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平田 芳信*; 金子 文俊*; Radulescu, A.*; 西津 貴久*; 勝野 那嘉子*; 今泉 鉄平*; 元川 竜平; 熊田 高之; 中川 洋
Journal of Applied Glycoscience, 72(1), p.7201102_1 - 7201102_9, 2025/02
SANS/FTIR-ATR同時測定システムを用いて、逆分解過程におけるジャガイモデンプンの複数の構造変化を記録した。SANSパターンでは、肩のようなピークが時間とともに顕著になる。二重らせん構造が整然と並んだ量を示すピーク強度Imaxは時間の経過とともに増加し、レトログラデーションによってデンプンがナノスケールで整然と再構築されたことが示された。FTIR-ATRスペクトルでは、1042cm
と1016cmの吸収の比率が増加し、デンプンの短距離秩序構造の量が逆行分解中に増加したことが示された。
の平衡値の半分を得るまでの時間は、Imaxのそれよりも大きかった。デンプンの短距離秩序構造の変化は、ナノ構造の変化よりも先に収束することが観察された。これらの結果は、二重らせん構造がアミロペクチン側鎖によって最初に形成され、その後、これらの二重らせん構造が整然と配列することを示している。
capture and release at high pressures on a unique large-pore mesoporous carbonSzab
, L.*; 井上 瑞基*; 関根 由莉奈; 元川 竜平; 松本 悠佑*; Nge, T. T.*; Ismail, E.*; 一ノ瀬 泉*; 山田 竜彦*
ChemSusChem, p.e202402034_1 - e202402034_13, 2025/00
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)テクニカルリグニンを使用して、約20
30nmの細孔サイズを持つ大細孔メソポーラスカーボンを開発した。ソフトテンプレート過程において、コポリマーテンプレートからユニークな円筒形の超分子凝集体が形成された。この特異なナノ構造は、PluronicテンプレートとPEGグラフト化リグニン誘導体(グリコールリグニン)の両方にポリエチレングリコール(PEG)セグメントが存在するために形成した。結果として得られた大細孔メソポーラスカーボンにおいて、毛管凝縮により270Kで 飽和圧力に近い条件においてCOの吸収が大幅に増加した。
上田 祐生; Micheau, C.; 阿久津 和宏*; 徳永 紘平; 山田 雅子*; 山田 悟史*; Bourgeois, D.*; 元川 竜平
Langmuir, 40(46), p.24257 - 24271, 2024/11
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)本研究では、パーフルオロヘキサン中のフルオラスリン酸エステル(TFP)からなるフルオラス抽出系において、n-ヘキサン中の有機リン酸エステル(THP)からなる類似の有機抽出系と比較して、より高い金属イオン抽出性能に寄与する主要因を分子レベルで理解するために、硝酸溶液からのZr(IV)イオンの抽出の巨視的挙動を微視的構造情報と相関させた。拡張X線吸収微細構造、中性子反射率測定、中性子小角散乱により、それぞれZr(IV)イオン周辺の局所配位構造、界面における抽出剤分子の蓄積、バルク抽出相における抽出剤分子の構造が明らかになった。その結果、いずれの抽出系においても、界面には抽出剤分子はあまり蓄積しなかった。フルオラス抽出系では、硝酸との接触により凝集体が形成され、Zr(IV)抽出後も残存した。一方、有機抽出系では、二量体のみが形成された。Zr(IV)イオン周辺の局所的な配位構造とバルク抽出相における抽出剤分子の構造の違いが、フルオラス抽出系における高いZr(IV)抽出性能に寄与していると推測している。特に、フルオラス相中のZr(IV)濃度が増加しても凝集体の大きさはほとんど変化せず、これはフルオラス抽出系で相分離が起こらないことと密接に関係していると考えられる。
上田 祐生; Micheau, C.; 元川 竜平
四季, 64, p.2 - 6, 2024/09
本稿では、2種類のマロンアミド抽出系における選択性と抽出速度の違いを理解するために、バルク有機相と界面における抽出剤の組織化について調べた結果について紹介する。バルク有機相における抽出剤の組織化は、X線小角散乱法(SAXS)により、界面における抽出剤の組織化は、有機相-水相界面における界面張力測定(IFT)と空気-有機相界面における中性子反射率測定(NR)により検証した。
青柳 登; 元川 竜平; 奥村 雅彦; 上田 祐生; 斉藤 拓巳*; 西辻 祥太郎*; 田口 富嗣*; 蓬田 匠; 佐崎 元*; 池田 篤史
Communications Chemistry (Internet), 7, p.128_1 - 128_13, 2024/06
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)Dissipative structures often appear as an unstable counterpart of ordered structures owing to fluctuations that do not form a homogeneous phase. Even a multiphase mixture may simultaneously undergo one chemical reaction near equilibrium and another one that is far from equilibrium. Here, we observed in real-time crystal seed formation and simultaneous nanocrystal aggregation proceeding from tetravalent cerium complexes to ceria nanoparticles in an acidic aqueous solution and investigated the resultant hierarchical nanoarchitecture. The formed particles exhibited two very different size ranges. The hierarchically assembled structures in solutions were ceria colloids, viz. primary core clusters of crystalline ceria and secondary clusters assembled through surface ions. Such self-assembly is widespread in multi-component complex fluids, paradoxically moderating hierarchical reactions. Stability and instability are not only critical but also complementary for co-optimization around the nearby free energy landscape prior to bifurcation.
