Interaction Of Lanthanides Research Articles

Thermally stable Sm3+ -doped alkali zinc alumino borosilicate (AZABS) glass for warm white light generation and w-LED applications.

Samarium ion (Sm3+ )-doped alkali zinc alumino borosilicate (AZABS) glass was synthesized via quick melt quench technique. Various spectroscopic studies like optical absorption, photoluminescence (PL) emission, PL excitation, temperature-dependent PL and PL decay kinetics were performed on the as prepared glass system. Under 402 nm excitation, three sharp bands at wavelengths 563, 599 and 645 nm corresponding to transitions 4 G5/2 → 6 H5/2 , 6 H7/2 and 6 H9/2 , respectively, can be seen in the PL emission spectra. The 0.25 mol% Sm3+ glass has the highest intensity for these emissions. The lanthanide interaction in the glass matrix is dipole-dipole in nature as was proven from Dexter's analysis. The direct bandgap of 0.25 mol% Sm3+ -doped AZABS glass was calculated to be 2.88 eV. The lifetimes of the as prepared glass range from 1.93 ms for the lowest concentration of Sm3+ to 0.75 ms for the highest. From temperature dependent PL studies, the activation energy for 0.25 mol% Sm3+ -doped AZABS glass was found to be 0.19 eV which shows high thermal stability of this glass. We propose to utilize these Sm3+ -doped AZABS glasses for white-light emitting diodes (w-LEDs) and solid-state lighting (SSL) applications.

How tobacco (Nicotiana tabacum) BY-2 cells cope with Eu(III) - a microspectroscopic study.

The extensive use of lanthanides in science, industry and high-technology products is accompanied by an anthropogenic input of rare earth elements into the environment. Knowledge of a metal's environmental fate is essential for reasonable risk assessment and remediation approaches. In the present study, Eu(III) was representatively used as a luminescent probe to study the chemical environment and to elucidate the molecular interactions of lanthanides with a suspension cell culture of Nicotiana tabacum BY-2. Biochemical methods were combined with luminescence spectroscopy, two-dimensional microspectroscopic mappings, and data deconvolution methods to resolve the bioassociation behavior and spatial distribution of Eu(III) in plant cells. BY-2 cells were found to gradually take up the metal after exposure to 100 μM Eu(III) without significant loss of viability. Time-resolved luminescence measurements were used to specify the occurrence of Eu(III) species as a function of time, revealing the transformation of an initial Eu(III) species into another after 24 h exposure. Chemical microscopy and subsequent iterative factor analysis reveal the presence of four distinct Eu(III) species located at different cellular compartments, e.g., the cell nucleus, nucleolus and cell walls, which could be assigned to intracellular binding motifs. In addition, a special type of bioaccumulation occurs through the formation of a Eu(III)-containing oxalate biomineral, which is already formed within the first 24 hours after metal exposure. Oxalate crystals were also obtained in analogous experiments with Gd and Sm. These results indicate that tobacco BY-2 cells induce the precipitation of metal oxalate biominerals for detoxification of lanthanides, although they also bind to other cellular ligands at the same time.

Convenient Confinement: Interplay of Solution Conditions and Graphene Oxide Film Structure on Rare Earth Separations

Graphene oxide (GO) membranes are excellent candidates for a range of separation applications, including rare earth segregation and radionuclide decontamination. Understanding nanoscale water and ion behavior near interfacial GO is critical for groundbreaking membrane advances, including improved selectivity and permeability. We experimentally examine the impact of solution conditions on water and lanthanide interactions with interfacial GO films and connect these results to GO membrane performance. The investigation of the confined films at the air-water interface with a combination of surface-specific spectroscopy and X-ray scattering techniques allows us to understand water and ion behaviors separately. Sum frequency generation spectroscopy reveals a dramatic change in interfacial water organization because of graphene oxide film deprotonation. Interfacial X-ray fluorescence measurements show a 17× increase in adsorbed lanthanide to the GO film from subphase pH 3 to pH 9. Liquid surface X-ray reflectivity data show an additional 2.7 e- per Å2 for GO films at pH 9 versus pH 3 as well. These results are connected to GO membrane performance, which show increased selectivity and decreased flux for membranes filtering pH 9 solutions. We posit insoluble lanthanide hydroxides form at higher pHs. Taken together, these results highlight the importance of interfacial experiments on model GO systems.

