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.

Globular pattern formation of hierarchical ceria nanoarchitectures

Aoyagi, Noboru; Motokawa, Ryuhei; Okumura, Masahiko; Ueda, Yuki; Saito, Takumi*; Nishitsuji, Shotaro*; Taguchi, Tomitsugu*; Yomogida, Takumi; Sazaki, Gen*; Ikeda, Atsushi

Communications Chemistry (Internet), 7, p.128_1 - 128_13, 2024/06

https://doi.org/10.1038/s42004-024-01199-y

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.

Interpenetration of rubber and silane coupling agent on an inorganic substrate revealed by spin-contrast-variation neutron reflectivity

Kumada, Takayuki; Iwahara, Daisuke*; Nishitsuji, Shotaro*; Akutsu, Kazuhiro*; Miura, Daisuke; Motokawa, Ryuhei; Sugita, Tsuyoshi; Torikai, Naoya*; Amino, Naoya*; Oku, Takayuki; et al.

Journal of Physical Chemistry C, 128(21), p.8797 - 8802, 2024/05

https://doi.org/10.1021/acs.jpcc.4c00963

We elucidated the entanglement of polybutadiene and silane coupling agent (SCA) molecules bound to Si substrates using spin-contrast-variation (SCV) neutron reflectivity (NR). In an annealed integral blend film of polybutadiene and SCA, a SCA layer generated on the Si substrate was composed of 70 vol. percent SCA molecules extended perpendicularly from the silicon substrate and entangled with 30 vol. percent polybutadiene molecules. By contrast, in an SCA-precoated polybutadiene film, the SCA-precoated layer is composed of densely packed SCA molecules forming crystal-like structure, and thus did not become entangled with the postcoated polybutadiene molecules. This poor entanglement resulted in poor binding between polybutadiene and Si substrate.

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

Heterogeneous aggregation of humic acids studied by small-angle neutron and X-ray scattering

Saito, Takumi*; Motokawa, Ryuhei; Okubo, Takahiro*; Miura, Daisuke*; Kumada, Takayuki

Environmental Science & Technology, 57(26), p.9802 - 9810, 2023/07

https://doi.org/10.1021/acs.est.3c02028

Neutron resonance absorption imaging of simulated high-level radioactive waste in borosilicate glass

Oba, Yojiro; Motokawa, Ryuhei; Kaneko, Koji; Nagai, Takayuki; Tsuchikawa, Yusuke; Shinohara, Takenao; Parker, J. D.*; Okamoto, Yoshihiro

Scientific Reports (Internet), 13, p.10071_1 - 10071_8, 2023/06

https://doi.org/10.1038/s41598-023-37157-2