Recent Progress in Ionic Liquid Extraction for the Separation of Rare Earth Elements.

This review summarizes recent progress in solvent extraction of rare earth elements (REEs) using an ionic liquid (IL) as the extraction solvent. These IL extraction systems are advantageous owing to the affinity of ILs for both charged and neutral hydrophobic species, in contrast to conventional organic solvent extraction systems. Herein, REE extraction studies using ILs are detailed and classified based on the type of extraction system, namely extraction using anionic ligands, extraction using neutral ligands, synergistic extraction, extraction without extractants, and a specific system using task-specific ionic liquids (TSILs). In IL extraction systems, the extracted complexes are often different from those in organic solvent systems, and the REE extraction and separation efficiencies are often significantly enhanced. Synergistic IL extraction is an effective approach to improving the extractability and separability of REEs. The development of novel TSILs suitable for IL extraction systems is also effective for REE separation.

Extraction Ability of 4-Benzoyl-3-phenyl-5-isoxazolone towards 4f-Ions into Ionic and Molecular Media.

The distribution constants of 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) and deprotonated one (PBI-) between hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C1C4im][Tf2N]) and aqueous phases were determined, together with the acid-dissociation constant of HPBI. The solvent extraction of three selected lanthanoid ions (La3+, Eu3+, and Lu3+) with HPBI from aqueous nitrate phase into [C1C4im][Tf2N] has been investigated. Application of the ionic liquid as the extracting phase greatly enhanced the extraction performance of HPBI for lanthanoid ions compared with that in the chloroform system. A slope analysis was conducted in order to compare the results of the solution 4f-ion coordination chemistry in ionic and molecular media. The composition of the extracted species was established to be anionic tetrakis entities, Ln(PBI)4-, for light, middle, and heavy lanthanoid ions in an ionic environment (Ln denotes lanthanoid ion). Nevertheless, the typical neutral chelate lanthanoid complexes of the type Ln(PBI)3 have been detected when the conventional molecular diluent chloroform was applied as an organic phase.

Japan Flavour and Fragrance Materials Association's (JFFMA) safety assessment of food-flavouring substances uniquely used in Japan that belong to the class of aliphatic primary alcohols, aldehydes, carboxylic acids, acetals and esters containing additional oxygenated functional groups.

We performed a safety evaluation using the procedure devised by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) of the following four flavouring substances that belong to the class of 'aliphatic primary alcohols, aldehydes, carboxylic acids, acetals, and esters containing additional oxygenated functional groups' and are uniquely used in Japan: butyl butyrylacetate, ethyl 2-hydroxy-4-methylpentanoate, 3-hydroxyhexanoic acid and methyl hydroxyacetate. Although no genotoxicity study data were found in the published literature, none of the four substances had chemical structural alerts predicting genotoxicity. All four substances were categorised as class I by using Cramer's classification. The estimated daily intake of each of the four substances was determined to be 0.007-2.9 µg/person/day by using the maximised survey-derived intake method and based on the annual production data in Japan in 2001, 2005 and 2010, and was determined to be 0.250-600.0 µg/person/day by using the single-portion exposure technique and based on average-use levels in standard portion sizes of flavoured foods. Both of these estimated daily intake ranges were below the threshold of toxicological concern for class I substances, which is 1800 µg/person/day. Although no information from in vitro and in vivo toxicity studies for the four substances was available, these substances were judged to raise no safety concerns at the current levels of intake.

The Japan Flavour and Fragrance Materials Association's (JFFMA) safety assessment of acetal food flavouring substances uniquely used in Japan.

Using the procedure devised by the Joint FAO/WHO Expert Committee on Food Additives (JECFA), we performed safety evaluations on five acetal flavouring substances uniquely used in Japan: acetaldehyde 2,3-butanediol acetal, acetoin dimethyl acetal, hexanal dibutyl acetal, hexanal glyceryl acetal and 4-methyl-2-pentanone propyleneglycol acetal. As no genotoxicity study data were available in the literature, all five substances had no chemical structural alerts predicting genotoxicity. Using Cramer's classification, acetoin dimethyl acetal and hexanal dibutyl acetal were categorised as class I, and acetaldehyde 2,3-butanediol acetal, hexanal glyceryl acetal and 4-methyl-2-pentanone propyleneglycol acetal as class III. The estimated daily intakes for all five substances were within the range of 1.45-6.53 µg/person/day using the method of maximised survey-derived intake based on the annual production data in Japan from 2001, 2005, 2008 and 2010, and 156-720 µg/person/day using the single-portion exposure technique (SPET), based on the average use levels in standard portion sizes of flavoured foods. The daily intakes of the two class I substances were below the threshold of toxicological concern (TTC) - 1800 µg/person/day. The daily intakes of the three class III substances exceeded the TTC (90 µg/person/day). Two of these, acetaldehyde 2,3-butanediol acetal and hexanal glyceryl acetal, were expected to be metabolised into endogenous products after ingestion. For 4-methyl-2-pentanone propyleneglycol acetal, one of its metabolites was not expected to be metabolised into endogenous products. However, its daily intake level, based on the estimated intake calculated by the SPET method, was about 1/15 000th of the no observed effect level. It was thus concluded that all five substances raised no safety concerns when used for flavouring foods at the currently estimated intake levels. While no information on in vitro and in vivo toxicity for all five substances was available, their metabolites were judged as raising no safety concerns at the current levels of intake.