Interaction of lanthanide and actinide with BaHfO3 perovskite: A case study with cerium and uranium

AbstractSpeciation of actinide (An) and lanthanide (Ln) in technologically important ceramics is very important from both fundamental as well as technological aspects. The intrinsic structural flexibility of perovskite containing AO6 and BO12 polyhedra makes them suitable and rich hosts for An and Ln. In this work, emphasis was given to deciphering information such as oxidation state, local dopant site, charge compensating defects, excited state kinetics, and so forth in BaHfO3 (BHO) related to dopant uranium (BHO‐U) and cerium (BHO‐Ce). Several spectroscopic techniques namely, time‐resolved photoluminescence (TRPL), positron annihilation lifetime spectra (PALS), and thermoluminescence (TL) spectroscopy coupled with density functional theory (DFT) were employed to probe the same. Ce and U though are distributed at both Ba and Hf sites, Ce prefers the former, while U prefers the latter site. Uranium on the other hand stabilizes as U6+ in the form of octahedral uranate ion giving green emission. PALS suggested the formation of defects in BHO‐Ce and BHO‐U with oxygen vacancies predominating in the former whereas BHO‐U perovskites are loaded with cation vacancies and vacancy clusters. These cation vacancies are responsible for lower TL output in BHO‐U. TL measurements also suggested cerium doping leads to a higher density of deeper traps in BHO‐Ce compared to uranium doping in BHO‐U which is in concurrence with DFT results and may have implications in designing afterglow phosphors based on perovskite. We believe this work would have a long‐term impact on exploring the potential of perovskite for nuclear waste host and afterglow phosphors applications.

NIR-I-Responsive Single-Band Upconversion Emission through Energy Migration in Core-Shell-Shell Nanostructures.

Here we report a new strategy to tune both excitation and emission peaks of upconversion nanoparticles (UCNPs) into the first infrared biowindow (NIR-I, 650-900 nm) with high NIR-I-to-NIR-I upconversion efficiency. By introducing the sensitizer Nd3+ , activator Er3+ , energy migrator Yb3+ and energy manipulator Mn2+ into specific region to construct proposed energy migration processes in the designed core-shell-shell nanoarchitecture, back energy transfer (BET) from activator to sensitizer or migrator can be greatly blocked and the NIR-to-red upconversion emission can be efficiently promoted. Consequently, BET-induced photon quenching and the undesired green-emitting radiative transition are entirely eliminated, leading to high-efficiency single-band red upconversion emission upon 808 nm NIR-I laser excitation. Our findings provide insights into fundamental lanthanide interactions and advance the development of UCNPs for bioapplications with techniques that overturn traditional limitations.

NIR‐I‐Responsive Single‐Band Upconversion Emission through Energy Migration in Core–Shell–Shell Nanostructures

AbstractHere we report a new strategy to tune both excitation and emission peaks of upconversion nanoparticles (UCNPs) into the first infrared biowindow (NIR‐I, 650–900 nm) with high NIR‐I‐to‐NIR‐I upconversion efficiency. By introducing the sensitizer Nd3+, activator Er3+, energy migrator Yb3+ and energy manipulator Mn2+ into specific region to construct proposed energy migration processes in the designed core–shell–shell nanoarchitecture, back energy transfer (BET) from activator to sensitizer or migrator can be greatly blocked and the NIR‐to‐red upconversion emission can be efficiently promoted. Consequently, BET‐induced photon quenching and the undesired green‐emitting radiative transition are entirely eliminated, leading to high‐efficiency single‐band red upconversion emission upon 808 nm NIR‐I laser excitation. Our findings provide insights into fundamental lanthanide interactions and advance the development of UCNPs for bioapplications with techniques that overturn traditional limitations.

La(III), Ce(III), Gd(III), and Eu(III) Complexation with Tris(hydroxymethyl)aminomethane in Aqueous Solution.

