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Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation - a case study of uranyl(vi) hydrolysis.

ABSTRACT: This study of aqueous metal speciation is an advanced combination of theoretical and experimental methods. Continuous wave (CW) and time-resolved laser-induced fluorescence spectroscopy (TRLFS) data of uranyl(vi) hydrolysis were analyzed using parallel factor analysis (PARAFAC). Distribution patterns of five major species were thereby derived under a fixed uranyl concentration (10-5 M) over a wide pH range from 2 to 11. UV (180 nm to 370 nm) excitation spectra were extracted for individual species. Time-dependent density functional theory (TD-DFT) calculations revealed ligand excitation (water, hydroxo, oxo) in this region and ligand-to-metal charge transfer (LMCT) responsible for luminescence. Thus excitation in the UV region is extreme ligand sensitive and specific. Combining findings from PARAFAC and DFT the [UO2(H2O)5]2+ cation (aquo complex 1?:?0) and four hydroxo complexes (1?:?1, 3?:?5, 3?:?7 and 1?:?3) were identified. The methodological concept used here is applicable to luminescent metals in general and thus enables acquisition of refined structural and thermodynamical data of lanthanide and actinide complexation.

SUBMITTER: Drobot B

PROVIDER: S-EPMC5811152 | biostudies-other | 2015 Feb

REPOSITORIES: biostudies-other

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Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation - a case study of uranyl(vi) hydrolysis.

Drobot Björn B Steudtner Robin R Raff Johannes J Geipel Gerhard G Brendler Vinzenz V Tsushima Satoru S

Chemical science 20141028 2

This study of aqueous metal speciation is an advanced combination of theoretical and experimental methods. Continuous wave (CW) and time-resolved laser-induced fluorescence spectroscopy (TRLFS) data of uranyl(vi) hydrolysis were analyzed using parallel factor analysis (PARAFAC). Distribution patterns of five major species were thereby derived under a fixed uranyl concentration (10<sup>-5</sup> M) over a wide pH range from 2 to 11. UV (180 nm to 370 nm) excitation spectra were extracted for indiv ...[more]

PMID: 29560182

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Project description:Naturally occurring uranium is a widespread contaminant present in the water resources around the abandoned uranium mines in the southwest United States. A novel method for rapid uranium detection has been recently developed that relies on the sequestering of uranium by amidoximated polyacrylonitrile (AO-PAN) polymer mats and uses the Raman-active (ν1) symmetric stretch as the signal. The Raman signals obtained from uranium bearing AO-PAN were challenging to interpret due to an unknown uranyl speciation on the surface of the mats. Herein, we provide the synthesis and structural characterization of six model coordination compounds that contain acetamidoxime/benzamidoxime (AAO/BAO) coordinated to the uranyl cation: [UO2(η1-AAO)(NO3)2(H2O)] (1), [UO2(η1-AAO)2(NO3)2] (2), [UO2(η2-BAO)2(CH3OH)2] (3), [(UO2)3(η2-BAO)3(μ2-NO3)3] (4), [(UO2)4(μ3-O)2(μ2-BAO)4(η1-BAO)4(H2O)2](NO3)4 (5), and [(UO2)4(μ3-O)2(μ2-BAO)4(η1-BAO)6Na(NO3)2](NO3)3 (6). Solid-state Raman spectra of 1-6 showed dramatic differences in the uranyl ν1 symmetric stretch depending on the coordination of the amidoxime functional group. The assignments made from the solid-state Raman spectra were used to deconvolute the solution-state Raman spectra of uranyl-acetamidoxime/benzamidoxime methanol solutions at different metal to ligand molar ratios. At low molar ratios (1 U:1 AAO/BAO and 1 U:2 AAO/BAO) the dominant species is the uranyl coordinated via the η1-oxygen atom of the oxime group, while at high molar ratios (1 U:3 AAO/BAO and 1 U:4 AAO/BAO) the dominant species are a tetrameric uranyl-μ3-O-η1-amidoxime complex similar to compounds 5 and 6 and a uranyl-η2-amidoxime complex similar to compounds 3 and 4. Solid-state Raman spectra showed good agreement with Raman signals obtained from the uranyl-AO-PAN mats, demonstrating that binding motifs between uranyl and amidoxime in compounds 5 and 6 are the most representative of the uranyl species on the surface of the AO-PAN mats.

Dataset Information

Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation - a case study of uranyl(vi) hydrolysis.

Publications

Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation - a case study of uranyl(vi) hydrolysis.

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