熊田 高之; 元川 竜平; 岩瀬 裕希*
Journal of Applied Crystallography, 57(Part 3), p.728 - 733, 2024/06
被引用回数：1 パーセンタイル：60.30(Chemistry, Multidisciplinary)We found that intensity of small-angle neutron scattering (SANS) from ultrahigh-purity aluminium (5N-Al) was lower than that from aluminium alloys by a factor of 40 in maximum, and thus replaced a 500 mm-diameter aluminium alloy neutron window by the 5N-Al window at SANS-J. We succeeded in decreasing the intensity of background in range of the magnitude of scattering vector Q between 0.02 and 0.2 nm by a factor of 10 in maximum. This result indicates that, the 5N-Al window, which is made thicker to compensate lower tensile strength, generates much lower background than the aluminium alloy windows. The 5N-Al window is suitable for large-diameter neutron window in SANS diffractometers and windows in their environmental apparatus, which cannot be made of single crystalline silicon due to its poor fracture strength, processability, and/or affinity with metallic materials.
Guerinoni, E.*; Giusti, F.*; Dourdain, S.*; Dufr
che, J.-F.*; 元川 竜平; 上田 祐生; 青柳 登; Zemb, T.*; Pellet-Rostaing, S.*
Journal of Molecular Liquids, 403, p.124820_1 - 124820_11, 2024/06
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)In uranium production, liquid-liquid extraction using the AMEX (AMine EXtraction) process employs tertiary amines solubilized in an aliphatic diluent. Practical constraints as phase stability problems and co-extraction of competitive elements highlight the need for in-depth investigation and optimization. Modifying gradually the alkyl chain structure of tertiary amines, we investigate here the large variation in extraction performance in terms of Gibbs free energy of transfer using the ienaic decomposition taking into account long range interactions. We show hereby that structuration of the solvent phase can change uranium distribution by 2 orders of magnitude, which is incompatible with standard complexation theory of liquid-liquid extraction. We observe that co-extracted water is required to obtain extraction while extraction is quenched and no pair core can be formed when less than four as effective aggregation number. We conclude that the film term in the ienaic decomposition of the Gibbs energy of transfer, is the one that governs extraction performance. It shows that metal transfer is beyond complexation, and that organization of the solvent phase must be considered to quantitatively interpret the distribution coefficients.
中西 洋平*; 柴田 基樹*; 澤田 諭*; 近藤 寛朗*; 元川 竜平; 熊田 高之; 山本 勝宏*; 三田 一樹*; 宮崎 司*; 竹中 幹人*
Polymer, 306, p.127209_1 - 127209_7, 2024/06
被引用回数：2 パーセンタイル：61.66(Polymer Science)Adding silane coupling agents to rubber/silica particles systems improves their mechanical properties and the dispersion of the particles. The improvement is believed to be attributed to the enhanced adsorption of rubber molecules on the surface of silica particles by the silane coupling agent. However, the enhancement of the adsorption by silane coupling agent has not been clarified quantitatively yet. In this study, we have investigated the difference in (i) the adsorption of rubber on silica surfaces and (ii) the aggregation of silica particles in rubber/silica particle systems with and without silane coupling agents by using contrast variation neutron scattering (CV-SANS). The CVSANS results quantitatively clarified the adsorption layer's thickness and the degree of aggregation for both systems. In the case of the system without silane coupling agents, the adsorption layers do not exist around the particles, and the particles tend to aggregate. On the other hand, the adsorption layers of about 5.3 nm are formed on the surface of the particles in the system with silane coupling agents, and the addition of silane coupling agents suppressed the aggregation.
熊田 高之; 中川 洋; 三浦 大輔; 関根 由莉奈; 元川 竜平; 廣井 孝介; 稲村 泰弘; 奥 隆之; 大石 一城*; 森川 利明*; et al.
波紋, 34(2), p.50 - 53, 2024/05
本研究では、スピンコントラスト変調小角散乱法を用いてグルコース濃厚糖溶液を急冷すると氷結晶は平面上になり、その厚みは氷晶生成臨界半径と同程度の数ナノメートルしかないことを明らかにした。本研究は、グルコース分子が氷結晶の特定面に付着してその方向の成長を完全に止めてしまうことを示唆している。
Micheau, C.; 上田 祐生; 元川 竜平; 阿久津 和宏*; 山田 悟史*; 山田 雅子*; Moussaoui, S. A.*; Makombe, E.*; Meyer, D.*; Berthon, L.*; et al.
