RESUMO
Technologically critical rare-earth elements are notoriously difficult to separate, owing to their subtle differences in ionic radius and coordination number1-3. The natural lanthanide-binding protein lanmodulin (LanM)4,5 is a sustainable alternative to conventional solvent-extraction-based separation6. Here we characterize a new LanM, from Hansschlegelia quercus (Hans-LanM), with an oligomeric state sensitive to rare-earth ionic radius, the lanthanum(III)-induced dimer being >100-fold tighter than the dysprosium(III)-induced dimer. X-ray crystal structures illustrate how picometre-scale differences in radius between lanthanum(III) and dysprosium(III) are propagated to Hans-LanM's quaternary structure through a carboxylate shift that rearranges a second-sphere hydrogen-bonding network. Comparison to the prototypal LanM from Methylorubrum extorquens reveals distinct metal coordination strategies, rationalizing Hans-LanM's greater selectivity within the rare-earth elements. Finally, structure-guided mutagenesis of a key residue at the Hans-LanM dimer interface modulates dimerization in solution and enables single-stage, column-based separation of a neodymium(III)/dysprosium(III) mixture to >98% individual element purities. This work showcases the natural diversity of selective lanthanide recognition motifs, and it reveals rare-earth-sensitive dimerization as a biological principle by which to tune the performance of biomolecule-based separation processes.
Assuntos
Proteínas de Bactérias , Elementos da Série dos Lantanídeos , Lantânio , Multimerização Proteica , Disprósio/química , Disprósio/isolamento & purificação , Íons/química , Elementos da Série dos Lantanídeos/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Lantânio/química , Neodímio/química , Neodímio/isolamento & purificação , Methylocystaceae , Proteínas de Bactérias/química , Proteínas de Bactérias/metabolismo , Cristalografia por Raios X , Estrutura Quaternária de ProteínaRESUMO
Rare-earth elements, which include the lanthanide series, are key components of many clean energy technologies, including wind turbines and photovoltaics. Because most of these 4f metals are at high risk of supply chain disruption, the development of new recovery technologies is necessary to avoid future shortages, which may impact renewable energy production. This paper reports the synthesis of a non-natural biogenic material as a potential platform for bioinspired lanthanide extraction. The biogenic material takes advantage of the atomically precise structure of a 2D crystalline protein lattice with the high lanthanide binding affinity of hydroxypyridinonate chelators. Luminescence titration data demonstrated that the engineered protein layers have affinities for all tested lanthanides in the micromolar-range (dissociation constants) and a higher binding affinity for the lanthanide ions with a smaller ionic radius. Furthermore, competitive titrations confirmed the higher selectivity (up to several orders of magnitude) of the biogenic material for lanthanides compared to other cations commonly found in f-element sources. Lastly, the functionalized protein layers could be reused in several cycles by desorbing the bound metal with citrate solutions. Taken together, these results highlight biogenic materials as promising bioadsorption platforms for the selective binding of lanthanides, with potential applications in the recovery of these critical elements from waste.
Assuntos
Quelantes/química , Metais Terras Raras/análise , Proteínas/química , Concentração de Íons de Hidrogênio , Elementos da Série dos Lantanídeos/análise , Elementos da Série dos Lantanídeos/isolamento & purificação , Elementos da Série dos Lantanídeos/metabolismo , Ligantes , Metais Terras Raras/isolamento & purificação , Metais Terras Raras/metabolismo , Proteínas/metabolismo , Piridinas/química , EspectrofotometriaRESUMO
This work furthers the development of counter-current chromatography as an industrial separation process method. It was demonstrated that the industrial counter-current chromatography methods, in particular, for the separation groups of rare earth metals, can be implemented in a modified cascade of centrifugal mixer-settler extractors. The retention behavior of rare earth elements (samarium, europium, gadolinium, terbium, dysprosium and yttrium) on the pilot chromatographic unit consisting of 70 serially connected centrifugal mixer-settler extractors was experimentally studied under isocratic elution conditions using the mixture of 30 vol.% Cyanexâ572 + 10 vol.% tributylphosphate in a hydrocarbon diluent as the stationary phase and aqueous nitric acid as the mobile phase. Theoretical analysis of experimental studies showed an acceptable agreement between the assumptions of the theory and experimental results.