Lanthanides such as cerium(III), europium(III), and gadolinium(III) are widely used for designing fluorescent probes or magnetic resonance imaging contrasting agents for biological systems. The synthesis and study of lanthanide complexes in buffer solutions imitating biological fluids are often complicated because of a lack of data on the lanthanide interactions with buffer solution components. Therefore, Ln(III) [where Ln(III) = La(III), Ce(III), Gd(III), Eu(III)] complexation with a widely used buffer agent, tris(hydroxymethyl)aminomethane (Tris), in aqueous solution is studied using potentiometry, spectrofluorimetry, and 139La NMR spectroscopy. The stoichiometric composition of complexes is determined using mass spectrometry. The thermodynamic stability constants of Ln(III)-Tris complexes are calculated from potentiometric and spectral data; the difficulties in the study of these systems, reliability, and accuracy of the obtained constants are discussed. The possible structures of free Tris and its complexes with lanthanides(III) are optimized on the density functional theory/PBE0 level; the peculiarities of metal-ligand bonds were studied by Quantum Theory Atoms in Molecules analysis.

Binding of lanthanide salts to zwitterionic phospholipid micelles

As the use of lanthanide salts in biophysical systems increases and the separation of lanthanides from nuclear and other wastes with extraction processes has become an important technological challenge, a deeper understanding of the behavior of lanthanides at lipid interfaces is urgently needed. In this work the interaction of lanthanide salts with zwitterionic phospholipids is probed using aqueous micelles of the surfactant dodecyl phosphocholine (DPC), which are useful membrane-mimetic model systems, widely used for the solubilization of membrane proteins in aqueous solutions. Because more than one species exists in lanthanide salt solutions, even at the pH value of 4 used in this experiment, the major goal of this investigation is to examine which species are actually binding to the micelles. Using static and time-dependent europium fluorescence, strong indications are obtained that both the Eu3+ cation and its 1:1 chloride, nitrate, or sulfate complexes bind to the micelles, whereas the europium species do not appear to interact strongly with DPC molecules below the cmc. From isothermal titration calorimetry (ITC) measurements it is found that the lanthanide interaction with DPC micelles increases to the right of the lanthanide series and is - surprisingly – endothermic, underlying the important role of hydration effects in the interaction. The anion of the lanthanide salt strongly influences the thermodynamics: perchlorate and sulfate salts give extraordinary results, switching the interaction to exothermic. A multi-level phenomenological electrostatic model of the europium fluorescence lifetimes strongly suggests that in the case of nitrate salts both Ln3+ and LnNO32+ ions bind to the micelles. Overall a detailed molecular picture of the complexity of lanthanide-lipid interactions at interfaces is emerging from these experiments and the associated modelling effort.

Lanthanides compete with calcium for binding to cadherins and inhibit cadherin-mediated cell adhesion.

Lanthanides are rare-earth metals with a broad range of applications in biological research and medicine. In addition to their unique magnetic and spectroscopic properties, lanthanides are also effective mimics of calcium and can stimulate or inhibit the function of calcium-binding proteins. Cadherins are a large family of calcium-binding proteins that facilitate cell adhesion and play key roles in embryo development, tissue homeostasis and tumour metastasis. However, whether lanthanides can bind cadherins and functionally replace calcium binding has not been comprehensively explored. In this study, we investigated the effect of lanthanide binding on cadherin structure and function using terbium, which is a commonly used lanthanide for protein spectroscopy and a proposed anti-cancer agent. We demonstrate that terbium can compete with calcium for binding to calcium-binding sites in cadherins. Terbium binding to cadherins abolished their cell adhesive activity and rendered cadherins sensitive to proteolysis by trypsin. Molecular dynamics simulations indicate that replacement of calcium by terbium results in structural rearrangements and increases the flexibility of the cadherin ectodomain. These changes in structure and dynamics are likely to underlie the inability of lanthanide-bound cadherins to support cell adhesion. Taken together, our findings further knowledge on lanthanide interactions with calcium-binding proteins and provide new insight into the influence of metal chemistry on cadherin structure, dynamics and function.

