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@ARTICLE{Mentel:189321,
      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 / Discussions},
      volume       = {15},
      number       = {2},
      issn         = {1680-7375},
      address      = {Katlenburg-Lindau},
      publisher    = {EGU},
      reportid     = {FZJ-2015-02499},
      pages        = {2791 - 2851},
      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 vapours and possibly
                      contributes a~significant fraction to atmospheric SOA. ELVOC
                      are highly oxidized multifunctional molecules (HOM), formed
                      by sequential rearrangement of peroxy radicals and
                      subsequent O2 addition. Key for efficiency in early particle
                      growth is that formation of HOM is induced by one attack of
                      the oxidant (here O3) and 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 homologues 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 equipped with a
                      NO3−-Chemical Ionization (CI) source. In case of O3 acting
                      as 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 analysing the observed
                      mass spectra and narrow 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 cyloalkenes
                      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
                      constraint rings even higher oxidation degree were possible,
                      either by simple H-shift of the tertiary H-atom or by
                      initialisation 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          = {582 - Plant Science (POF3-582) / 243 - Tropospheric trace
                      substances and their transformation processes (POF3-243) /
                      HITEC - Helmholtz Interdisciplinary Doctoral Training in
                      Energy and Climate Research (HITEC) (PHD-PROGRAM-20170404)},
      pid          = {G:(DE-HGF)POF3-582 / G:(DE-HGF)POF3-243 /
                      G:(DE-Juel1)HITEC-20170406},
      typ          = {PUB:(DE-HGF)16},
      doi          = {10.5194/acpd-15-2791-2015},
      url          = {https://juser.fz-juelich.de/record/189321},
}