Assuntos
Distribuição Contracorrente , Elementos da Série dos Lantanídeos/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Disprósio/química , Disprósio/isolamento & purificação , Európio/química , Európio/isolamento & purificação , Gadolínio/química , Gadolínio/isolamento & purificação , Samário/química , Samário/isolamento & purificação , Térbio/química , Térbio/isolamento & purificação , Ítrio/química , Ítrio/isolamento & purificaçãoRESUMO
The current knowledge of the half-lives (T1/2) of several radiolanthanides is either affected by a high uncertainty or is still awaiting confirmation. The scientific information deriving from this imprecise T1/2 data has a significant impact on a variety of research fields, e.g., astrophysics, fundamental nuclear sciences, and nuclear energy and safety. The main reason for these shortcomings in the nuclear databases is the limited availability of suitable sample material together with the difficulties in performing accurate activity measurements with low uncertainties. In reaction to the urgent need to improve the current nuclear databases, the long-term project "ERAWAST" (Exotic Radionuclides from Accelerator Waste for Science and Technology) was launched at Paul Scherrer Institute (PSI). In this context, we present a wet radiochemical separation procedure for the extraction and purification of dysprosium (Dy), terbium (Tb), gadolinium (Gd), and samarium (Sm) fractions from highly radioactive tantalum specimens, in order to obtain 154Dy, 157-158Tb, 148,150Gd, and 146Sm samples, needed for T1/2 determination studies. Ion-exchange chromatography was successfully applied for the separation of individual lanthanides. All separations were conducted in aqueous phase. The separation process was monitored via γ-spectrometry using suitable radioactive tracers. Both the purity and the quantification of the desired radiolanthanides were assessed by inductively coupled plasma mass spectrometry. Test experiments revealed that, prior to the Dy, Tb, Gd, and Sm separation, the removal of hafnium, lutetium, and barium from the irradiated tantalum material was necessary to minimize the overall dose rate exposure (in the mSv/h range), as well to obtain pure lanthanide fractions. With the herein proposed separation method, exotic 154Dy, 157-158Tb, 148,150Gd, and 146Sm radionuclides were obtained in sufficient amounts and purity for the preparation of samples for envisaged half-life measurements. During the separation process, fractions containing holmium, europium, and promethium radionuclides were collected and stored for further use.
Assuntos
Elementos da Série dos Lantanídeos/isolamento & purificação , Radioquímica/métodos , Radioisótopos/química , Cromatografia por Troca Iônica , Európio/isolamento & purificação , Meia-Vida , Hólmio/isolamento & purificação , Elementos da Série dos Lantanídeos/química , Extração Líquido-Líquido/métodos , Espectrometria de Massas , Promécio/isolamento & purificação , Espectrometria gama , Tantálio/químicaRESUMO
The alpha-emitter 225Ac (t1/2 = 9.92 d) is currently under development for targeted alpha-particle therapy of cancer, and accelerator production of 225Ac via proton irradiation of thorium targets requires robust separations of 225Ac from chemically similar fission product lanthanides. Additionally, the lanthanide elements represent critical components in modern technologies, and radiolanthanides such as 140Nd (t1/2 = 3.37 d) also have potential application in the field of nuclear medicine. The ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][NTf2]), combined with the diglycolamide extractant, N,N-dioctyldiglycolamic acid (DODGAA), was adsorbed on macroporous resin support to produce a solvent impregnated resin (SIR) that was investigated for separations of 225Ac and lanthanides. The equilibrium distribution coefficients (Kd) of the rare earth elements (Sc(III), Y(III), Ln(III)), 225Ac(III), Th(IV), and U(VI) on the prepared DODGAA/[Bmim][NTf2]-SIR were determined from batch adsorption experiments in HCl and HNO3 media. The DODGAA/[Bmim][NTf2]-SIR exhibited preferential uptake of the heavier lanthanide elements while allowing for the separation of the lighter lanthanides. Column separations utilizing the DODGAA/[Bmim][NTf2]-SIR were effective at separating the lighter lanthanides from each other, and separating 225Ac from a mixture of lanthanides, 213Bi, and 225Ra without the need for additional complexing agents.