Assessment of the toxic effects of mixtures of three lanthanides (Ce, Gd, Lu) to aquatic biota

Lanthanide (LNs) release into the environment is expected to greatly increase in the coming years due to a high demand for new technologies. However there is a gap in the ecological risk assessment of these metals because most of the ecotoxicological studies have been performed with only one element, although they are usually found in nature as a group. This research evaluated the effects of mixtures of three lanthanides, cerium (Ce), gadolinium (Gd), and lutetium (Lu), representative of the light, middle and heavy rare earth elements, respectively, on seven aquatic species (A. fischeri, R. subcapitata, C. vulgaris, B. calyciflorus, H. incongruens, D. magna and D. rerio). Lanthanide content decreased over time in all toxicity test media and it was observed that LN sedimentation starts at the beginning of the tests with a steep decline of the available LN amount. Potential toxic effects of LNs were observed only in five species of the seven studied, predominantly in the unicellular organism (A. fischeri) and in the organisms belonging to the lower trophic levels (R. subcapitata and B. calyciflorus). The multi-toxicity approach performed in this study showed synergistic effects in tests performed with the bacteria A. fischeri and the algae R. subcapitata, and antagonistic effects for the rotifer B. calyciflorus. Although predicting the response of aquatic organisms exposed to multi-elements is not an easy task and can be masked by potential interactions with other compounds or even by nutrient removal. The variation in toxic action among species observed in this study reveals that lanthanide interaction in toxicity mechanisms should not be discarded, and supports that further studies with LN mixtures are required to properly understand their toxic behaviour in nature ecosystems.

Probing Energy Migration through Precise Control of Interfacial Energy Transfer in Nanostructure.

A novel mechanistic strategy for probing the energy migration through constructing the interfacial energy transfer (IET) in a core-shell-shell nanostructure is reported. In this design, the trilayer nanostructure is composed of a sensitizing core, a migratory interlayer, and a detective shell layer that interact with each other only by IET and the latter two shell layers are nonresponsive to the incident irradiation. This model is well applied in investigating the energy migration over the Tb, Gd, and Yb sublattices, and the results show that the Gd sublattice holds the best energy migratory performance. Moreover, the finding of energy migration over the Yb sublattice enables the 808 nm excited long-lived upconversion of Tb3+ and Eu3+ , which exhibits unique time-gating performance for information security. The results provide a facile and powerful nanosized model for an in-depth understanding of the fundamentals involving lanthanide interactions, which will further help excite new chances for the frontier applications of lanthanide-based luminescent materials.

Mononuclear and binuclear lanthanide acetates with chelating and bridging triethanolamine ligands

The interaction of lanthanide acetates with triethanolamine in pyridine medium yields mononuclear cationic complexes [Ln(teaH3)2(MeCOO)](MeCOO)2·0.5Py (teaH3 = N(CH2CH2OH)3, Py – pyridine) in cases Ln = Ce (1) and Pr (2), and binuclear heteroleptic complexes containing deprotonated triethanolamine [Ln2(MeCOO)4(teaH2)2] (Ln = Gd (3), Dy (4), Ho (5), and Er (6)). In the complexes of the first type, tetradentate chelating triethanolamine is a neutral ligand, while the metal core of the complexes of the second type is formed of lanthanide ions and bridging oxygen atoms of deprotonated teaH3. In the processes of thermal decomposition of complexes, systematic changes related to the character of the Ln3+ ions are noted. The complexes 1–6 were characterized by dc magnetic measurements, the Dy, Ho, and Er derivatives were also investigated in ac field. In the Gd complex, antiferromagnetic interactions between the Gd3+ ions were found. Results for complex 3, along with the literature data for eight complexes with the [Gd2O2] core, allowed to complement and to confirm the correlation between the value of the exchange interaction energy JGd–Gd′ and the interionic distances DGd…Gd′ for the complexes of this type that we found earlier. Complex of Dy exhibits field-induced slow relaxation of the magnetization.

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium Kd's > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes.

