Investigation on uranyl interaction with bioactive ligands. Synthesis and structural studies of the uranyl complexes with glycine and <i>N</i>-(2-mercaptopropionyl)glycine

Keramidas, Anastasios D.; Rikkou, Maria D.; Drouza, Chryssoula; Raptopoulou, Catherine P.; Terzis, A.; Pashalidis, Ioannis

doi:10.1524/ract.2002.90.9-11_2002.549

Cited by 20 publications

(14 citation statements)

References 16 publications

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“…Over the past few years, an intense scientific effort has taken place to develop specific chelators for metal ions, including actinides, to combat environmental contamination caused by heavy metals, which is considered a serious and widespread health problem due to their high toxicity. − Uranium has been the primary target for separation from the radioactive waste produced by nuclear industries and chelation therapy to be removed from human body . In the last few decades, multidentate complexing agents with oxygen donor atoms, based on phosphonic ligands − or siderophore-based units , and polysulfides, − have been identified as effective uranium chelators.…”

Section: Introductionmentioning

confidence: 99%

Bis(hydroxylamino)triazines: High Selectivity and Hydrolytic Stability of Hydroxylamine-Based Ligands for Uranyl Compared to Vanadium(V) and Iron(III)

et al. 2018

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The development of ligands with high selectivity and affinity for uranium is critical in the extraction of uranium from human body, radioactive waste, and seawater. A scientific challenge is the improvement of the selectivity of chelators for uranium over other heavy metals, including iron and vanadium. Flat ligands with hard donor atoms that satisfy the geometric and electronic requirements of the UO exhibit high selectivity for the uranyl moiety. The bis(hydroxylamino)(triazine) ligand, 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (Hbihyat), a strong binder for hard metal ions (Fe, Ti, V, and Mo), reacted with [UO(NO)(HO)]·4HO in aqueous solution and resulted in the isolation of the complexes [UO(bihyat)(HO)], [UO(bihyat)], and {[UO(bihyat)(μ-OH)]}. These three species are in equilibrium in aqueous solution, and their abundance varies with the concentration of Hbihyat and the pH. Reaction of Hbihyat with [UO(NO)(HO)]·4HO in CHCN gave the trinuclear complex [UO(bihyat)(μ-bihyat)], which is the major species in organic solvents. The dynamics between the UO and the free ligand Hbihyat in aqueous and dimethyl sulfoxide solutions; the metal binding ability of the Hbihyat over pyridine-2,6-dicarboxylic acid (Hdipic) or glutarimidedioxime for UO, and the selectivity of the Hbihyat to bind UO in comparison to VO and Fe in either UO/VO or UO/Fe solutions were examined by NMR and UV-vis spectroscopies. The results revealed that Hbihyat is a superior ligand for UO with high selectivity compared to Fe and VO, which increases at higher pHs. Thus, this type of ligand might find applications in the extraction of uranium from the sea and its removal from the environment and the human body.

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Section: Introductionmentioning

confidence: 99%

Bis(hydroxylamino)triazines: High Selectivity and Hydrolytic Stability of Hydroxylamine-Based Ligands for Uranyl Compared to Vanadium(V) and Iron(III)

et al. 2018

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“…X-ray structural studies of solid uranyl-glycine complexes show that the carboxylate rather than the amino group binds to oxophilic uranium. Here, glycine does rarely act as a chelating ligand with its C O 2 − and N H 2 0 ends forming a 5-membered ring. , Usually, mono- or bidentate carboxylate coordination by the R-CO 2 − ligand is observed in the crystals, forming a four-membered ring in the latter case. All that may hold true also in (non-basic) aqueous solutions.…”

Section: Introductionmentioning

confidence: 99%

Uranyl-Glycine-Water Complexes in Solution: Comprehensive Computational Modeling of Coordination Geometries, Stabilization Energies, and Luminescence Properties

et al. 2011

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Comprehensive computational modeling of coordination structures, thermodynamic stabilities, and luminescence spectra of uranyl-glycine-water complexes [UO(2)(Gly)(n)aq(m)](2+) (Gly = glycine, aq = H(2)O, n = 0-2, m = 0-5) in aqueous solution has been carried out using relativistic density functional approaches. The solvent is approximated by a dielectric continuum model and additional explicit water molecules. Detailed pictures are obtained by synergic combination of experimental and theoretical data. The optimal equatorial coordination numbers of uranyl are determined to be five. The energies of several complex conformations are competitively close to each other. In non-basic solution the most probable complex forms are those with two water ligands replaced by the bidentate carboxyl groups of zwitterionic glycine. The N,O-chelation in non-basic solution is neither entropically nor enthalpically favored. The symmetric and antisymmetric stretch vibrations of the nearly linear O-U-O unit determine the luminescence features. The shapes of the vibrationally resolved experimental solution spectra are reproduced theoretically with an empirically fitted overall line-width parameter. The calculated luminescence origins correspond to thermally populated, near-degenerate groups of the lowest electronically excited states of (3)Δ(g) and (3)Φ(g) character, originating from (U-O)σ(u) → (U-5f)δ(u),ϕ(u) configurations of the linear [OUO](2+) unit. The intensity distributions of the vibrational progressions are consistent with U-O bond-length changes around 5 1/2 pm. The unusually high intensity of the short wavelength foot is explained by near-degeneracy of vibrationally and electronically excited states, and by intensity enhancement through the asymmetric O-U-O stretch mode. The combination of contemporary computational chemistry and experimental techniques leads to a detailed understanding of structures, thermodynamics, and luminescence of actinide compounds, including those with bioligands.

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“…Uranyl(VI) halides commonly form six-coordinate complexes of the general formula UO 2 X 2 L 2 , where L is a neutral ligand that serves to cap the uranium coordination sphere. These complexes overwhelmingly occur as the trans isomer (A; Chart 1); of the few structurally characterized examples in which the two halide ligands are situated at adjacent equatorial sites, these compounds are either hydrated [2] (or possess ligands L with terminal O-H groups) [3,4], suffer from poor solubility [5], or have been obtained in unspecified yield from non-uranyl precursors [6]. Given the synthetic importance of stereochemical control in metal halide systems, a rational methodology to anhydrous uranyl(VI) cis-dihalide complexes that can serve as suitable starting materials with reagents in nonprotic solvents remains an unrealized goal.…”

mentioning

confidence: 99%

Convenient syntheses of uranyl(VI) cis-dihalide complexes as anhydrous starting materials

Duval

Kannan

Barnes

2006

Inorganic Chemistry Communications

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Investigation on uranyl interaction with bioactive ligands. Synthesis and structural studies of the uranyl complexes with glycine and N-(2-mercaptopropionyl)glycine

Cited by 20 publications

References 16 publications

Bis(hydroxylamino)triazines: High Selectivity and Hydrolytic Stability of Hydroxylamine-Based Ligands for Uranyl Compared to Vanadium(V) and Iron(III)

Bis(hydroxylamino)triazines: High Selectivity and Hydrolytic Stability of Hydroxylamine-Based Ligands for Uranyl Compared to Vanadium(V) and Iron(III)

Uranyl-Glycine-Water Complexes in Solution: Comprehensive Computational Modeling of Coordination Geometries, Stabilization Energies, and Luminescence Properties

Convenient syntheses of uranyl(VI) cis-dihalide complexes as anhydrous starting materials

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