Assuntos
Actínio/isolamento & purificação , Cromatografia por Troca Iônica/métodos , Glicolatos/química , Imidazóis/química , Elementos da Série dos Lantanídeos/química , Líquidos Iônicos/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Porosidade , Solventes/química , Espectrofotometria AtômicaRESUMO
Elemental analysis of rare earth elements is essential in a variety of fields including environmental monitoring and nuclear safeguards; however, current techniques are often labor intensive, time consuming, and/or costly to perform. The difficulty arises in preparing samples, which requires separating the chemically and physically similar lanthanides. However, by transitioning these separations to the microscale, the speed, cost, and simplicity of sample preparation can be drastically improved. Here, all fourteen non-radioactive lanthanides (lanthanum through lutetium minus promethium) are separated by ITP for the first time in a serpentine fused-silica microchannel (70 µm wide × 70 µm tall × 33 cm long) in <10 min at voltages ≤8 kV with limits of detection on the order of picomoles. This time includes the 2 min electrokinetic injection time at 2 kV to load sample into the microchannel. The final leading electrolyte consisted of 10 mM ammonium acetate, 7 mM α-hydroxyisobutyric acid, 1% polyvinylpyrrolidone, and the final terminating electrolyte consisted of 10 mM acetic acid, 7 mM α-hydroxyisobutyric acid, and 1% polyvinylpyrrolidone. Electrophoretic electrodes are embedded in the microchip reservoirs so that voltages can be quickly applied and switched during operation. The limits of detection are quantified using a commercial capacitively coupled contactless conductivity detector (C4 D) to calculate ITP zone lengths in combination with ITP theory. Optimization of experimental procedures and reproducibility based on statistical analysis of subsequent experimental results are addressed. Percent error values in band length and conductivity are ≤8.1 and 0.37%, respectively.
Assuntos
Isotacoforese/instrumentação , Dispositivos Lab-On-A-Chip , Elementos da Série dos Lantanídeos , Técnicas Analíticas Microfluídicas/instrumentação , Condutividade Elétrica , Desenho de Equipamento , Isotacoforese/métodos , Elementos da Série dos Lantanídeos/análise , Elementos da Série dos Lantanídeos/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Limite de DetecçãoRESUMO
Adjacent lanthanides are among the most challenging elements to separate, to the extent that current separations materials would benefit from transformative improvement. Ordered mesoporous carbon (OMC) materials are excellent candidates, owing to their small mesh size and uniform morphology. Herein, OMC materials were physisorbed with bis-(2-ethylhexyl) phosphoric acid (HDEHP) and sorption of Eu3+ was investigated under static and dynamic conditions. The HDEHP-OMC materials displayed higher distribution coefficients and loading capacities than current state-of-the-art materials. Using a small, unpressurized column, a separation between Eu3+ and Nd3+ was achieved. Based on these experimental results, HDEHP-OMC have shown potential as a solid phase sorbent for chromatographic, intragroup, lanthanide separations.