Characteristics of water and ion exchange of Elodea nuttallii cells at high concentrations of lanthanides

Changes of diffusive permeability of membranes of Elodea nuttallii cells following a short-term (60 min) treatment with high concentrations of lanthanides were recorded by the 1H NMR-diffusometry and conductometry methods. The 1-h infiltration of segments of Elodea nuttallii internodes in 10 mM solutions of nitrates of La, Nd and Lu resulted in the increased leakage of electrolytes from cells, but has no effect on a water diffusive permeability of membranes. In samples subjected to a 30 min pretreatment with a water channel inhibitor HgCl2 the water diffusive permeability of membranes (Pd) drops down under the influence of lanthanides, as well as an outcome of electrolytes. To explain the observed effects the change of spontaneous curvature of membrane lipid layer has been taken into consideration. The interaction of lanthanides with lipids of plasmalemma leads to the negative spontaneous curvature of lipid layer at which membrane channels are unclosed. Blocking of the ionic and water channels by mercury ions compensate the effect of change of spontaneous curvature of lipid layer.

Effect of Pr(NO3)3, Sm(NO3)3, and Gd(NO3)3 on Aqueous Solution Properties of Urea: A Volumetric, Viscometric, Surface Tension, and Friccohesity Study at 298.15 K and 0.1 MPa

Density, viscosity, surface tension, and friccohesity are reported for the hexahydrate nitrate salts of praseodymium, samarium, and gadolinium from 0.025 to 0.155 mol·kg−1 in water and in a 0.1 mol·kg−1 aqueous urea solution at 298.15 K and atmospheric pressure. From the densities, the apparent molar volumes, limiting apparent molar volumes, and apparent molar transfer volumes have been calculated as were viscosity B coefficients from the viscosities. These physicochemical parameters are discussed in terms of hydrogen bonding and ion–hydrophilic interactions. An attempt has thus been made to investigate the influence of urea on the interaction of lanthanide nitrates with water and the critical role being played by urea as a structure breaker.

Adsorption of Euplotes octocarinatus centrin on glassy carbon electrodes as substrates to study europium–protein interactions

The adsorption of N-terminal domain of ciliate Euplotes octocarinatus centrin (N-EoCen) onto a glassy carbon (GC) electrode was studied by cyclic voltammetry and electrochemical impedance spectroscopy. The adsorption process obeys Langmuir isotherm adsorption equation. Based on the adsorption, direct immobilization of N-EoCen onto the glassy carbon surface was used for construction of an N-EoCen-modified GC electrode. Then the electrode was used to probe the binding mode of europium ions with N-EoCen. The results show that with the increasing concentration of europium ions, the redox peaks of probe increase gradually. Simultaneously, the peak separation decrease and peak currents of the redox reaction increase. In addition, two binding sites in N-EoCen show no-equiv signal of CV change: the signal is slightly changed by the binding of the first europium ions and largely did by the binding of the second europium ions. It can be attributed to the change of conformation or aggregation of protein after binding of europium ions. It offers a viable model for illustrating the interaction of lanthanides with EoCen. Through the titration curve the process of combination can be explored.

Interaction of rare earth elements with a brown marine alga in multi-component solutions

The present study elucidates the underlying mechanisms involved in the interaction of lanthanides (lanthanum, cerium, europium and ytterbium) with a brown marine alga, Turbinaria conoides in quaternary mixtures. Competition between the lanthanides in occupying the binding sites of T. conoides was clearly identified, which was due to competitive ion-exchange mechanism. This competition affected the affinity of T. conoides towards each lanthanide. In comparison to single-component lanthanide system, uptake capacities in quaternary systems decreased by 75.8, 72.5, 65.0 and 70.2% for La, Ce, Eu and Yb, respectively. Biosorption mechanism was confirmed through SEM/EDX and pH-edge data, which implies that when virgin T. conoides are exposed to lanthanide solutions, La 3+ cations may replace some of the alkali and alkaline earth metals naturally present in the cell wall through ion-exchange mechanism; and this phenomenon was favored at pH 5, under examined conditions. Quaternary biosorption isotherms were successfully modeled using the extended Langmuir model with a constant interaction factor. The model predictions agreed well with the experimental data. The magnitude of Eu competition over lanthanides was significant, yielding a lowest interaction factor ( η = 0.91) for Eu over other lanthanides. Biosorption kinetics revealed that more than 91% of sorption process was completed within 60 min for all lanthanides, followed by slow attainment of equilibrium in around 3 h. Desorption was successful with 0.05 M HCl and the algal biomass was reused for three cycles without significant loss in original lanthanide uptake capacity.

