Role of Alkyl Chain Branching in the Self-Assembly of Nitrilotriacetamide-Based Lanthanide Extractants

Ueda, Yuki; Kobayashi, Toru; Nakamura, Satoshi; Ban, Yasutoshi; Kaneta, Yui; Nabatame, Nozomi; Micheau, C.; Tokunaga, Kohei; Nakabe, Rintaro; Kaneko, Masashi*; et al.

Langmuir, 42(1), p.1613 - 1626, 2026/01

https://doi.org/10.1021/acs.langmuir.5c05651

Understanding the structural factors governing the metal ions selectivity of solvent extraction systems is crucial for developing advanced processes for partitioning and transmutation of high-level radioactive waste. Here, we systematically investigated the effect of alkyl side-chain branching in nitrilotriacetamide (NTAamide) extractants on the extraction of lanthanum (La) and neodymium (Nd), chosen as representative lanthanides. Four extractants having each eight carbon atoms as one of the amide chains with identical molecular weights but different degrees of alkyl branching were examined. Distribution ratios were measured as a function of HNO concentration, and the local coordination structures of La and Nd were analyzed by extended X-ray absorption fine structure (EXAFS), while supramolecular aggregation in the organic phase was characterized by small-angle neutron scattering (SANS). EXAFS analysis revealed that the inner-sphere coordination environment of La and Nd was essentially unaffected by the degree of alkyl branching. In contrast, SANS results showed that extractants with fewer branched alkyl groups formed larger aggregates at low HNO concentrations, particularly in the case of Nd, where aggregation was found to facilitate extraction and prevent precipitation of poorly soluble complexes. These findings demonstrate that alkyl branching strongly influences supramolecular aggregation, which in turn governs extraction behavior. This work highlights the potential of nanoscale structural control as a new design concept for improving selectivity in lanthanide and actinide solvent extraction systems.

Spin-singlet ground state with spin gap in = antiferromagnetic tetramer compound YbSiO

Hase, Masashi*; Kaneko, Koji; Tabata, Chihiro; Yamauchi, Hiroki; Tsujii, Naohito*; Dnni, A.*

Physical Review B, 111(9), p.094403_1 - 094403_9, 2025/03

https://doi.org/10.1103/PhysRevB.111.094403

Preliminary studies on ion-pair extractions of Zr, Hf, Nb, and Ta using extractants having tertiary N atom from HSO and HF

Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*

Chemistry Letters, 53(9), p.upae164_1 - upae164_4, 2024/09

https://doi.org/10.1093/chemle/upae164

Ion-pair extractions enable to recover the anionic metal ions, such as TcO and ReO, using cationic extractant. Recently the noble metals in hydrochloric acid are extracted by extractants having secondary and tertiary amino N atoms in their structures. Following this, extractions of Zr, Hf, Nb and Ta, metal anions present in sulfonic and hydrofluoric acids, are examined using this technique. Zr and Hf in HSO, and Zr, Hf, Nb and Ta in HF can be extracted by NTAamide, MIDOA and TOA, and a basic information on their extraction behavior is obtained in this work.

Single helicity of the triple- triangular skyrmion lattice state in the cubic chiral helimagnet EuPtSi

Matsumura, Takeshi*; Tabata, Chihiro; Kaneko, Koji; Nakao, Hironori*; Kakihana, Masashi*; Hedo, Masato*; Nakama, Takao*; Onuki, Yoshichika*

Physical Review B, 109(17), p.174437_1 - 174437_8, 2024/05

https://doi.org/10.1103/PhysRevB.109.174437

Extraction of Rh(III) from hydrochloric acid by protonated NTAamide(C6) and analogous compounds and understanding of extraction equilibria by using UV spectroscopy and DFT calculations

Sasaki, Yuji; Kaneko, Masashi; Ban, Yasutoshi; Kinoshita, Ryoma; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*

Analytical Sciences, 39(9), p.1575 - 1583, 2023/09

https://doi.org/10.1007/s44211-023-00376-8

Extraction of Rh from HCl can be performed by NTAamide(C6) (hexahexyl-nitrilotriacetamide) and other related compounds into n-dodecane. We use ion-pair extraction of anionic species of Rh-chloride and protonated extractant. Rh behave as anion in hydrochloric acid and the tertiary nitrogen atom in extractant may be protonated to produce the quaternary amine in acidic condition. From the present work, the maximum distribution ratio of Rh(III) is 16. The D(Rh) values are changeable during preparation of the aqueous solutions because different Rh-Cl-HO complexes are formed in HCl media and show the slow exchange rate between Cl and HO. Using the UV spectrum, Rh-chloride solution having the peak of spectrum at 504 nm can be extracted effectively, where RhCl(HO) and RhCl(HO) exist mainly from DFT calculation. Stoichiometry of one-one complex of Rh and NTAamide is obtained from slope analysis, and 85 mM of concentrated Rh ion can be extracted.