Assuntos
Carbono/química , Técnicas de Química Analítica/métodos , Cromatografia , Elementos da Série dos Lantanídeos/isolamento & purificação , Ácidos Fosfóricos/químicaRESUMO
The aim of this work is to evaluate the rare earth elements (REEs) recovery from fluid catalytic cracking spent catalyst (FCC-SC) by chemical and biochemical strategies while also examining a route for the valorization of biodiesel-derived glycerin (RG), which is presently unprofitable to refine. Recovery tests for REEs were performed with no pretreatment of the FCC-SC. A chemical leaching investigation was carried out using HCl, HNO3, NaOH, CaCl2 and citric acid aqueous solutions (1 mol L-1, at 30, 50, 60 or 70 ± 1 °C). The leaching tests carried out with 1 mol L-1 citric acid at 50 °C provided the best recovery of La (27%). Subsequent bioleaching tests were carried out with four strains of Yarrowia lipolytica to evaluate their potential to produce organic acids using RG as the main carbon source. The FCC-SC contains some REEs, predominantly La. Remarkable biorecovery rates for REEs (namely, La (53%), Ce and Nd (both 99%)) were achieved using the Y. lipolytica IM-UFRJ 50678 fermented medium at 50 °C. Thus, here, a sustainable approach to recovering metals from spent cracking catalyst using RG under low-cost and non-energy-intensive processing conditions is reported.
Assuntos
Biotecnologia/métodos , Elementos da Série dos Lantanídeos/isolamento & purificação , Indústria de Petróleo e Gás , Eliminação de Resíduos/métodos , Yarrowia/metabolismo , Catálise , Ácido Cítrico/química , Glicerol/químicaRESUMO
Combining the merits of soft-templating and perchlorate oxidation methods, the first-case investigation of niobium alkylphosphonates has uncovered their unique morphology, backbone composition, thermal behavior and huge potentiality as radioanalytical separation materials. These hierarchically porous solids are random aggregates of densely stacked nanolayers perforated with worm-like holes or vesicular voids, manifesting the massif-, tower-like "polymer brush" elevated up to â¼150nm driven by the minimal surface free energy principle. These coordination polymers consist of distorted niobium (V) ions strongly linked with tetrahedral alkylphosphonate building units, exposing uncoordinated phosphonate moieties and defective metal sites. Despite the amorphous features, they demonstrate multimodal porosity covering continuous micropores, segregated mesopores and fractional macropores, beneficial for the sequestration by active Lewis acid-base center. Evidenced by the maximum distribution coefficients of thorium, lanthanides reaching 9.0×104, 9.5×104mLg-1 and large separation factor at pH≤1 20-element cocktail, this category of niobium alkylphosphonates are capable of harvesting thorium, lanthanides directly from the radionuclide surrogate, comparable to or even surpass the performance of the metal (IV) arylphosphonates counterparts. They also display appreciable SFEu/Sm â¼20 in 1molL-1 HNO3, shedding light on dual approaches to achieve the isolation of americium from curium. A combinatorial radioanalytical separation protocol has been proposed to enrich thorium and europium, revealing facile utilization of these highly stable, phosphonated hybrids in sustainable development of radioanalytical separation.
Assuntos
Nióbio/química , Polímeros/química , Tório/isolamento & purificação , Elementos da Série dos Lantanídeos/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Ácidos de Lewis/química , Organofosfonatos/química , Porosidade , Tório/químicaRESUMO
Solid phase extraction is gaining attention from separation scientists due to its high chromatographic utility. Though both grafted and impregnated forms of solid phase extraction resins are popular, the later is easy to make by impregnating a given organic extractant on to an inert solid support. Solid phase extraction on an impregnated support, also known as extraction chromatography, combines the advantages of liquid-liquid extraction and the ion exchange chromatography methods. On the flip side, the impregnated extraction chromatographic resins are less stable against leaching out of the organic extractant from the pores of the support material. Grafted resins, on the other hand, have a higher stability, which allows their prolong use. The goal of this article is a brief literature review on reported actinide and lanthanide separation methods based on solid phase extractants of both the types, i.e., (i) ligand impregnation on the solid support or (ii) ligand functionalized polymers (chemically bonded resins). Though the literature survey reveals an enormous volume of studies on the extraction chromatographic separation of actinides and lanthanides using several extractants, the focus of the present article is limited to the work carried out with amide based ligands, viz. monoamides, diamides and diglycolamides. The emphasis will be on reported applied experimental results rather than on data pertaining fundamental metal complexation.
