate
                      Research (HITEC) (HITEC-20170406)},
      pid          = {G:(DE-HGF)POF3-243 / G:(DE-Juel1)HITEC-20170406},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000357117500012},
      doi          = {10.5194/acp-15-6745-2015},
      url          = {https://juser.fz-juelich.de/record/202148},
}