The synthesis and spectroscopic characterization of an aromatic uranium amidoxime complex

Bernstein, Karl J.; Do‐Thanh, Chi‐Linh; Penchoff, Deborah A.; Cramer, S. Alan; Murdock, Christopher R.; Lu, Zheng; Harrison, Robert J.; Camden, Jon P.; Jenkins, David M.

doi:10.1016/j.ica.2014.06.023

Cited by 21 publications

(26 citation statements)

References 58 publications

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“…The most stable geometries of the uranyl complexes obtained at the M06/SSC/6-311++G(d,p) level of theory are shown in Figure 4. Consistent with previous calculations 13,27 and X-ray diffraction data, 14,17 imide dioxime ligands exhibit tridentate binding with the uranyl ion through two oxime oxygen atoms and imide nitrogen atom. As was observed previously, 13,14,17,27 the central imide nitrogen is deprotonated to allow a tridentate uranyl coordination.…”

Section: Resultssupporting

confidence: 90%

“…Later, Bernstein et al studied the uranyl complex of this ligand extensively and showed that only one equivalent of this ligand crystallizes with the uranyl ion in a tridendate mode. 17 Unlike glutarimidedioxime, no uranyl binding constants were reported for naphthalimidedioxime. To supplement this lack of data, in this work, we expand our previous calculations for oxime ligands to predict and compare the equilibrium constants for the formation of 1:1 uranyl complexes with H 2 ′L and H 2 ″L in the mono-and dianionic forms.…”

Section: +mentioning

confidence: 99%

“…In the case of naphthalimidedioxime, the ligand is protolytically stabilized by incorporating a fused aromatic ring, which decreases the electrophilicity of the imide-carbon centers by resonance stabilization. Later, Bernstein et al studied the uranyl complex of this ligand extensively and showed that only one equivalent of this ligand crystallizes with the uranyl ion in a tridendate mode . Unlike glutarimidedioxime, no uranyl binding constants were reported for naphthalimidedioxime.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Naphthalimidedioxime Ligand-Containing Fibers for Uranium Adsorption from Seawater

Chatterjee

Bryantsev

Brown

et al. 2015

Ind. Eng. Chem. Res.

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A novel ligand-functionalized adsorbent material was prepared using a combination of radiation-induced graft polymerization (RIGP) and click chemistry (1,3 cycloaddition reaction). The design of the ligand-containing amidoxime functionality is based on its chelating efficiency with uranium. In this process, RIGP is used to graft polymer chains on fiber substrates, where the fibers are prepared by irradiating and treating polyethylene (PE) with different bulk ratios of vinyl benzyl chloride and acrylic acid or itaconic acid. Furthermore, chemical modifications of these fibers are performed using a two-step process, where novel bisimidoxime ligands are incorporated into fibers. These ligands contain imidedioxime, which is known to be a uranophile. Also, the core structure of the ligand containing three donor atoms facilitates the formation of chelate with uranyl ion in media such as seawater. Density functional theory calculations were performed to quantify the binding strength with the uranyl ion. When tested with simulated seawater with a uranium concentration of 6 ppm at pH 8.0−8.3, the developed materials showed moderate to high uranium (∼35−50 g U/kg adsorbent) adsorption capacity.

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Section: Resultssupporting

confidence: 90%

Section: +mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of Naphthalimidedioxime Ligand-Containing Fibers for Uranium Adsorption from Seawater

Chatterjee

Bryantsev

Brown

et al. 2015

Ind. Eng. Chem. Res.

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“…The 830 and 900 cm –1 bands are attributed to the symmetric (ν s ) and asymmetric (ν as ) stretching of the uranyl ion, respectively. The uranyl modes in the SEHRS (ν as , 900 cm –1 ) and SERS (ν s , 830 cm –1 ) spectra are shifted lower by approximately 30 cm –1 with respect to the Raman and IR positions obtained from solid uranyl nitrate hexahydrate, 25 indicating the binding of the uranyl ion by the 4-MBA ligand. 23…”

Section: Resultsmentioning

confidence: 91%

Utilizing Molecular Hyperpolarizability for Trace Analysis: A Surface-Enhanced Hyper-Raman Scattering Study of Uranyl Ion