Comprehensive extraction study using N,N-dioctyldiglycolamic acid.

We report on the acid dissociation constants (Ka) of diglycolamic acid-type ligands together with comprehensive data on the extraction performance of N,N-dioctyldiglycolamic acid (DODGAA) for 54 metal ions. The pKa of the diglycolamic acid framework was determined to be 3.54 ± 0.03 in water (0.1 M LiCl, 25°C) by potentiometric titration, indicating that DODGAA is strongly acidic compared with acetic acid. DODGAA can quantitatively transfer various metal ions among the 54 metal ions through a proton-exchange reaction, and provides excellent extraction performance and separation ability for rare-earth metal ions, In(III), Fe(III), Hg(II), and Pb(II) among the 54 metal ions.

Highly selective synergism for the extraction of lanthanoid(III) ions with ß-diketones and trioctylphosphine oxide in an ionic liquid.

Selective synergism for the extraction of lanthanoids(III) (Ln) with ß-diketones such as 2-thenoyltrifluoroacetone, 2-naphthoyltrifluoroacetone, and benzoylacetone has been investigated in the presence of trioctylphosphine oxide as a hydrophobic neutral ligand in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as an ionic liquid. The extractability of heavier Ln was remarkably enhanced, resulting in a significant improvement in the separation of Ln. It was found that the present synergism is ascribed to the formation of cationic ternary complexes, followed by ion exchange into the ionic liquid.

Highly efficient extraction separation of lanthanides using a diglycolamic acid extractant.

Liquid-liquid extraction of lanthanide ions (Ln(3+)) using N,N-dioctyldiglycolamic acid (DODGAA) was comprehensively investigated, together with fluorescence spectroscopic characterization of the resulting extracted complexes in the organic phase. DODGAA enables the quantitative partitioning of all Ln(3+) ions from moderately acidic solutions, while showing selectivity for heavier lanthanides, and provides remarkably high extraction separation performance for Ln(3+) compared with typical carboxylic acid extractants. Furthermore, the mutual separation abilities of DODGAA for light lanthanides are higher than those of organophosphorus extractants. Slope analysis, loading tests, and electrospray ionization mass spectrometry measurements demonstrated that the transfer of Ln(3+) with DODGAA proceeded through a proton-exchange reaction, forming a 1:3 complex, Ln(DODGAA)3. The stripping of Ln(3+) from the extracting phase was successfully achieved under acidic conditions. Time-resolved laser-induced fluorescence spectroscopy revealed that the extracted Eu(3+) ions were completely dehydrated by complexation with DODGAA.

The JFFMA assessment of flavoring substances structurally related to menthol and uniquely used in Japan.

Using the procedure devised by the Joint FAO/WHO Expert Committee on Food Additives (JECFA), we performed safety evaluations on four flavoring substances structurally related to menthol (L-menthyl 2-methylbutyrate, DL-menthyl octanoate, DL-menthyl palmitate, and DL-menthyl stearate) uniquely used in Japan. While no genotoxicity study data were available in the literature, all four substances had no chemical structural alerts predictive of genotoxicity. Moreover, they all four are esters consisting of menthol and simple carboxylic acids that were assumed to be immediately hydrolyzed after ingestion and metabolized into innocuous substances for excretion. As menthol and carboxylic acids have no known genotoxicity, it was judged that the JECFA procedure could be applied to these four substances. According to Cramer's classification, these substances were categorized as class I based on their chemical structures. The estimated daily intakes for all four substances were within the range of 1.54-4.71 µg/person/day and 60-1250 µg/person/day, using the methods of Maximized Survey-Derived Intake and Single Portion Exposure Technique, respectively, based on the annual usage data of 2001, 2005, and 2010 in Japan. As the daily intakes of these substances were below the threshold of concern applied to class I substances viz., 1800 µg/person/day, it was concluded that all four substances raise no safety concerns when used for flavoring foods under the currently estimated intake levels.

