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.

Nanostructure analysis of composite materials using polarized neutrons and polarized protons

Kumada, Takayuki

Shiki, 63, p.2 - 5, 2024/07

We introduce recent studies of spin-contrast-variation neutron scatterings, which utilizes the property that scattering power of neutron against proton remarkably depends on their relative spin directions, to reveal nanostructure of composite materials.

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

Nanometer-thick crystalline ice plates in rapidly-frozen glucose solution observed by spin-contrast-variation small-angle neutron scattering

Kumada, Takayuki; Nakagawa, Hiroshi; Miura, Daisuke; Sekine, Yurina; Motokawa, Ryuhei; Hiroi, Kosuke; Inamura, Yasuhiro; Oku, Takayuki; Oishi, Kazuki*; Morikawa, Toshiaki*; et al.

Hamon, 34(2), p.50 - 53, 2024/05

Spin-contrast-variation (SCV) small-angle neutron scattering (SANS) enabled us to determine structure of nano-ice crystals that were generated in rapidly frozen sugar solution. In the frozen glucose solution, we found that the nano-ice crystals formed a planar structure with a radius larger than several tens of nanometers and a thickness of 2-3 nm, which was close to the critical nucleation size of ice crystals in supercooled water. This result suggests that the glucose molecules were preferentially bound to a specific face of nano-ice crystals, and then blocked the crystal growth perpendicular to that face.

Synthesis of heat-resistant living polymer particles by one-step reversible addition-fragmentation chain transfer precipitation polymerization of styrene and -phenylmaleimide

Yamazaki, Shun*; Kaneko, Naoya*; Kato, Atsuya*; Watanabe, Kohei*; Aoki, Daisuke*; Taniguchi, Tatsuo*; Karatsu, Takashi*; Ueda, Yuki; Motokawa, Ryuhei; Okura, Koki*; et al.

Polymer, 298, p.126846_1 - 126846_11, 2024/04

https://doi.org/10.1016/j.polymer.2024.126846

Upgrade of the small-angle neutron scattering diffractometer SANS-J at JRR-3

Kumada, Takayuki; Motokawa, Ryuhei; Oba, Yojiro; Nakagawa, Hiroshi; Sekine, Yurina; Micheau, C.; Ueda, Yuki; Sugita, Tsuyoshi; Birumachi, Atsushi; Sasaki, Miki; et al.

Journal of Applied Crystallography, 56(6), p.1776 - 1783, 2023/12

https://doi.org/10.1107/S1600576723009731

The combination of the existing position-sensitive photomultiplier and the He main detector with focusing devices, and the newly installed front detectors in SANS-J at JRR-3 covers small-angle neutron scattering signals in the range of the magnitude of the scattering vector Q from 0.002 to 6 nm-1 gaplessly with three standard device layouts. The installation of the front detector and a graphical user interface system largely improved the usability of SANS-J.

Structural changes of polystyrene particles in subcritical and supercritical water revealed by in situ small-angle neutron scattering

Shibata, Motoki*; Nakanishi, Yohei*; Abe, Jun*; Arima, Hiroshi*; Iwase, Hiroki*; Shibayama, Mitsuhiro*; Motokawa, Ryuhei; Kumada, Takayuki; Takata, Shinichi; Yamamoto, Katsuhiro*; et al.

Polymer Journal, 55(11), p.1165 - 1170, 2023/11

https://doi.org/10.1038/s41428-023-00817-1

Polymer photonic crystals prepared by triblock copolymerization-induced microphase separation

Isozaki, Yuka*; Higashiharaguchi, Seiya*; Kaneko, Naoya*; Yamazaki, Shun*; Taniguchi, Tatsuo*; Karatsu, Takashi*; Ueda, Yuki; Motokawa, Ryuhei

Chemistry Letters, 51(6), p.625 - 628, 2022/06

https://doi.org/10.1246/cl.220089

Proton chelating ligands drive improved chemical separations for rhodium

Narita, Hirokazu*; Nicolson, R. M.*; Motokawa, Ryuhei; Ito, Fumiyuki*; Morisaku, Kazuko*; Goto, Midori*; Tanaka, Mikiya*; Heller, W. T.*; Shiwaku, Hideaki; Yaita, Tsuyoshi; et al.

Inorganic Chemistry, 58(13), p.8720 - 8734, 2019/07

https://doi.org/10.1021/acs.inorgchem.9b01136

Phase-transition kinetics of magnetic skyrmions investigated by stroboscopic small-angle neutron scattering

Nakajima, Taro*; Inamura, Yasuhiro; Ito, Takayoshi*; Oishi, Kazuki*; Oike, Hiroshi*; Kagawa, Fumitaka*; Kikkawa, Akiko*; Taguchi, Yasujiro*; Kakurai, Kazuhisa*; Tokura, Yoshinori*; et al.

Physical Review B, 98(1), p.014424_1 - 014424_5, 2018/07

https://doi.org/10.1103/PhysRevB.98.014424

We investigated the phase-transition kinetics of magnetic skyrmion lattice (SkL) in MnSi by means of stroboscopic small-angle neutron scattering (SANS). Temporal evolutions of SANS patterns were measured with time resolution of 13 ms while sweeping temperature as fast as 50 Ks. It turned out that the paramagnetic-to-SkL transition immediately occurs upon traversing the equilibrium phase boundary on the rapid cooling, whereas the SkL-to-conical transition can be kinetically avoided to realize the low-temperature metastable SkL with a long-range magnetic order. The formation of the metastable SkL was found to be strongly dependent not only on cooling rate, but also on magnetic eld and trajectory in the H-T phase diagram.