Complex formation between UO22+ and α-isosaccharinic acid: insights on a molecular level

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dc.identifier.uri Brinkmann, Hannes eng Patzschke, Michael eng Kaden, Peter eng Raiwa, Manuel eng Rossberg, André eng Kloditz, Roger eng Heim, Karsten eng Moll, Henry eng Stumpf, Thorsten eng 2021-08-03T09:54:48Z 2021-08-03T09:54:48Z 2019
dc.identifier.citation Brinkmann, H.; Patzschke, M.; Kaden, P.; Raiwa, M.; Rossberg, A. et al.: Complex formation between UO22+ and α-isosaccharinic acid: insights on a molecular level. In: Dalton Transactions 498 (2019), Nr. 38, 13440. DOI: eng
dc.description.abstract Cellulosic materials present as tissue, paper, wood, or filter materials in low and intermediate level waste will degrade under alkaline conditions if water ingresses in a cementitious backfilled repository. The main degradation product is isosaccharinic acid. Complex formation with isosaccharinic acid may adversely affect the retention of radionuclides by the sorption or formation of solid phases. Hence, this compound is of particular concern in the context of nuclear waste disposal. Structural information of complexes is limited to spherical metal centers and little is known about the interaction of uranyl (UVIO22+) with isosaccharinic acid. Therefore, the interaction of UO22+ with α-isosaccharinate (ISA) was studied under acidic conditions focusing particularly on the structural characterization of the formed complexes. Attenuated total reflection Fourier-transform infrared (ATR-FTIR), nuclear magnetic resonance (NMR), UV-Vis, extended X-ray absorption fine structure (EXAFS) spectroscopy and electrospray-ionization mass spectrometry (ESI-MS) were combined with theoretical calculations to obtain a process understanding on the molecular level. The dominant binding motifs in the formed complexes are 5- and 6-membered rings involving the carboxylic group as well as the α- or β-hydroxy group of ISA. Two concentration dependent complex formation mechanisms were identified involving either mono- ([UO2(ISA)(H2O)3]+) or binuclear ([(UO2)2(ISA)(H2O)6]3+) species. Furthermore, this study unveils the interaction of UO22+ with the protonated α-isosaccharinic acid (HISA) promoting its transformation to the corresponding α-isosaccharinate-1,4-lactone (ISL) and inhibiting the formation of polynuclear UO22+–ISA species. Future studies on related systems will benefit from the comprehensive knowledge concerning the behavior of ISA as a complexing agent gained in the present study. eng
dc.language.iso eng eng
dc.publisher London : Royal Society of Chemistry
dc.relation.ispartofseries Dalton Transactions 498 (2019), Nr. 38 eng
dc.rights CC BY 3.0 Unported eng
dc.rights.uri eng
dc.subject Absorption spectroscopy eng
dc.subject Complexation eng
dc.subject Degradation eng
dc.subject Electrodeposition eng
dc.subject Electrospray ionization eng
dc.subject Extended X ray absorption fine structure spectroscopy eng
dc.subject Fourier transform infrared spectroscopy eng
dc.subject Mass spectrometry eng
dc.subject Nuclear magnetic resonance eng
dc.subject Nuclear magnetic resonance spectroscopy eng
dc.subject Waste disposal eng
dc.subject X ray absorption eng
dc.subject.ddc 540 | Chemie eng
dc.title Complex formation between UO22+ and α-isosaccharinic acid: insights on a molecular level eng
dc.type article eng
dc.type Text eng
dc.relation.essn 1477-9234
dc.relation.issn 1477-9226
dc.relation.doi 10.1039/C9DT01080G
dc.description.version publishedVersion eng
tib.accessRights frei zug�nglich eng

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