Extraction behavior and selective separation of lead(II) using N,N-dioctyldiglycol amic acid.

Selective separation of lead ions (Pb(2+)) from aqueous solutions containing multiple divalent metal ions (Pb(2+), Cu(2+), Cd(2+), Zn(2+), Mn(2+), Co(2+), and Ni(2+)) was investigated using liquid-liquid extraction. N,N-Dioctyldiglycol amic acid (DODGAA) enabled quantitative extraction and efficient separation of Pb(2+) from the metal ion mixture under mildly acidic conditions. Compared with conventional commercial extractants, DODGAA provided better extraction and excellent selectivity for Pb(2+). The extraction of Pb(2+) with DODGAA proceeded through a proton-exchange reaction and formed a 1:2 complex, Pb(DODGAA)(2). The Pb(2+) was readily stripped from the extracting phase under acidic conditions, and the organic solution with DODGAA could be recycled.

Specific cooperative effect of a macrocyclic receptor for metal ion transfer into an ionic liquid.

An intramolecular cooperative extraction system for the removal of strontium cations (Sr(2+)) from water by use of a novel macrocyclic receptor (H(2)ßDA18C6) composed of diaza-18-crown-6 and two ß-diketone fragments in ionic liquid (IL) is reported, together with X-ray spectroscopic characterization of the resulting extracted complexes in the IL and chloroform phases. The covalent attachment of two ß-diketone fragments to a diazacrown ether resulted in a cooperative interaction within the receptor for Sr(2+) transfer, which remarkably enhanced the efficiency of Sr(2+) transfer relative to a mixed ß-diketone and diazacrown system. The intramolecular cooperative effect was observed only in the IL extraction system, providing a 500-fold increase in extraction performance for Sr(2+) over chloroform. Slope analysis and potentiometric titration confirmed that identical extraction mechanisms operated in both the IL and chloroform systems. Extended X-ray absorption fine structure spectroscopy revealed that the average distance between Sr(2+) and O atoms in the Sr(2+) complex was shorter in IL than in chloroform. Consequently, Sr(2+) was held by H(2)ßDA18C6 more rigidly in IL than in chloroform, representing an important factor dominating the magnitude of the intramolecular cooperative effect of H(2)ßDA18C6 for Sr(2+). Furthermore, competitive extraction studies with alkaline earth metal ions revealed that the magnitude of the intramolecular cooperative effect depended on the suitability between metal ion size and the cavity size of H(2)ßDA18C6. Sr(2+) was successfully recovered from IL by controlling the pH in the receiving phase, and the extraction performance of H(2)ßDA18C6 in IL was maintained after five repeated uses.

Validation of the (Q)SAR combination approach for mutagenicity prediction of flavor chemicals.

Most exposure levels of flavor in food are considered to be extremely low. If at all, genotoxic properties should be taken into account in safety evaluations. We have recently established a (quantitative) structure-activity relationship, (Q)SAR, combination system, which is composed of three individual models of mutagenicity prediction for industrial chemicals. A decision on mutagenicity is defined as the combination of predictive results from the three models. To validate the utility of our (Q)SAR system for flavor evaluation, we assessed 367 flavor chemicals that had been evaluated mainly by JECFA and for which Ames test results were available. When two or more models gave a positive evaluation, the sensitivity was low (19.4%). In contrast, when one or more models gave a positive evaluation, the sensitivity increased to 47.2%. The contribution of this increased sensitivity was mainly due to the result of the prediction by Derek for Windows, which is a knowledge-based model. Structural analysis of false negatives indicated some common sub-structures. The approach of improving sub-structural alerts could effectively contribute to increasing the predictability of the mutagenicity of flavors, because many flavors possess categorically similar functional sub-structures or are composed of a series of derivatives.

Synergistic effect of 18-crown-6 derivatives on chelate extraction of lanthanoids(III) into an ionic liquid with 2-thenoyltrifluoroacetone.

The synergistic effect of 18-crown-6 derivatives, such as 18-crown-6 (18C6), cis-dicyclohexano-18-crown-6 (DC18C6) and dibenzo-18-crown-6 (DB18C6), on the extraction of trivalent lanthanoids (Ln(3+)) into an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, with 2-thenoyltrifluoroacetone (Htta) was investigated. The extractability of lighter Ln(3+) was enhanced by adding 18C6 or DC18C6, whereas no enhancement of the extractability was observed by adding DB18C6. Moreover, the synergistic effect by the crown ether (CE) was increased along with the decrease in the atomic number of Ln. In the synergistic extraction system, Ln(3+) was extracted as cationic ternary complexes Ln(tta)(2)(CE)(+) and Ln(tta)(CE)(2+), and it was suggested that the formation of the Ln(tta)(CE)(2+) complex as an extracted species results in the large synergistic effect. This synergistic effect originated in a size-fitting effect of CE on complexation to Ln(3+).

