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

Dennison, Genevieve H.; Bochet, Christian G.; Curty, Christophe; Ducry, Julien; Nielsen, David J.; Sambrook, Mark R.; Zaugg, Andreas; Johnston, Martin R.

doi:10.1002/ejic.201600105

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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

01.03.2016

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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

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