Calix[6]arene‐Picolinamide Extractants for Radioactive Waste Treatment: Effect of Additional Carboxy Binding Sites in the Pyridine 6‐Positions on Complexation, Extraction Efficiency and An/Ln Separation

Macerata, Elena; Sansone, Francesco; Baldini, Laura; Ugozzoli, Franco; Brisach, Frédéric; Haddaoui, Jaouad; Hubscher-Bruder, Véronique; Arnaud‐Neu, Françoise; Ungaro, Rocco; Casnati, Alessandro

doi:10.1002/ejoc.200901479

Cited by 23 publications

(17 citation statements)

References 37 publications

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“…However, it was demonstrated that the addition of the dicarbollide anion strongly improved the extraction efficiency and that it is possible to reach the desired values of D M (metal ion distribution coefficient = [M] org /[M] aq at equilibrium) at the target pH value by varying the dicarbollide concentration. 16,17 It was verified that the enhanced extracting capability of the Calix/Br n CD mixture with respect to calixarene alone was not due to the extracting capability of the synergiser. 16 The experimental conditions for the extraction tests performed on La 3+ aqueous solutions were chosen after some preliminary radioactive extraction experiments.…”

Section: Extraction Resultsmentioning

confidence: 92%

“…16,17 It was verified that the enhanced extracting capability of the Calix/Br n CD mixture with respect to calixarene alone was not due to the extracting capability of the synergiser. 16 The experimental conditions for the extraction tests performed on La 3+ aqueous solutions were chosen after some preliminary radioactive extraction experiments. Since nitrobenzene was used as a diluent in the preliminary extraction tests for the ESI experiments but no data for 1 in nitrobenzene was available in the literature, the ligand behaviour in this diluent was established.…”

Section: Extraction Resultsmentioning

confidence: 92%

“…The synthesis of 37,38,39,40,41,42-hexakis{3-[(pyridine-6-methoxycarbonyl-2-carboxy)-amino]-propoxy}calix [6]arene (1) was undertaken by a literature method. 16…”

Section: Experimental Generalmentioning

confidence: 99%

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Assessing the mechanism of the synergistic action of calixarenes and Co-dicarbollides in lanthanide extractions

et al. 2010

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The extraction pathway of lanthanide ions from simulated nuclear waste solutions and the synergistic effects of a calixarene and a cobalt dicarbollide anion (CD) have been investigated on a model system by the combined use of electrospray ionization MS, FTMS ICR, together with 1 H and 11 B high field NMR spectroscopy techniques. Moreover, the extracting capabilities of the calixarene/BrCD mixture were determined by liquid-liquid extraction tests. An enhanced extraction efficiency of the calixarene/BrCD mixture with respect to the calixarene alone was observed. MS analysis allowed the assessment of a supramolecular ternary association, while the NMR data gave information on the calixarene binding sites for lanthanide ions. Herein, we report the experimental evidence of the formation of a ternary lanthanide/calixarene/ Co-dicarbollide aggregate, which allowed us for the first time to assess the mechanism of the synergistic action of calixarenes and CD anions in lanthanide ion extraction.In the fascinating framework of supramolecular chemistry, calixarenes play a primary role as receptors of a large variety of molecular and ionic guest systems, as extensively reviewed in the literature. 1 In the past few years, calixarenes functionalized with metal-binding groups have shown outstanding extraction properties for metal ions of paramount interest for environmental control: the extraction of Cs, Sr, actinides and lanthanides from acidic nuclear waste solutions can be cited as examples. 2 In particular, the separation of actinides (An) from lanthanides (Ln) is an urgent and important problem in the management of waste resulting from the reprocessing of fuels from nuclear plants. 3 Spent nuclear fuels contain moderate amounts of long-lived minor actinides (Np, Am, Cm) and many fission products, among which Lns represent some of the major components. The selective extraction of minor actinides and their subsequent transmutation into short lived or non-radioactive isotopes is a vital process in the management of waste. 4-7 This extraction process, however, needs efficient, chemically-selective and radiochemically-resistant ligands. 8 Therefore, in the last few decades, great efforts have been made in developing efficient extractants for application in new separative processes. 9-11 A large number of cation extractants based on calixarenes, in which pre-organization has been shown to favour specificity of extraction, have been extensively studied, either alone or in mixtures, with synergistic agents such as lipophilic Co-dicarbollide anions. 12-14 Thanks to a synergistic effect among the components, the extraction efficiency of calixarene-based ligands is strongly improved by the addition of lipophilic Co-bis-dicarbollide anions. However, no clear explanation for this improved extraction efficiency has been proposed at a molecular level.In the presence of a lipophilic synergiser, the extraction process ( Fig. 1) with these macrocycles, at present, is believed to consist of these basic steps: (i) the neutral calixarene ligand...

