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@ARTICLE{Berns:59679,
author = {Berns, A. E. and Bertmer, M. and Schäffer, A. and Meier,
R. J. and Vereecken, H. and Lewandowski, H.},
title = {{T}he 15{N}-{CPMAS} spectra of simazine and its
metabolites: measurements and quantum chemical calculations},
journal = {European journal of soil science},
volume = {58},
issn = {1351-0754},
address = {Oxford [u.a.]},
publisher = {Wiley-Blackwell},
reportid = {PreJuSER-59679},
pages = {882 - 888},
year = {2007},
note = {Record converted from VDB: 12.11.2012},
abstract = {DFT calculations are a powerful tool to support NMR studies
of xenobiotics such as decomposition studies in soil. They
can help interpret spectra of bound residues, for example,
by predicting shifts for possible model bonds. The described
bound-residue models supported the hypothesis of a free
amino side chain already suspected by comparison with the
experimental data of the standards. No match was found
between the calculated shifts of amide bondings of the amino
side chains (free or substituted) and the experimental NMR
shifts of a previous study. In the present paper,
first-principles quantum chemical calculations were used to
support and check the interpretation of the 15N cross
polarization-magic angle spinning nuclear magnetic resonance
(15N-CPMAS NMR) spectra of simazine and its metabolites.
Density functional theory (DFT) calculations were performed
using Gaussian 03 and the nuclear magnetic shielding tensors
were calculated using the Gauge-Independent Atomic Orbital
(GIAO) method and B3LYP/6–311+G(2d,p) model chemistry.
Good agreement was reached between the calculated and
measured chemical shifts of the core nitrogens and the
lactam and lactim forms of the hydroxylated metabolites
could be clearly distinguished. The calculated spectra
showed that these metabolites exist preferentially in the
lactam form, an important fact when considering the possible
interactions of such hydroxylated metabolites with the soil
matrix. Although the calculated bound-residue models in the
present study only partly matched the experimental data,
they were nevertheless useful in helping to interpret the
experimental NMR results of a previous study. To get a
better match between the calculated and the measured shifts
of the side-chain nitrogens the calculations need to be
further developed, taking into account the influence of
neighbouring molecules in the solid state. Altogether,
quantum chemical calculations are very helpful in the
interpretation of NMR spectra. In the future, they can also
be very useful for the prediction of NMR shifts, in
particular when it is not possible to measure the
metabolites due to a lack of material or in cases where
practical experiments cannot be conducted.},
cin = {ICG-4 / JARA-ENERGY / JARA-SIM},
ddc = {630},
cid = {I:(DE-Juel1)VDB793 / $I:(DE-82)080011_20140620$ /
I:(DE-Juel1)VDB1045},
pnm = {Terrestrische Umwelt},
pid = {G:(DE-Juel1)FUEK407},
shelfmark = {Soil Science},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000248479300003},
doi = {10.1111/j.1365-2389.2007.00927.x},
url = {https://juser.fz-juelich.de/record/59679},
}