Syntheses, spectroscopic analysis, and structural determination of two novel nine-coordinate mononuclear Na4[EuIII(Dtpa)(H2O)]2 · 11.5H2O and binuclear (NH4)4[EuIII(Dtpa)]2 · 10H2O complexes

Gao, Jingqun; Wu, Tong; Wang, J.; Bai, Yuan; Wang, Sai; Xu, Yongnan; Li, Y.; Zhang, X. D.

doi:10.1134/s1070328412060048

Cited by 11 publications

(7 citation statements)

References 33 publications

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“…The calculations only considered the formation of ML − complexes with Am 3+ and Eu 3+ for this comparative work. The calculated EuL − bond distances for carboxylate oxygen (2.30−2.43 Å) and amine nitrogen (2.67− 2.86 Å) atoms in Table 4 are consistent with the corresponding X-ray- 32,33 and DFT-calculated bond lengths for the related EuDTPA 2− complex. 50 Replacing one carboxylate functionality with a 2-pyridylmethyl group results in a longer bond distance between Eu 3+ and the N 3 amine nitrogen atom compared to average Eu−N 1,2 bond lengths.…”

Section: ■ Discussionsupporting

confidence: 80%

Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants

et al. 2018

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The novel metal chelator N-2-(pyridylmethyl)diethylenetriamine-N,N',N″,N″-tetraacetic acid (DTTA-PyM) was designed to replace a single oxygen-donor acetate group of the well-known aminopolycarboxylate complexant diethylenetriamine-N,N,N',N″,N″-pentaacetic acid (DTPA) with a nitrogen-donor 2-pyridylmethyl. Potentiometric, spectroscopic, computational, and radioisotope distribution methods show distinct differences for the 4f and 5f coordination environments and enhanced actinide binding due to the nitrogen-bearing heterocyclic moiety. The Am, Cm, and Ln complexation studies for DTTA-PyM reveal an enhanced preference, relative to DTPA, for trivalent actinide binding. Fluorescence studies indicate no changes to the octadentate coordination of trivalent curium, while evidence of heptadentate complexation of trivalent europium is found in mixtures containing EuHL complexes at the same aqueous acidity. The denticity change observed for Eu suggests that complex protonation occurs on the pyridyl nitrogen. Formation of the CmHL complex is likely due to the protonation of an available carboxylate group because the carbonyl oxygen can maintain octadentate coordination through a rotation. The observed suppressed protonation of the pyridyl nitrogen in the curium complexes may be attributed to stronger trivalent actinide binding by DTTA-PyM. Density functional theory calculations indicate that added stabilization of the actinide complexes with DTTA-PyM may originate from π-back-bonding interactions between singly occupied 5f orbitals of Am and the pyridyl nitrogen. The differences between the stabilities of trivalent actinide chelates (Am, Cm) and trivalent lanthanide chelates (La-Lu) are observed in liquid-liquid extraction systems, yielding unprecedented 4f/5f differentiation when using DTTA-PyM as an aqueous holdback reagent. In addition, the enhanced nitrogen-donor softness of the new DTTA-PyM chelator was perturbed by adding a fluorine onto the pyridine group. The comparative characterization of N-(3-fluoro-2-pyridylmethyl)diethylenetriamine-N,N',N″,N″-tetraacetic acid (DTTA-3-F-PyM) showed subdued 4f/5f differentiation due to the presence of this electron-withdrawing group.

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Section: ■ Discussionsupporting

confidence: 80%

Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants

et al. 2018

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“…Note that the EuEDTA and DEPA complexes are chiral; in solution, they exist in an equilibrium of the "Δ" and "Λ" enantiomeric forms. 29,30 The simulations are well consistent with the experiment in that the predicted CID ratios (2 × 10 −4 to 1 ×10 −3 ) agree with the experimental range of dissymmetry factors found for the EDTA and DEPA complexes and bare Eu 3+ ion. The CPL/total fluorescence ratio is predicted much more reliably than the actual intensities, because absolute values of the transition moments are not known.…”

Section: Analytical Chemistrysupporting

confidence: 77%

“…The mannose complexes were chosen as their geometry maximizes the number of Eu···O interactions. Note that the EuEDTA and DEPA complexes are chiral; in solution, they exist in an equilibrium of the “Δ” and “Λ” enantiomeric forms. , …”

Section: Resultsmentioning

confidence: 99%

“…The Gaussian program was used to provide model geometries. X-ray geometries , of the NaEuEDTA and Na 2 EuDEPA complexes were used as starting geometries and optimized by energy minimization using the B3LYP functional, 6-311++G** basis set (the MWB28 pseudopotential and basis set for Eu), and polarizable continuum model (PCM) for the water environment.…”

Section: Methodsmentioning

confidence: 99%

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Detection of Sugars via Chirality Induced in Europium(III) Compounds

Průša

Kessler

et al. 2016

Anal. Chem.

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Detection and resolution of simple monosaccharides are difficult tasks because their structure is quite similar. The present study shows that circularly polarized luminescence (CPL) induced in europium complexes provides very specific spectral patterns for fructose, mannose, glucose, and galactose. Differences were also observed between bare Eu(3+) ion and its complexes, when interacting with these sugars. The CPL spectra were measured on a Raman optical activity (ROA) spectrometer, which ensured high fluorescence intensity owing to the strong 532 nm laser excitation. The induced fluorescence was recorded in the same spectrum as the vibrational Raman bands. On the basis of the ligand field theory, most fluorescence spectral peaks could be assigned to f-shell europium transitions. Additional information on the interaction of the lanthanide with the sugar component was provided by measurement of time-dependent fluorescence, as formation of different complexes led to variations in fluorescence decay times. In nuclear magnetic resonance (NMR), the paramagnetic metal ion interacting with the sugars caused specific changes in (13)C chemical shifts. The spectroscopic data and molecular dynamics modeling showed that the interaction between the monosaccharides and Eu ion is rather weak due to the competition of the OH sugar groups with water molecules. However, multiple binding modes are possible, which contributes to the complexity and specificity of the spectra. The induced chirality and fluorescence spectra thus appear to be convenient means for monosaccharide detection and identification.

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“…Absorptions at 3075-2885 cm − 1 , 1485-1440 cm − 1 and 1351-1329 cm − 1 were assigned to alkyl stretching mode ν(C-H) [14,15]. Bands at 3354-3290 cm −1 and 1572 cm −1 were attributed to ν(N-H) vibration in MSN/APTES whereas bands at 1734 cm −1 and 1701 cm −1 were attributed to ν(C_O) vibration in MSN/APTES-DTPA indicating the presence of amino and ester groups on the surface, respectively [11,16]. The infrared results suggest that the functionalization process occurs on the silica's surface with the formation of Si-O-Si-R groups.…”

Section: Ftirmentioning

confidence: 99%

Synthesis, characterization, and biodistribution studies of 99m Tc-labeled SBA-16 mesoporous silica nanoparticles

Barros

Ferraz

Dantas

et al. 2015

Materials Science and Engineering: C

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Syntheses, spectroscopic analysis, and structural determination of two novel nine-coordinate mononuclear Na4[EuIII(Dtpa)(H2O)]2 · 11.5H2O and binuclear (NH4)4[EuIII(Dtpa)]2 · 10H2O complexes

Cited by 11 publications

References 33 publications

Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants

Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants

Detection of Sugars via Chirality Induced in Europium(III) Compounds

Synthesis, characterization, and biodistribution studies of 99m Tc-labeled SBA-16 mesoporous silica nanoparticles

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