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@ARTICLE{Huschek:716,
author = {Huschek, G. and Hollmann, D. and Kurowski, N. and
Kaupenjohann, M. and Vereecken, H.},
title = {{R}e-evaluation of the conformational structure of
sulfadiazine species using {NMR} and ab initio {DFT} studies
and its implication on sorption and degradation},
journal = {Chemosphere},
volume = {72},
issn = {0045-6535},
address = {Amsterdam [u.a.]},
publisher = {Elsevier Science},
reportid = {PreJuSER-716},
pages = {1448 - 1454},
year = {2008},
note = {The authors gratefully acknowledge the financial support
provided by the German Research Foundation (DFG - Deutsche
Forschungsgemeinschaft) for Research Unit 566 Veterinary
Medicines in Soil. We would also like to thank Dr. A. Koch
for his excellent technical and analytical support.},
abstract = {In the environment, the sorption and the degradation of
organic pollutants are of increasing interest. The
investigation of the chemical structures provides a basis
for the development of a suitable binding model approach and
for the mechanistic understanding of the chemical fate
processes. The aim of this study was the identification of
different species of the antibiotic compound sulfadiazine
(SDZ) using (1)H and (13)C NMR experiments and ab initio
density functional theory (DFT) calculations. In the
neutral, aprotic solvent dimethylsulfoxide-d(6) (DMSO-d(6)),
a new sulfadiazine structure containing an O-H-N hydrogen
bond was identified. In the protic solvent water-d(2) and in
dependence on pH and the position of the amidogen hydrogen
atom nine possible SDZ conformations were analyzed and five
structures were identified. Good conformity between theory
and calculation of (1)H NMR was observed. Unfortunately,
(13)C NMR is not sensitive enough for comparison and
differentiation. In order to verify the identified
structures, additional NBO/NLMO (natural localized molecular
orbital) analyses were conducted (calculation of net atomic
charges, bond polarity, atomic valence, and electron
delocalization). Finally, conformation optimizations were
performed in order to investigate the stability of the SDZ
species. We showed that SDZ contains no S=O double bond, but
that it has two S-O single bonds. Surprisingly, negative
charges were observed at the pyrimidine nitrogen atom. With
these results, the known structure of SDZ was revised.
Studies of the geometrical structure and the torsion angles
showed that SDZ is very flexible and can be easily fitted to
the sorbent. These observations would explain the strong
sorbance and hence the rapid formation of non-extractable
residues in the environment because SDZ acts as a strong
ligand. These results show that that the sulfonamide
hydrogen is important for the biological activity but the
pyrimidine nitrogen and the sulfonamide oxygen is
responsible for the sorbance in environment.},
keywords = {Absorption / Hydrogen-Ion Concentration / Magnetic
Resonance Spectroscopy: methods / Models, Molecular /
Molecular Structure / Sulfadiazine: chemistry / Sulfadiazine
(NLM Chemicals) / J (WoSType)},
cin = {ICG-4 / JARA-ENERGY / JARA-SIM},
ddc = {333.7},
cid = {I:(DE-Juel1)VDB793 / $I:(DE-82)080011_20140620$ /
I:(DE-Juel1)VDB1045},
pnm = {Terrestrische Umwelt},
pid = {G:(DE-Juel1)FUEK407},
shelfmark = {Environmental Sciences},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:18602132},
UT = {WOS:000259166200008},
doi = {10.1016/j.chemosphere.2008.05.038},
url = {https://juser.fz-juelich.de/record/716},
}