% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Gabriel:56261,
author = {Gabriel, F. L. P. and Cyris, M. and Jonkers, N. and Giger,
W. and Günther, K. and Kohler, H.-P. E.},
title = {{E}lucidation of the ipso-substitution mechanism for
side-chain cleavage of alpha-quaternary 4-nonylphenols and
4-t-butoxyphenol in {S}phingobium xenophagum {B}ayram},
journal = {Applied and environmental microbiology},
volume = {73},
issn = {0099-2240},
address = {Washington, DC [u.a.]},
publisher = {Soc.},
reportid = {PreJuSER-56261},
pages = {3320 - 3326},
year = {2007},
note = {Record converted from VDB: 12.11.2012},
abstract = {Recently we showed that degradation of several nonylphenol
isomers with alpha-quaternary carbon atoms is initiated by
ipso-hydroxylation in Sphingobium xenophagum Bayram (F. L.
P. Gabriel, A. Heidlberger, D. Rentsch, W. Giger, K.
Guenther, and H.-P. E. Kohler, J. Biol. Chem.
280:15526-15533, 2005). Here, we demonstrate with
18O-labeling experiments that the ipso-hydroxy group was
derived from molecular oxygen and that, in the major pathway
for cleavage of the alkyl moiety, the resulting nonanol
metabolite contained an oxygen atom originating from water
and not from the ipso-hydroxy group, as was previously
assumed. Our results clearly show that the alkyl cation
derived from the alpha-quaternary nonylphenol
4-(1-ethyl-1,4-dimethyl-pentyl)-phenol through
ipso-hydroxylation and subsequent dissociation of the
4-alkyl-4-hydroxy-cyclohexadienone intermediate
preferentially combines with a molecule of water to yield
the corresponding alcohol and hydroquinone. However, the
metabolism of certain alpha,alpha-dimethyl-substituted
nonylphenols appears to also involve a reaction of the
cation with the ipso-hydroxy group to form the corresponding
4-alkoxyphenols. Growth, oxygen uptake, and 18O-labeling
experiments clearly indicate that strain Bayram metabolized
4-t-butoxyphenol by ipso-hydroxylation to a hemiketal
followed by spontaneous dissociation to the corresponding
alcohol and p-quinone. Hydroquinone effected high oxygen
uptake in assays with induced resting cells as well as in
assays with cell extracts. This further corroborates the
role of hydroquinone as the ring cleavage intermediate
during degradation of 4-nonylphenols and 4-alkoxyphenols.},
keywords = {Biodegradation, Environmental / Cyclohexanes: metabolism /
Cyclohexenes / Gas Chromatography-Mass Spectrometry /
Metabolic Networks and Pathways / Molecular Structure /
Oxygen: metabolism / Oxygen Isotopes: metabolism / Phenols:
metabolism / Sphingomonas: chemistry / Sphingomonas: growth
$\&$ development / Sphingomonas: metabolism / Cyclohexanes
(NLM Chemicals) / Cyclohexenes (NLM Chemicals) / Oxygen
Isotopes (NLM Chemicals) / Phenols (NLM Chemicals) /
cyclohexadienone (NLM Chemicals) / 4-nonylphenol (NLM
Chemicals) / 4-butoxyphenol (NLM Chemicals) / Oxygen (NLM
Chemicals) / J (WoSType)},
cin = {ICG-3},
ddc = {570},
cid = {I:(DE-Juel1)ICG-3-20090406},
pnm = {Terrestrische Umwelt},
pid = {G:(DE-Juel1)FUEK407},
shelfmark = {Biotechnology $\&$ Applied Microbiology / Microbiology},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:17369338},
pmc = {pmc:PMC1907130},
UT = {WOS:000246680500024},
doi = {10.1128/AEM.02994-06},
url = {https://juser.fz-juelich.de/record/56261},
}