Assuntos
Elementos da Série Actinoide/isolamento & purificação , Amidas/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Extração em Fase Sólida , Ligantes , Polímeros/química , Extração em Fase Sólida/normasRESUMO
Lanthanides possess similar chemical properties rendering their separation from one another a challenge of fundamental chemical and global importance given their incorporation into many advanced technologies. New separation strategies combining green chemistry with low cost and high efficiency remain highly desirable. We demonstrate that the subtle bonding differences among trivalent lanthanides can be amplified during the crystallization of borates, providing chemical recognition of specific lanthanides that originates from Ln3+ coordination alterations, borate polymerization diversity and soft ligand coordination selectivity. Six distinct phases are obtained under identical reaction conditions across lanthanide series, further leading to an efficient and cost-effective separation strategy via selective crystallization. As proof of concept, Nd/Sm and Nd/Dy are used as binary models to demonstrate solid/aqueous and solid/solid separation processes. Controlling the reaction kinetics gives rise to enhanced separation efficiency of Nd/Sm system and a one-step quantitative separation of Nd/Dy with the aid of selective density-based flotation.
Assuntos
Boratos/química , Química Verde/métodos , Elementos da Série dos Lantanídeos/isolamento & purificação , Cristalização , Cinética , Estrutura MolecularRESUMO
For the first time, an ion imprinted polymer (IIP) able to selectively extract simultaneously all the lanthanide ions was successfully synthesized in acetonitrile using Nd3+ as a template ion, methacrylic acid as a complexing monomer, and ethylene glycol dimethacrylate as a cross-linker. A non-imprinted polymer (NIP) was synthesized under the same conditions as those of the IIP, but in the absence of the template ion. After the removal of the template ions, grounding and sieving, the IIP particles were packed in solid phase extraction (SPE) cartridges. The selectivity of the IIP was evaluated by comparing its behavior with the one of the NIP. Each SPE step (percolation, washing, and elution) was optimized in order to find the best compromise between the selectivity and the extraction recoveries. Using the optimized SPE conditions, the extraction recoveries of eight lanthanide ions representative of the lanthanide family were higher than 77% with an average value of 83% with the IIP, whereas, in the case of the NIP, they ranged between 14 and 36% and they were below 3% for the interfering ions from alkali, transition, and post-transition metal families with the IIP. A first evaluation of the reproducibility of the SPE profiles was carried out by performing statistical tests on the data obtained with several cartridges filled with particles obtained from two different IIP and NIP syntheses. Promising results were obtained. The specific capacity, i. e. the adsorption capacity of Nd3+ ions by the specific cavities of the imprinted polymer, was about 9 mg of Nd3+ per gram of IIP (60 µmol g-1), which is more than enough for the extraction of the lanthanide ions at trace levels. The breakthrough volume was about 1 mL per mg of IIP, leading to an enrichment factor of 15, which allows not only to selectively extract the lanthanides but also to concentrate them. Finally, the imprinted polymer was successfully used to selectively extract lanthanides from tap and river waters spiked at 1 µg L-1.
