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.

Particle arrangements and optical changes induced by the water swelling of melanin-like polydopamine layers

Watanabe, Taku*; Maejima, Yui*; Ueda, Yuki; Motokawa, Ryuhei; Takabatake, Ai*; Takeda, Shinichi*; Fudoji, Hiroshi*; Kishikawa, Keiki*; Koori, Michinari*

Langmuir, 41(34), p.22762 - 22773, 2025/09

https://doi.org/10.1021/acs.langmuir.5c01855

The assembled structures of melanin particles, i.e., colloidal particles coated with a melanin-like polydopamine (PDA) layer, create vivid structural colors. While the thickness of the PDA layer influences the particle arrangement and optical properties, the underlying mechanism has remained controversial. We demonstrate that the water swelling characteristics of PDA are crucial factors governing the dispersion and aggregation of these particles in solution. Detailed comparisons between dry and wet conditions revealed that the PDA layer readily absorbs water molecules, which leads to significant swelling in the thicker layers. The swelling of the PDA layers determined whether the particles remained dispersed or partially aggregated in the water, ultimately controlling the particle arrangement in the dry state once the water evaporated. These findings provide insights into the self-assembly of colloidal particles and offer a strategy for tuning the periodic particle order. This feature is pivotal for various applications in optical and sensing technologies.

Effects of the size of fillers on viscoelasticity in the glassy state of poly(styrene--butadiene) reinforced by carbon black

Watanabe, Yuki*; Kumagawa, Daiki*; Karitani, Shu*; Inoue, Tadashi*; Iwabuki, Hitoshi*; Nakanishi, Yohei*; Shibata, Motoki*; Motokawa, Ryuhei; Sugita, Tsuyoshi; Ueda, Yuki; et al.

Macromolecules, 58(16), p.8641 - 8648, 2025/08

https://doi.org/10.1021/acs.macromol.5c01357

Characterization of micelles of the thermo-responsive zwitterionic surfactant, 3-(-nonyl N,N-dimethylammonio)-propyl sulfate, present in isotropic solutions above its upper critical solution temperature

Tanji, Tamao*; Kusunoki, Yuto*; Nakagawa, Taichi; Takase, Tsugiko*; Ueda, Yuki; Motokawa, Ryuhei; Hinze, W. L.*; Takagai, Yoshitaka*

Langmuir, 41(21), p.13184 - 13191, 2025/06

https://doi.org/10.1021/acs.langmuir.5c00818

Fluorous and organic extraction systems; A Comparison from the perspectives of coordination structures, interfaces, and bulk extraction phases

Ueda, Yuki; Micheau, C.; Akutsu, Kazuhiro*; Tokunaga, Kohei; Yamada, Masako*; Yamada, Norifumi*; Bourgeois, D.*; Motokawa, Ryuhei

Langmuir, 40(46), p.24257 - 24271, 2024/11

https://doi.org/10.1021/acs.langmuir.4c02268

Microscopic structures in liquid-liquid extraction, such as structuration between extractants or extracted complexes in bulk organic phases and at interfaces, can influence macroscopic phenomena, such as the distribution behavior of solutes, including extraction efficiency, selectivity, and phase separation of the organic phase. In this study, we correlated the macroscopic behavior of the extraction of Zr(IV) ions from nitric acid solutions with microscopic structural information in order to understand at the molecular level the key factors contributing to the higher metal ion extraction performance in the fluorous extraction system comprising fluorous phosphate (TFP) in perfluorohexane as compared to the analogous organic extraction system comprising organic phosphate (THP) in n-hexane. Extended X-ray absorption fine structure, neutron reflectometry, and small-angle neutron scattering revealed the local coordination structure around the Zr(IV) ion, the accumulation of extractant molecules at the interface, and the structuration of extractant molecules in the bulk extraction phase, respectively. In the fluorous extraction system, extractant aggregates with were formed after contact with nitric acid. In contrast, in the organic extraction system, only extractant dimers were formed. We speculate that differences in the local coordination structure around the Zr(IV) ion and the structuration of the extractant molecules in the bulk extraction phase contribute to the high Zr(IV) extraction performance in the fluorous extraction system. In particular, the size of the aggregates hardly changed with increasing Zr(IV) concentration in the fluorous phase, which may be closely related to the absence of phase splitting in the fluorous extraction system.

None

Ueda, Yuki; Micheau, C.; Motokawa, Ryuhei

Shiki, 64, p.2 - 6, 2024/09

https://www.j-neutron.com/img/Vol64_r3.pdf

no abstracts in English

Impact of branching position and degree on uranium extraction by amines; A Supramolecular and thermodynamic study

Guerinoni, E.*; Giusti, F.*; Dourdain, S.*; Dufrche, J.-F.*; Motokawa, Ryuhei; Ueda, Yuki; Aoyagi, Noboru; Zemb, T.*; Pellet-Rostaing, S.*

Journal of Molecular Liquids, 403, p.124820_1 - 124820_11, 2024/06

https://doi.org/10.1016/j.molliq.2024.124820

Organization of malonamides from the interface to the organic bulk phase

Micheau, C.; Ueda, Yuki; Motokawa, Ryuhei; Akutsu, Kazuhiro*; Yamada, Norifumi*; Yamada, Masako*; Moussaoui, S. A.*; Makombe, E.*; Meyer, D.*; Berthon, L.*; et al.

Journal of Molecular Liquids, 401, p.124372_1 - 124372_12, 2024/05

https://doi.org/10.1016/j.molliq.2024.124372

Benchmark analysis by Beremin model and GTN model in CAF Subcommittee

Nagoshi, Yasuto*; Fukahori, Takuya*; Okada, Hiroshi*; Takahashi, Akiyuki*; Shimodaira, Masaki; Ueda, Takashi*; Ogawa, Takuya*; Yashirodai, Kenji*; Takahashi, Yukio*; Ohata, Mitsuru*

Transactions of the 27th International Conference on Structural Mechanics in Reactor Technology (SMiRT 27) (Internet), 9 Pages, 2024/03

no abstracts in English

Occurrence of radioactive cesium-rich micro-particles (CsMPs) in a school building located 2.8 km south-west of the Fukushima Daiichi Nuclear Power Plant

Fueda, Kazuki*; Komiya, Tatsuki*; Minomo, Kenta*; Horie, Kenji*; Takehara, Mami*; Yamasaki, Shinya*; Shiotsu, Hiroyuki; Onuki, Toshihiko*; Grambow, B.*; Law, G. T. W.*; et al.

Chemosphere, 328, p.138566_1 - 138566_12, 2023/07

https://doi.org/10.1016/j.chemosphere.2023.138566