Production of highly charged heavy ions by 18 GHz superconducting electron cyclotron resonance at Research Center for Nuclear Physics.

An 18 GHz superconducting electron cyclotron resonance ion source has been installed as a subject of the azimuthally varying field cyclotron upgrade project (K. Hatanaka et al., in Proceedings of the 17th International Conference on Cyclotrons and Their Applications, Tokyo, Japan, 18-22 October 2004, pp. 115-117), in order to increase beam currents and to extend the variety of ions. The production development of several ions has been performed since 2006 and some of them have already been used for user experiments [T. Yorita et al., Rev. Sci. Instrum. 79, 02A311 (2008)]. Further optimizations for each component such as the material of plasma electrode, material, and shape of bias probe and mirror field have been continued and more intense ion beams have been obtained for O, N, and Ar. For the purpose of obtaining highly charged Xe with several microamperes, the optimization of position and shape of plasma electrode and bias disk has also been done and highly charged Xe(32+) beam has been obtained successfully.

Dimensional change measurements of conventional and flowable composite resins using a laser displacement sensor.

The polymerization shrinkage values of commercial flowable and conventional composites were measured with a newly developed laser displacement sensor. Compressive strength and filler content were also measured. Compared to conventional composites, the flowable composites required a longer time - not exceeding 4 minutes - to reach a constant polymerization shrinkage rate. In terms of shrinkage ratio, it was less than 1.5% for conventional composites at 90 minutes, which was lower than that of flowable composites, i.e. more than 2.0%. The compressive strength of conventional composites was higher than that of flowable composites. A highly significant correlation between filler content and polymerization shrinkage at 90 minutes was observed, and polymerization shrinkage tended to decrease as filler content increased. In light of the results obtained in this study, the newly developed displacement meter with a laser displacement sensor proved to be effective for in-depth investigation of the polymerization shrinkage of dental composites.

Cooperative intramolecular interaction of diazacrown ether bearing beta-diketone fragments on an ionic liquid extraction system.

A novel extractant beta-diketone-substituted diaza-18-crown-6 demonstrated very efficient extraction of Sr(2+) due to an intramolecular synergistic effect on the ionic liquid extraction system and recovery of Sr(2+) from the ionic liquid was successfully achieved under acidic conditions.

Ionic liquid synergistic cation-exchange system for the selective extraction of lanthanum(III) using 2-thenoyltrifluoroacetone and 18-crown-6.

A novel synergistic extraction system was investigated for the possible selective separation of light lanthanoids using an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, as an extraction solvent and 2-thenoyltrifluoroacetone and 18-crown-6 as extractants. Trivalent lanthanum was efficiently extracted as a cationic ternary complex by the cation-exchange process, whereas europium and lutetium showed relatively low extractability without forming respective ternary complexes. This result is thought to originate in a size-fitting effect of 18-crown-6 to lanthanum and the unique nature of the ionic liquid as a chelate extraction solvent.

Development of an 18 GHz superconducting electron cyclotron resonance ion source at RCNP.

An 18 GHz superconducting electron cyclotron resonance ion source has recently been developed and installed in order to extend the variety and the intensity of ions at the RCNP coupled cyclotron facility. Production of several ions such as O, N, Ar, Kr, etc., is now under development and some of them have already been used for user experiments. For example, highly charged heavy ion beams like (86)Kr(21+,23+) and intense (16)O(5+,6+) and (15)N(6+) ion beams have been provided for experiments. The metal ion from volatile compounds method for boron ions has been developed as well.

Development of dental composite resin utilizing low-shrinking and low-viscous monomers.

To lower the viscosity of composite resins, experimental composite resins were produced using low-viscosity monomer mixtures of newly developed polyfunctional acrylates, and the mechanical and physical properties of the hardened composites were investigated. Mechanical (i.e., compressive, diametral tensile, and bending) strength of a polymer obtained from one new monomer mixture without fillers was similar to that of a bis-GMA/TEGDMA (2/1 weight ratio) based polymer. As for the hardened composites, the mechanical strength of composites produced using the new monomer mixtures showed a different tendency from that of bis-GMA based composites. Further, even the viscosity of composite pastes with high filler content was markedly lower than that of bis-GMA based composites. In terms of setting shrinkage, the composites consisting of new monomer mixtures exhibited significantly smaller shrinkage than the bis-GMA based composites, and decreased with increase in filler content.