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Supramolecular agent–simulant correlations for the luminescence based detection of V-series chemical warfare agents with trivalent lanthanide complexes

  • Dennison, Genevieve H. Land Division, Defence Science and Technology Group, Fishermans Bend Melbourne , Australia - Flinders Centre for Nanoscale Science and Technology, School of Chemical and Physical Sciences, Flinders University Adelaide, Australia
  • Bochet, Christian G. Department of Chemistry, University of Fribourg, Switzerland
  • Curty, Christophe Organic Chemistry Branch, Federal Office of Civil Protection (FOCP), Spiez, Switzerland
  • Ducry, Julien Department of Chemistry, University of Fribourg, Switzerland - Organic Chemistry Branch, Federal Office of Civil Protection (FOCP), Spiez, Switzerland
  • Nielsen, David J. Land Division, Defence Science and Technology Group, Fishermans Bend Melbourne , Australia
  • Sambrook, Mark R. CBR Division, Defence Science and Technology Laboratory, Porton Down, United Kingdom
  • Zaugg, Andreas Organic Chemistry Branch, Federal Office of Civil Protection (FOCP), Spiez, Switzerland
  • Johnston, Martin R. Flinders Centre for Nanoscale Science and Technology, School of Chemical and Physical Sciences, Flinders University Adelaide, Australia
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    01.03.2016
Published in:
  • European Journal of Inorganic Chemistry. - 2016, vol. 2016, no. 9, p. 1348-1358
English Solution spectroscopic investigations into the interactions of eight potential bidentate V-series organophosphorus chemical warfare agent (OP CWA) simulants with [Eu(phen)₂(NO₃)₃]·2H₂O demonstrated that the chemical and structural composition of the secondary binding site within the simulant was of paramount importance. Only simulants containing both phosphoryl/phosphonyl and amine moieties generated analogous spectroscopic behaviours to V-series OP CWAs seen in previous studies. The results demonstrated that the bidentate chelation mechanism was driven by the phosphoryl/phosphonyl moieties and that the presence of the amine moieties induced a significant secondary dynamic luminescence quenching mechanism. The binding modes of the simulants VO and TEEP to trivalent lanthanides (Eu and La) were further investigated using ¹H and ³¹P NMR spectroscopic titrations and kinetic IR experiments. VO, with both the phosphonyl and amine binding sites was found to be the most appropriate simulant for V-series OP CWAs in supramolecular studies with trivalent lanthanide ions and we recommend VO for use in supramolecular studies of this type.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
Identifiers
Persistent URL
https://folia.unifr.ch/unifr/documents/304911
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