Preliminary studies of XANES and DFT calculation of Ru extraction by imino-diacetamide and related compounds

Sasaki, Yuji; Nakase, Masahiko*; Kaneko, Masashi; Kobayashi, Toru; Takeshita, Kenji*; Matsumiya, Masahiko*

Analytical Sciences, 5 Pages, 2023/00

https://doi.org/10.1007/s44211-023-00453-y

We conducted three field researches on Ru-extraction, XANES, and DFT-calculation. The order of the distribution ratio, D(Ru), from acid, HCl HSO HNO HClO, by MIDOA is studied by XANES spectra, which indicates the valency change of Ru in HCl media and supports the ion pairing extraction of anionic Ru ion and cationic MIDOA. The same extractant trend, NTAamide MIDOA IDOA, due to D values as the energy gap of HOMO and LUMO could be found by DFT calculation, which suggests that the reaction heat has a positive correlation with extractability for extractant.

Fully chelating NO-pentadentate planar ligands designed for the strongest and selective capture of uranium from seawater

Mizumachi, Takumi*; Sato, Minami*; Kaneko, Masashi; Takeyama, Tomoyuki*; Tsushima, Satoru*; Takao, Koichiro*

Inorganic Chemistry, 61(16), p.6175 - 6181, 2022/04

https://doi.org/10.1021/acs.inorgchem.2c00306

Based on unique 5-fold equatorial coordination of UO, water-compatible pentadentate planar ligands, Hsaldian and its derivatives, were designed as strong and selective capture of UO in seawater. In the simulated seawater condition (0.5 M NaCl + 2.3 mM HCO/CO, pH 8), saldian shows the strongest complexation with UO to form UO(saldian) (log = 28.05 0.07), which is more than 10 order of magnitude greater than amidoxime-based or -inspired ligand systems most commonly employed for U capture from seawater. Good selectivity for UO from other metal ions coexisting in seawater was also demonstrated.

Density functional study aiming to elucidate separation mechanisms of minor actinides and rare earths

Kaneko, Masashi

Nihon Genshiryoku Gakkai-Shi ATOMO, 64(1), p.30 - 34, 2022/01

https://doi.org/10.3327/jaesjb.64.1_30

Partitioning of minor actinides from rare earths is one of the most important techniques to develop group separation of high-level radioactive liquid waste. In this issue, the results of prediction of separation performance between minor actinides and rare earths observed in solvent extraction and the separation mechanism by means of using density functional theory are explained.

Mutual separation of Ln and An using TODGA and DTBA with high organic acid concentrations

Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*; Nakase, Masahiko*; Takeshita, Kenji*

Solvent Extraction and Ion Exchange, 40(6), p.620 - 640, 2022/00

https://doi.org/10.1080/07366299.2021.2024650

Owing to the chemical behavior of trivalent lanthanide and actinide ions with similar ionic radii, realizing this separation is still challenging. All lanthanides, Am, and Cm can be extracted using diglycolamide (DGA), and relatively high An/Ln separation efficiencies have been obtained using diethylenetriamine-triacetic-bisamide (DTBA). To improve the previous results as well as the separation conditions, we used organic acids for pH adjustment. The advantages of this modification included low HNO, DTBA concentrations and pH stability owing to the addition of lactic acid. Under these modified conditions, the recovery rates observed were as follows: 97.1% for Nd with the co-existence of 1.59% Am in organic phase, and 98.4% for Am with the co-existence of 2.95% Nd in aqueous phase.

Density functional theory study on the Ir Mssbauer spectroscopic parameters of Vaska's complexes and their oxidative adducts

Kaneko, Masashi; Nakashima, Satoru*

Inorganic Chemistry, 60(17), p.12740 - 12752, 2021/09

https://doi.org/10.1021/acs.inorgchem.1c00239

In the present study, density functional theory (DFT) calculation was applied to Vaska's complexes of formula -[IrCl(CO)(PPh)], and their oxidative adducts with small molecules (YZ) including H, i.e., -[IrCl(YZ)(CO))(PPh)], to successfully correlate the electronic states of the complexes with the corresponding Ir Mssbauer spectroscopic parameters. After confirming the reproducibility of the DFT methods for elucidating the equilibrium structures and Ir Mssbauer isomer shifts of the octahedral Ir complexes, the isomer shifts and quadrupole splitting values of Vaska's complexes and their oxidative adducts were calculated. A bond critical point analysis revealed that the tendency in the isomer shifts was correlated with the strength of the covalent interaction in the coordination bonds. In an electric field gradient (EFG) analysis of the oxidative adducts, the sign of the principal axis was found to be positive for the complex with YZ = Cl and negative for the complex with YZ = H. This reversal of the sign of the EFG principal axis was caused by the difference in the electron density distribution for the coordination bonds between Ir and YZ, according to a density of states analysis.