Assuntos
Elementos da Série dos Lantanídeos/isolamento & purificação , Impressão Molecular , Ácidos Polimetacrílicos/síntese química , Rios/química , Extração em Fase Sólida/métodos , Água/química , Acetonitrilas/química , Elementos da Série dos Lantanídeos/análise , Ácidos Polimetacrílicos/químicaRESUMO
Due to the similar chemical properties of actinides An(iii) and lanthanides Ln(iii), their separation in spent nuclear fuel reprocessing is extremely challenging. A 1,10-phenanthroline dipicolinamide-based ligand (PhenBHPPA) has been identified to possess a selectivity for Am(iii) over Eu(iii) and could potentially be used for group actinide extraction. In this study, quasi-relativistic density functional theoretical calculations have been used to disclose the interaction mechanisms of Am(iii) and Eu(iii) complexes with PhenBHPPA. The electronic structures, bonding nature, QTAIM (Quantum Theory of Atoms in Molecules) analyses and thermodynamic behaviors of the Am(iii) and Eu(iii) complexes with PhenBHPPA have been explored in detail. According to the Wiberg bond indices (WBIs) and QTAIM analyses, interactions between the ligand and metal cations (Am(iii) and Eu(iii)) exhibit a weakly covalent character. Thermodynamic analyses show that the charged complexes [ML(NO3)2](+) appear to be the most stable species in the complexation processes. Moreover, it is more energetically favorable for PhenBHPPA to bind to Am(iii) compared to Eu(iii). Our study could render new insights into understanding the selectivity of the ligand towards minor actinides and the separation of An(iii) from Ln(iii) via liquid-liquid extraction.
Assuntos
Amerício/química , Complexos de Coordenação/química , Európio/química , Fenantrolinas/química , Ácidos Picolínicos/química , Teoria Quântica , Elementos da Série Actinoide/isolamento & purificação , Amidas/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Extração Líquido-Líquido , Modelos Moleculares , Estrutura Molecular , TermodinâmicaRESUMO
Lanthanides (Ln's) are the major components of rare earth elements, which are critical components of many high-value products. The ions of adjacent Ln's have the same valence and very similar ionic radii. They cannot be separated using conventional adsorption or ion exchange processes. Current production of high-purity Ln's is based on multiple sequential and parallel solvent extraction processes, which require large amounts of toxic solvents and result in serious negative impact on the environment. In this study, a ligand-assisted elution chromatography process for the separation of Ln's was developed for the first time for titania, which is a robust and inexpensive inorganic sorbent. A selective ligand for Ln's, ethylenediaminetetraacetic acid (EDTA), was found to adsorb on the sorbent. The adsorbed EDTA became strong adsorption sites for the Ln's. Desorption of Ln's was driven by reversible reactions of Ln's with EDTA in the mobile phase. The overall sorbent selectivity for the reaction and adsorption process was approximately equal to the ratio of the sorbent selectivity to the ligand selectivity. The separation mechanisms were tested and verified using rate model simulations and experimental data for the separation of praseodymium (Pr), neodymium (Nd), and samarium (Sm). Simulations based on the model were used to design efficient linear gradient elution and stepwise elution processes. The purity and yield of all three Ln's were found to be above 95% in the designed processes. Stepwise elution can be implemented in a continuous process for increasing sorbent productivity and reducing costs for large-scale separation. Ligand assisted elution processes are much simpler and more environmentally friendly than the conventional solvent extraction processes.
Assuntos
Cromatografia/métodos , Elementos da Série dos Lantanídeos/isolamento & purificação , Adsorção , Ácido Edético/química , LigantesRESUMO
Separation of Y from other rare earth elements (REE) is difficult because of similarity of its ionic radius to ionic radii of Tb, Dy and Ho. In the new RP-HPLC system with C18 column, tetra-n-butyl ammonium hydroxide (TBAOH) as an ion interaction reagent (IIR), nitrilotriacetic acid (NTA) as a complexing agent at pH=2.8-3.5, and post column derivatization with Arsenazo III, yttrium is eluted in the region of light REE, between Nd and Sm and is base line separated from Nd and Sm and even from promethium. Simple model employing literature data on complex formation of REE with NTA and based on anion exchange mechanism was developed to foresee the order of elution of individual REE. The model correctly predicted that lanthanides up to Tb will be eluted in the order of increasing Atomic Number (At.No.) but all heavier REE will show smaller retention factors than Tb. Concurrent UV/VIS detection at 658nm and the use of radioactive tracers together with γ-ray spectrometric measurements made possible to establish an unique elution order of elution of REE: La, Ce, Pr, Nd, Pm, Y, Sm, Er, Ho, Tm, Yb, Eu, Lu, Dy+Gd, Tb, Sc. The real place of Y however, in this elution series differs from that predicted by the model (Y between Sm and Eu). The method described in this work enables selective separation of Y from La, Ce, Pr, Nd, Pm, Sm and all heavier REE treated as a group.