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Section: Extraction Resultsmentioning

confidence: 92%

Section: Extraction Resultsmentioning

confidence: 92%

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Assessing the mechanism of the synergistic action of calixarenes and Co-dicarbollides in lanthanide extractions

et al. 2010

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“…The reaction was realized in a semi-industrial scale unit [24] . A dual envelop reactor of 30 litres capacity was used.…”

Section: General Methodsmentioning

confidence: 99%

The First Inexpensive, Simplified and Large Scale Synthesis of p-tert-butylcalix[7] and [9]arenes

Ferchichi¹,

Jeanneau²,

Sollier³

et al. 2011

CheM

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The nuclear industry and the rare earth elements mining need methods in order to separate lanthanides and actinides. Large organic macrocycles have demonstrated their contribution to this domain. Due to the lack of an efficient and reproducible method of synthesis, the chemistry of large p-tert-butylcalix[n] arenes (with 6 < n < 10) has been much less explored than the one of their inferior homologs. Excepted for the p-tert-butylcalix[8]arene which is obtained in good yields, the procedures described in the literature for the preparation of p-tert-butylcalix[7] and [9]arenes involve many steps of purification and lead to, in the very best case, a couple of grams of product, after one month of labor. In this work, a set of experiments with varying parameters has demonstrateed the crucial role of the solvent and of the amount of catalyst in the macrocyclization reaction. Then, a scale-up study was done, the procedure being adapted and realized on a semi industrial scale reactor. Finally, an original purification pathway avoiding the numerous silica-gel chromatographies and recrystallizations was set up and optimized. This simplified procedure opens gateways for the preparation of a few dozen grams of pure p-tertbutylcalix [7] and [9]arenes and should lead to the preparation of new selective complexants.

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“…Thanks to the knowledge acquired within the field of the SNF hydrometallurgical reprocessing [44][45][46][47], we are herein reporting, for the first time, the synthesis and application of the hydrophilic complexant 1,10-phenanthroline-2,9-dicarboxamide, N 2 ,N 9 -bis[1,3dihydroxy-2-(hydroxymethyl)propan-2-yl] (1) (see Figure 1) as Am(III) selective stripping agent in the i-SANEX process. Similarly, the simpler hydrophilic phenanthroline-based ligands PDA (2) and PDALC (3), presenting the same donor set but with different coordinating ability, were tested and compared to 1.…”

Section: Introductionmentioning

confidence: 99%

Hydrophilic 1,10-phenanthroline derivatives for selective Am(III) stripping into aqueous solutions

Scaravaggi

Macerata

Galletta

et al. 2014

J Radioanal Nucl Chem

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The novel and fully combustible hydrophilic 1,10-phenantroline-2,9-dicarboxamide (1) was synthesized and investigated as Am(III) stripping agent in a simulated advanced hydrometallurgical process, in comparison with two other 1,10-phenanthroline-based ligands 2 and 3. The stripping efficiency and the Am(III)/lanthanides(III) selectivity of the TODGA (org) / phen-derivative (aq) extracting system were studied under several experimental conditions by liquid-liquid extraction tests. The results obtained clarify the main limitations of these ligands in the scope of the hydrometallurgical reprocessing but also enable to get indications to steer future investigations in the domain of the selective An(III) recovery for the advanced reprocessing of Spent Nuclear Fuel by hydrophilic ligands.

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Calix[6]arene‐Picolinamide Extractants for Radioactive Waste Treatment: Effect of Additional Carboxy Binding Sites in the Pyridine 6‐Positions on Complexation, Extraction Efficiency and An/Ln Separation

Cited by 23 publications

References 37 publications

Assessing the mechanism of the synergistic action of calixarenes and Co-dicarbollides in lanthanide extractions

Assessing the mechanism of the synergistic action of calixarenes and Co-dicarbollides in lanthanide extractions

The First Inexpensive, Simplified and Large Scale Synthesis of p-tert-butylcalix[7] and [9]arenes

Hydrophilic 1,10-phenanthroline derivatives for selective Am(III) stripping into aqueous solutions

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