Theoretical Study of Metal−Ligand Interaction in Sm(III), Eu(III), and Tb(III) Complexes of Coumarin-3-Carboxylic Acid in the Gas Phase and Solution

The interaction of lanthanide(III) cations (Ln(III) = Sm(III), Eu(III), and Tb(III)) with the deprotonated form of the coumarin-3-carboxylic acid (cca-) has been investigated by density functional theory (DFT/B3LYP) and confirmed by reference MP2 and CCSD(T) computations. Solvent effects on the geometries and stabilities of the Ln(III) complexes were computed using a combination of water clusters and a continuum solvation model. The following two series of systems were considered: (i) Ln(cca)2+, Ln(cca)2+, Ln(cca)3 and (ii) Ln(cca)(H2O)2Cl2, Ln(cca)2(H2O)2Cl, Ln(cca)3. The strength and character of the Ln(III)-cca- bidentate bonding were characterized by calculated Ln-O bond lengths, binding energies, ligand deformation energies, energy partitioning analysis, sigma-donation contributions, and natural population analyses. The energy decomposition calculations predicted predominant electrostatic interaction terms to the Ln-cca bonding (ionic character) and showed variations of the orbital interaction term (covalent contributions) for the Ln-cca complexes studied. Electron distribution analysis suggested that the covalent contribution comes mainly from the interaction with the carboxylate moiety of cca-.

Structural and Magnetic Properties of Layered Copper(II) Coordination Polymers Intercalating s and f Metal Ions

The nanoporous coordination polymer [Cu(pyrimidin-2-olate-N1,N3)2]n (1C) of the sodalite zeotype sorbs a variety of metal nitrates [M(NO3)m, M = Na+, K+, Rb+, Tl+, Ca2+, Sr2+, Ba2+, Pb2+, La3+, Nd3+, Gd3+, Er3+] from H2O/MeOH solutions, with a concomitant structural change to a layered [Cu(pyrimidin-2-olate-N1,N3)2]n.[M(NO3)m]n/2 (MNO3@1L) coordination framework. Single-crystal X-ray diffraction analyses revealed that the layers are based on Cu4(pyrimidin-2-olate-N1,N3)4 square grids of copper(II) ions bridged by N1,N3 exobidentate ligands, displaying a structural motif of the metallacalix[4]arene type in pinched cone conformation. The interlayer space is occupied by the guest metal nitrates, each metal being coordinated by (at least) the four oxygen atoms of a metallacalix[4]arene. Magnetic measurements on the MNO3@1L series denoted a weak ferromagnetic ordering taking place below the Néel temperatures (typically close to 35 K), arising from spin-canting phenomena of the antiferromagnetically coupled copper centers. When M = Nd3+, Gd3+, or Er3+, additional magnetic ordering is observed at lower temperatures, which, on the basis of static and dynamic magnetic susceptibility measurements, can be attributed to copper- lanthanide interactions.

Formation of lanthanide(III) texaphyrin complexes with DNA controlled by the size of the central metal cation

Interaction of lanthanide(III) texaphyrins (LnTEX) with calf thymus DNA was studied by UV–Vis, CD, resonance light scattering spectroscopy and by laser flash photolysis. The thermal stability of the LnTEX/DNA complexes decreases with the increasing lanthanide ion radius: LuTEX > DyTEX > GdTEX > EuTEX > CeTEX ⩾ LaTEX. Texaphyrins LaTEX, LuTEX and GdTEX produce O 2( 1 Δ g) in methanol solutions. In a phosphate buffer, the concentration of O 2( 1 Δ g) produced by these texaphyrins bound to DNA is affected by the formation of aggregates on the DNA backbone.