Assuntos
Cromatografia Líquida de Alta Pressão , Cromatografia de Fase Reversa , Complexos de Coordenação/química , Metais Terras Raras/química , Ácido Nitrilotriacético/química , Ítrio/isolamento & purificação , Ânions/química , Complexos de Coordenação/isolamento & purificação , Concentração de Íons de Hidrogênio , Elementos da Série dos Lantanídeos/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Ítrio/químicaRESUMO
Two enantiomerically pure polytungstates, Na2[(CH3)2NH2]3{Naâ[Ce(III)(H2O)(CH3CH2OH)(L-tartH3)(H2Si2W19O66)]}·3.5H2O (L-1) and [(CH3)2NH2]7{Naâ[Ce(III)(H2O)(CH3CH2OH)(D-tartH3)(Si2W19O66)]}·2.5H2O (D-1), were successfully synthesized. Structural analysis indicates that chiral tartrate ligands directly connect with novel lacunary [Si2W19O66](10-) polytungstate units. Strong induced optical activity in the polyoxometalate (POM) units is manifested by circular dichroism spectroscopy. Z-scan analysis revealed that L-1 and D-1 are the first chiral POM-based complexes that exhibit two-photon absorption properties typical of the third-order nonlinear optical response.
Assuntos
Elementos da Série dos Lantanídeos/química , Compostos de Tungstênio/química , Dicroísmo Circular , Elementos da Série dos Lantanídeos/isolamento & purificação , Modelos Moleculares , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Estereoisomerismo , Compostos de Tungstênio/síntese químicaRESUMO
An ITP separation of eight lanthanides on a serpentine PMMA microchip with a tee junction and a 230-mm-long serpentine channel is described. The cover of the PMMA chip is 175 µm thick so that a C(4) D in microchip mode can be used to detect the lanthanides as they migrate through the microchannel. Acetate and α-hydroxyisobutyric acid are used as complexing agents to increase the electrophoretic mobility difference between the lanthanides. Eight lanthanides are concentrated within â¼ 6 min by ITP in the microchip using 10 mM ammonium acetate at pH 4.5 as the leading electrolyte and 10 mM acetic acid at â¼ pH 3.0 as the terminating electrolyte. In addition, a 2D numerical simulation of the lanthanides undergoing ITP in the microchip is compared with experimental results using COMSOL Multiphysics v4.3a.
Assuntos
Eletroforese em Microchip/instrumentação , Eletroforese em Microchip/métodos , Elementos da Série dos Lantanídeos/isolamento & purificação , Acetatos/química , Simulação por Computador , Desenho de Equipamento , Concentração de Íons de Hidrogênio , Hidroxibutiratos/química , Polimetil Metacrilato , Processamento de Sinais Assistido por ComputadorRESUMO
To understand intramolecular hydrogen bonding in effecting liquid-liquid extraction behavior of CMPO-calixarenes, three CMPO-modified calix[4]arenes (CMPO-CA) 5a-5c with hydrogen-bonded spacer were designed and synthesized. The impact of spacer rotation that is hindered by introduction of intramolecular hydrogen bonding upon extraction of La(3+), Eu(3+), Yb(3+), Th(4+), and UO2(2+) has been examined. The results show that 5b and 5c containing only one hydrogen bond with a less hindered rotation spacer extract La(3+) more efficiently than 5a containing two hydrogen bonds with a more hindered rotation spacer, demonstrating the importance of local rigidification of spacer in the design of extractants in influencing the coordination environment. The large difference in extractability between La(3+) and Yb(3+) (or Eu(3+)) by 5b (or 5c), and the small difference by 5a, suggests intramolecular hydrogen bonding do exert pronounced influence upon selective extraction of light and heavy lanthanides. Log-log plot analysis indicates a 1:1, 2:1 and 1:1 stoichiometry (ligand/metal) for the extracted complex formed between 5b and La(3+), Th(4+), UO2(2+), respectively. Additionally, their corresponding acyclic analogs 7a-7c exhibit negligible extraction toward these metal ions. These results reveal the possibility of selective extraction via tuning local chelating surroundings of CMPO-CA by aid of intramolecular hydrogen bonding.
