skip to main content

Title: Solution structure of a europium–nicotianamine complex supports that phytosiderophores bind lanthanides
We report the solution structure of a europium-nicotianamine complex predicted from ab initio molecular dynamics simulations with density functional theory. Emission and excitation spectroscopy show that the Eu 3+ coordination environment changes in the presence of nicotianamine, suggesting complex formation, such as what is seen for the Eu 3+ –nicotianamine complex structure predicted from computation. We modeled Eu 3+ –ligand complexes with explicit water molecules in periodic boxes, effectively simulating the solution phase. Our simulations consider possible chemical events ( e.g. coordination bond formation, protonation state changes, charge transfers), as well as ligand flexibility and solvent rearrangements. Our computational approach correctly predicts the solution structure of a Eu 3+ –ethylenediaminetetraacetic acid complex within 0.05 Å of experimentally measured values, backing the fidelity of the predicted solution structure of the Eu 3+ –nicotianamine complex. Emission and excitation spectroscopy measurements were also performed on the well-known Eu 3+ –ethylenediaminetetraacetic acid complex to validate our experimental methods. The electronic structure of the Eu 3+ –nicotianamine complex is analyzed to describe the complexes in greater detail. Nicotianamine is a metabolic precursor of, and structurally very similar to, phytosiderophores, which are responsible for the uptake of metals in plants. Although knowledge that nicotianamine binds europium more » does not determine how plants uptake rare earths from the environment, it strongly supports that phytosiderophores bind lanthanides. « less
; ; ; ;
Award ID(s):
Publication Date:
Journal Name:
Physical Chemistry Chemical Physics
Page Range or eLocation-ID:
4287 to 4299
Sponsoring Org:
National Science Foundation
More Like this
  1. Ligand selectivity to specific lanthanide (Ln) ions is key to the separation of rare earth elements from each other. Ligand selectivity can be quantified with relative stability constants (measured experimentally) or relative binding energies (calculated computationally). The relative stability constants of EDTA (ethylenediaminetetraacetic acid) with La 3+ , Eu 3+ , Gd 3+ , and Lu 3+ were predicted from relative binding energies, which were quantified using electronic structure calculations with relativistic effects and based on the molecular structures of Ln–EDTA complexes in solution from density functional theory molecular dynamics simulations. The protonation state of an EDTA amine group was varied to study pH ∼7 and ∼11 conditions. Further, simulations at 25 °C and 90 °C were performed to elucidate how structures of Ln–EDTA complexes varying with temperature are related to complex stabilities at different pH conditions. Relative stability trends are predicted from computation for varying Ln 3+ ions (La, Eu, Gd, Lu) with a single ligand (EDTA at pH ∼11), as well as for a single Ln 3+ ion (La) with varying ligands (EDTA at pH ∼7 and ∼11). Changing the protonation state of an EDTA amine site significantly changes the solution structure of the Ln–EDTA complex resulting inmore »a reduction of the complex stability. Increased Ln–ligand complex stability is correlated to reduced structural variations in solution upon an increase in temperature.« less
  2. We report here the characterization in solution (NMR, luminescence, MS) and the solid-state (X-ray crystallography, IR) of complexes between phenacyldiphenylphosphine oxide and five Ln( iii ) ions (Sm, Eu, Gd, Tb, Dy). Four single crystal X-ray structures are described here showing a 1 : 2 ratio between the Ln 3+ ions Eu, Dy, Sm and Gd and the ligand, where the phosphine oxide ligands are bound in a monodentate manner to the metal center. A fifth structure is reported for the 1 : 2 Eu(NO 3 ) 3 -ligand complex showing bidentate binding between the two ligands and the metal center. The solution coordination chemistry of these metal complexes was probed by 1 H, 13 C and 31 P NMR, mass spectrometry, and luminescence experiments. The title ligand has the capability to sensitize Tb 3+ , Dy 3+ , Eu 3+ and Sm 3+ leading to metal-centered emission in solutions of acetonitrile and methanol and in the solid state.
  3. Abstract Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals—corundum (α-Al 2 O 3 ), γ-alumina (γ-Al 2 O 3 ) and gibbsite (γ-Al(OH) 3 )—and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al 2 O 3 ) and γ-alumina (γ-Al 2 O 3 ) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weakmore »sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals. Graphical Abstract« less
  4. Four groups of rare-earth complexes, comprising 11 new compounds, with fluorinated O-donor ligands ([K(THF)6][Ln(OC4F9)4(THF)2] (1-Ln; Ln = Ce, Nd), [K](THF)x[Ln(OC4F9)4(THF)y] (2-Ln; Ln = Eu, Gd, Dy), [K(THF)2][Ln(pinF)2(THF)3] (3-Ln; Ln = Ce, Nd), and [K(THF)2][Ln(pinF)2(THF)2] (4-Ln; Ln = Eu, Gd, Dy, Y) have been synthesized and characterized. Single-crystal X-ray diffraction data were collected for all compounds except 2-Ln. Species 1-Ln, 3-Ln, and 4-Ln are uncommon examples of six-coordinate (Eu, Gd, Dy, and Y) and seven-coordinate (Ce and Nd) LnIII centers in all-O-donor environments. Species 1-Ln, 2-Ln, 3-Ln, and 4-Ln are all luminescent (except where Ln = Gd and Y), with the solid-state emission of 1-Ce being exceptionally blue-shifted for a Ce complex. The emission spectra of the six Nd, Eu, and Dy complexes do not show large differences based on the ligand and are generally consistent with the well-known free-ion spectra. Time-dependent density functional theory results show that 1-Ce and 3-Ce undergo allowed 5f → 4d excitations, consistent with luminescence lifetime measurements in the nanosecond range. Eu-containing 2-Eu and 4-Eu, however, were found to have luminescence lifetimes in the millisecond range, indicating phosphorescence rather than fluorescence. The performance of a pair of multireference models for prediction of the Ln = Nd,more »Eu, and Dy absorption spectra was assessed. It was found that spectroscopy-oriented configuration interaction as applied to a simplified model in which the free-ion lanthanide was embedded in ligand-centered Löwdin point charges performed as well (Nd) or better (Eu and Dy) than canonical NEVPT2 calculations, when the ligand orbitals were included in the treatment.« less
  5. Abstract

    New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light‐emitting materials. A new design of Eu‐containing polymer hydrogels showing fast self‐healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu–iminodiacetate (IDA) coordination in a hydrophilic poly(N,N‐dimethylacrylamide) matrix. Dynamic metal–ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self‐healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol–gel transition through the reversible formation and dissociation of Eu–IDA complexes upon various stimuli. It is demonstrated that Eu‐containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.