Trujillo

Camden

2018

ACS Omega

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Surface-enhanced hyper-Raman scattering (SEHRS), the nonlinear analog of surface-enhanced Raman scattering (SERS), provides unique spectral signatures arising from the molecular hyperpolarizability. In this work, we explore the differences between SERS and SEHRS spectra obtained from surface-bound uranyl ion. Exploiting the distinctive SEHRS bands for trace detection of the uranyl ion, we obtain excellent sensitivity (limit of detection = 90 ppb) despite the extreme weakness of the hyper-Raman effect. We observe that binding the uranyl ion to the carboxylate group of 4-mercaptobenzoic acid (4-MBA) leads to significant changes in the SEHRS spectrum, whereas the surface-enhanced Raman scattering (SERS) spectrum of the same complex is little changed. The SERS and SEHRS spectra are also examined as a function of both substituent position, using 2-MBA, 3-MBA, and 4-MBA, and the carbon chain length, using 4-mercaptophenylacetic acid and 4-mercaptophenylpropionic acid. These results illustrate that the unique features of SEHRS can yield more information than SERS in certain cases and represent the first application of SEHRS for trace analysis of nonresonant molecules.

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“…This study focuses on lanthanoid mononitrate as this is a highly important system in lanthanoid- and actinoid-separation because of the common binding of one or more nitrates stemming from the often use of nitric acid in the separation process 14,15 —as also noted by Glatz in cataloguing all of the industrial processing for handling spent nuclear fuel. 16 Because of the presence of nitric acid, nitrates bound to lanthanoids and actinoids have been observed in multiple separations, and synthesis and characterization studies with bis[(phosphino)methyl]pyridine-1-oxide (NOPOPO), 2 1,2-phenylenediphosphonates, 17 2,6-bis[(diphenylphosphino)methyl]pyridine N , P , P ′-trioxide, 18 2-((diphenylphosphino) methyl)pyridine, dioxide and 2,6-bis((diphenylphosphino)methyl)pyridineiV, P , P ′-trioxide, 19 decorated pyridine and pyridine n -oxide platforms, 3 tetra-n-donor extractants, 20 undiluted quaternary ammonium ionic liquid, 21 cyclic dilactams, 22 bis-1,2,3-triazolebipyridine, 23 and cyclic imide dioximes, 24 among others.…”

Section: Introductionmentioning

confidence: 99%

Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO₃)]²⁺ (with Ln = La to Lu)

et al. 2019

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Evaluating the efficiency of predictive methods is critical to the processes of upscaling laboratory processes to full-scale operations on an industrial scale. With regard to separation of lanthanoids, there is a considerable motivation to optimize these processes because of immediate use in nuclear fuel cycle operations, nuclear forensics applications, and rare-earth metal recovery. Efficient predictive capabilities in Gibbs free energies of reaction are essential to optimize separations and ligand design for selective binding needed for various radiochemical applications such as nuclear fuel disposition and recycling of lanthanoid fission products into useful radioisotope products. Ligand design is essential for selective binding of lanthanoids, as separating contiguous lanthanoids is challenging because of the similar behavior these elements exhibit. Modeling including electronic structure calculations of lanthanoid-containing compounds is particularly challenging because of the associated computational cost encountered with the number of electrons correlated in these systems and relativistic considerations. This study evaluates the predictive capabilities of various ab initio methods in the calculation of Gibbs free energies of reaction for [Ln(NO 3 )] 2+ compounds (with Ln = La to Lu), as nitrates are critical in traditional separation processes utilizing nitric acid. The composite methodologies evaluated predict Gibbs free energies of reaction for [Ln(NO 3 )] 2+ compounds within 5 kcal mol –1 in most cases from the target method [CCSD(T)-FSII/cc-pwCV∞Z-DK3+SO] at a fraction of the computational cost.

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The synthesis and spectroscopic characterization of an aromatic uranium amidoxime complex

Cited by 21 publications

References 58 publications

Synthesis of Naphthalimidedioxime Ligand-Containing Fibers for Uranium Adsorption from Seawater

Synthesis of Naphthalimidedioxime Ligand-Containing Fibers for Uranium Adsorption from Seawater

Utilizing Molecular Hyperpolarizability for Trace Analysis: A Surface-Enhanced Hyper-Raman Scattering Study of Uranyl Ion

Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO₃)]²⁺ (with Ln = La to Lu)

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The synthesis and spectroscopic characterization of an aromatic uranium amidoxime complex

Cited by 21 publications

References 58 publications

Synthesis of Naphthalimidedioxime Ligand-Containing Fibers for Uranium Adsorption from Seawater

Synthesis of Naphthalimidedioxime Ligand-Containing Fibers for Uranium Adsorption from Seawater

Utilizing Molecular Hyperpolarizability for Trace Analysis: A Surface-Enhanced Hyper-Raman Scattering Study of Uranyl Ion

Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO3)]2+ (with Ln = La to Lu)

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Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO₃)]²⁺ (with Ln = La to Lu)