Assuntos
Elementos da Série Actinoide/isolamento & purificação , Calixarenos/química , Carbamoil-Fosfato/química , Elementos da Série dos Lantanídeos/isolamento & purificação , Ligação de Hidrogênio , Extração Líquido-LíquidoRESUMO
Very low concentrations (pg mL(-1) or sub-pg mL(-1) level) along with the high salinity are the main problems in determining trace metal contents in seawater. This problem is mainly considered for investigations of naturally occurring YLOID (Y and Lanthanides) and Zr and Hf in order to provide precise and accurate results. The inductively coupled plasma mass spectrometry (ICP-MS), both in high and low resolution, offers many advantages including simultaneous analyses of all elements and their quantitative determination with detection limits of the order of pg mL(-1). However in the analysis of YLOID in seawater, a better determination needs an efficient combination of ICP-MS measurement with a pre-concentration technique. To perform an ultra-trace analysis in seawater, we have validated an analytical procedure involving an improved modified co-precipitation on iron hydroxides to ensure the simultaneous quantitative recovery of YLOID, Zr and Hf contents with measurement by a quadrupole ICP-MS. The validity of the method was assessed through a series of co-precipitation experiments and estimation of several quality control parameters for method validation, namely working range and its linearity, detection limit, quantification limit, precision and spike recoveries, and the methodological blank choice, are introduced, evaluated and discussed. Analysis of NASS-6, is the first report on the latest seawater reference material for YLOID, hafnium and zirconium.
Assuntos
Compostos Férricos/química , Háfnio/isolamento & purificação , Elementos da Série dos Lantanídeos/isolamento & purificação , Água do Mar/química , Oligoelementos/isolamento & purificação , Ítrio/isolamento & purificação , Zircônio/isolamento & purificação , Floculação , Limite de Detecção , Controle de Qualidade , Espectrofotometria AtômicaRESUMO
Multistep pH-peak-focusing countercurrent chromatography was developed for separation and enrichment of rare earth metal ions using a polyethylene glycol-Na(2)SO(4) aqueous two phase system (ATPS) and pH stepwise gradient elution. Metal ions in a sample solution are chromatographically extracted in a basic stationary phase (polymer-rich phase of the ATPS) containing a complexation ligand such as acetylacetone at the top of the countercurrent chromatography (CCC) column. After the sample solution is introduced, the mobile phases of which the pH values have been adjusted with buffer reagents are delivered into the column by stepwise gradient elution in order of decreasing pH. Each metal ion is concentrated at a pH border formed between the zones of different pH in the CCC column through extraction with a complexing agent into the stationary phase at the front side of the border (basic region) and back extraction into the mobile phase at the back side of the border (acidic region), moving toward the outlet of the column with the pH border. Mutual separations of La(III), Ce(III), Nd(III), Yb(III), and Sc(III) were achieved by the present method using five step pH gradient elution, and each rare earth metal ion was effectively enriched at each of the five pH borders. The mechanism for formation of pH profile of the column effluent and the potential of this technique for preparative scale separation are also discussed.