We report emerging circularly polarized luminescence (CPL) at 4f-4f transitions when lanthanide (EuIII and TbIII) tris(β-diketonate) embedded to cellulose triacetate (CTA), cellulose acetate butyrate (CABu), D-/L-glucose pentamethyl esters ( D-/ L-Glu), and D-/L-arabinose tetramethyl esters ( D-/ L-Ara) are in film states. Herein, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate (fod) and 2,2,6,6-tetramethyl-3,5-heptanedione (dpm) were chosen as the β-diketonates. The glum value of Eu(fod)3 in CABu are +0.0671 at 593 nm (5
D
0
→
7
F1) and -0.0059 at 613 nm (5
D
0
→
7
F2), respectively, while those in CTA are +0.0463 and -0.0040 at these transitions, respectively. The glum value of Tb(fod)3 in CABu are -0.0029 at 490 nm (5
D
4
→
7
F6), +0.0078 at 540 nm (5
D
4
→
7
F5), and -0.0018 at 552 nm (5
D
4
→
7
F5), respectively, while those in CTA are -0.0053, +0.0037, and -0.0059 at these transitions, respectively. D-/ L-Glu and D-/ L-Ara induced weaker glum values at 4f-4f transitions of Eu(fod)3, Tb(fod)3, and Tb(dpm)3. For comparison, Tb(dpm)3 in α-pinene showed clear CPL characteristics, though Eu(dpm)3 did not. A surplus charge neutralization hypothesis was applied to the origin of attractive intermolecular interactions between the ligands and saccharides. This idea was supported from the concomitant opposite tendency in upfield 19F-NMR and downfield 1H-NMR chemical shifts of Eu(fod)3 and the opposite Mulliken charges between F-C bonds (fod) and H-C bonds (CTA and D-/ L-Glu). An analysis of CPL excitation (CPLE) and CPL spectra suggests that (+)- and (-)-sign CPL signals of EuIII and TbIII at different 4f-4f transitions in the visible region are the same with the (+)-and (-)-sign exhibited by CPLE bands at high energy levels of EuIII and TbIII in the near-UV region.
Rare earths (RE), chemically uniform group of elements due to similar physicochemical behavior, are termed as lanthanides. Natural occurrence depends on the geological circumstances and has been of long interest for geologist as tools for further scientific research into the region of ores, rocks, and oceanic water. The review paper mainly focuses to provide scientific literature about rare earth elements (REEs) with potential environmental and health effects in understanding the research. This is the initial review of RE speciation and bioavailability with current initiative toward development needs and research perceptive. In this paper, we have also discussed mineralogy, extraction, geochemistry, analytical methods of rare earth elements. In this study, REEs with their transformation and vertical distribution in different environments such as fresh and seawater, sediments, soil, weathering, transport, and solubility have been reported with most recent literature along key methods of findings. Speciation and bioavailability have been discussed in detail with special emphasis on soil, plant, and aquatic ecosystems and their impacts on the environment. This review shows that REE gained more importance in last few years due to their detrimental effects on living organisms, so their speciation, bioavailability, and composition are much more important to evaluate their health risks and are discussed thoroughly as well.
We have developed a new class of lanthanide nano-clusters that self-assemble using flexible Schiff base ligands. Cd-Ln and Ni-Ln clusters, [Ln8Cd24(L(1))12(OAc)39Cl7(OH)2] (Ln = Nd, Eu), [Eu8Cd24(L(1))12(OAc)44], [Ln8Cd24(L(2))12(OAc)44] (Ln = Nd, Yb, Sm) and [Nd2Ni4(L(3))2(acac)6(NO3)2(OH)2], were constructed using different types of flexible Schiff base ligands. These molecular nano-clusters exhibit anisotropic architectures that differ considerably depending upon the presence of Cd (nano-drum) or Ni (square-like nano-cluster). Structural characterization of the self-assembled particles has been undertaken using crystallography, transmission electron microscopy and small-angle X-ray scattering. Comparison of the metric dimensions of the nano-drums shows a consistency of size using these techniques, suggesting that these molecules may share similar structural features in both solid and solution states. Photophysical properties were studied by excitation of the ligand-centered absorption bands in the solid state and in solution, and using confocal microscopy of microspheres loaded with the compounds. The emissive properties of these compounds vary depending upon the combination of lanthanide and Cd or Ni present in these clusters. The results provide new insights into the construction of novel high-nuclearity nano-clusters and offer a promising foundation for the development of new functional nanomaterials.
Lanthanide element in the methanation reaction gives an excellent catalytic performance at low reaction temperature. Praseodymium is one of lanthanide element and was chosen due to its properties which are thermally stable and provide excess of oxygen in the oxide lattice. Therefore, a catalyst of Ru/Mn/Pr (5:30:65)/Al2O3 (RMP, 5:30:65/Al2O3) was prepared via wetness impregnation method and the effect of calcination temperature on the catalyst performance was investigated using FTIR analysis. The RMP/Al2O3 catalyst calcined at 800 o C was chosen as an excel catalyst with CO2 conversion of 96.9% and CH4 formation of 45.1% at 350 o C reaction temperature. From the EDX mapping, it can be observed that the distribution of all element is homogeneous at 800 o C and 900 o C except Ru, O and Al at 1000 o C calcination temperature. The image from FESEM also shows the presence of some crystal shape on the catalyst surface. From the FTIR analysis, the peak stretching and bending mode of O-H bond decreased when the calcination temperature increased.
Real-time and visual monitoring of pollutants in the air is of great importance since they are usually cannot be seen, smelled, or touched. Lanthanide nano-cluster is a kind of luminescent sensor for various species. However, controlling synthesis of lanthanide nano-cluster remains experimentally challenging. In this work, four series of lanthanide-barium (Ln-Ba) nano-clusters of Dy2Ba (1), Tb2Ba2 (2), Ln4Ba3 (Ln = Tb, 3a; Eu, 3b), Tb4Ba4 (4) were assembled through precisely controlling the pH of the reactant solutions. The work features the first example that the number of cluster's nuclei changes regularly with the pH. Moreover, investigation reveals that nano-cluster 3a is a highly selective and sensitive sensor towards acetylacetone (acac) and aniline. Interestingly, easy-to-use sensing devices of test paper, agarose gel, and five kinds of film on CaCO3, polyfoam, coin, mask, and wall that based on 3a were fabricated by facile methods. The seven sensing devices showed remarkable ability to sense aniline and acac vapors with visibility to the naked eyes. This is the first work on multiple real-time and visual sensing devices based on the lanthanide nano-cluster.
Ion-imprinting polymers (IIPs) materials draw the great recognition because of the powerful selectivity to the desired metal ions. Therefore, the ion-imprinting polymer (Ce-IIP) was prepared by using cerium metal with amidoxime ligand as the complexing agent, in addition ethylene glycol dimethacrylate (EGDMA) and 2,2-azobisisobutyronitrile (AIBN) are crosslinking agent and free radical initiator, respectively. Aqueous HCl was applied to leach the cerium ions from the imprinted polymer for the creation of cavities of template, which is utilized for further cerium ions adsorption with high selectivity. The Ce-IIP was characterized by using ICP-MS, FE-SEM and also solid state analysis by UV-vis NIR spectroscopy. FT-IR study confirmed the complexation of the Ce-IIP was successful. The optimum pH was found to be 6 and the highest adsorption capacity was estimated about 145 mg g-1. Thus, the prepared Ce-IIP gave very good selectivity to cerium ions in the presence of lanthanide ions and also Ce-IIP can be reused 10 times without a substantial loss in adsorption capacity.