Journal of Molecular Liquids, 401, p.124372_1 - 124372_12, 2024/05
被引用回数：2 パーセンタイル：70.16(Chemistry, Physical)Supramolecular organization of amphiphilic extractant molecules is involved in metal cation selectivity and separation kinetics during solvent extraction. The relationship between extractant associates/aggregates formed in the organic bulk phase and at the liquid-liquid interface is poorly understood even though it affects the extraction mechanism. The nanoscopic structures of the extraction systems N,N,N',N'-tetrahexylmalonamide (THMA) in toluene and N,N'-dibutyl-N,N'-dimethyl-2-tetradecylmalonamide (DBMA) in n-heptane, used for either Pd(II) or Nd(III) selective extraction from an acidic aqueous phase, were examined. These systems present markedly different affinity for Pd(II) and Nd(III), and extraction kinetics. Extractant organization in the organic bulk phase and at the interface were compared by small-angle X-ray scattering, interfacial tension, and neutron reflectivity. THMA in toluene forms small associates in the organic bulk phase and accumulates in a diffuse layer at the interface, decreasing Pd(II) coordination probability and resulting in slow extraction. DBMA in n-heptane forms large aggregates and a compact, dense interfacial layer, resulting in rapid Pd(II) and Nd(III) extraction. Thus, Pd(II) extraction is driven by interfacial coordination alone, whereas the incorporation of Nd(III) into the core of large aggregates governs Nd(III) extraction in the interfacial layer. These results suggest that the interface should be described as a nanoscale interphase containing a high extractant concentration compared with the organic bulk phase.
熊田 高之; 岩原 大輔*; 西辻 祥太郎*; 阿久津 和宏*; 三浦 大輔; 元川 竜平; 杉田 剛; 鳥飼 直也*; 網野 直也*; 奥 隆之; et al.
Journal of Physical Chemistry C, 128(21), p.8797 - 8802, 2024/05
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)スピンコントラスト変調中性子反射率法を用いて自動車用ゴムタイヤに用いるブタジエンゴムがシランカップリング剤を通じてシリカ表面とどのように結合しているかを調べた。ブタジエンゴムとシランカップリング剤をシリコン基板にコートした後アニールした試料では、シリコン基板表面にシランカップリング剤とポリブタジエンが7:3の比で絡みあった膜が形成されるのに対し、シランカップリング剤をあらかじめコートした後にポリブタジエンをコートした試料では両者の絡み合いが足りないために容易に剥離してしまうことを突き止めた。
関根 由莉奈; 南川 卓也; 杉田 剛; 永川 栄泰*; 柴山 由樹; 元川 竜平; 深澤 倫子*
Nanoscale, 16(19), p.9400 - 9405, 2024/05
被引用回数：2 パーセンタイル：67.38(Chemistry, Multidisciplinary)凍結架橋法により強靱なカルボキシメチルセルロースナノファイバー(CMF)/ジルコニウム(Zr)複合ハイドロゲルを開発した。本ハイドロゲルは、Zrを含むHCl溶液を凍結CMFに添加し、それを解凍することによって調製した。作製したハイドロゲルはフッ化物に対して高い吸着性を示した。本研究により、ハイドロゲルと金属の複合体の開発に有用な知見を得た。
-phenylmaleimide山崎 駿*; 金子 直矢*; 加藤 敦也*; 渡邉 航平*; 青木 大輔*; 谷口 竜王*; 唐津 孝*; 上田 祐生; 元川 竜平; 大倉 滉生*; et al.
Polymer, 298, p.126846_1 - 126846_11, 2024/04
被引用回数：3 パーセンタイル：74.33(Polymer Science)Synthesis of heat-resistant, living polymer particles via one-step reversible addition-fragmentation chain transfer precipitation polymerization (RAFTPP) of styrene and -phenylmaleimide is reported. Gel permeation chromatography and nuclear magnetic resonance spectroscopy confirmed that the polymerization proceeded in a living manner. The scanning electron microscopy results showed that the monodisperse P(St-PhMI) RAFTPP particles with a diameter of 1.88 micrometer were successfully synthesized. The P(St-PhMI) RAFTPP showed excellent thermal stability with a high glass transition temperature and a 5 percent weight loss temperature. The surface concentration of the RAFT groups was determined to be 0.181 groups/square-nanometer due to fragmentation of the RAFT groups exposed on the particles. The small-angle neutron scattering measurements showed the particle formation mechanism, in which the swollen, growing polymer chains were consumed for particle formation. The introduction of grafted chains by surface-initiated RAFT polymerization demonstrated the possibility of further functionalization of P(St-PhMI) RAFTPP particles by exploiting their living nature.
He spin filter and small-angle X-ray scattering領木 研之*; 渡部 史*; 奥平 琢也*; 高橋 慎吾*; 奥 隆之; 廣井 孝介; 元川 竜平; 中村 洋*
Journal of Chemical Physics, 160(11), p.114907_1 - 114907_9, 2024/03
被引用回数：1 パーセンタイル：0.00(Chemistry, Physical)Small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) measurements were performed for deuterated and non-deuterated poly(ethylene glycol) (d-PEG and h-PEG, respectively) in DO and a DO/HO mixed solvent (Mix) to compere the scattering profiles. To determine the coherent scattering intensity of SANS, a He spin filter was utilized. The scattering profiles determined by SANS measurements were analyzed in terms of the wormlike chain model with touched beads along the contour of the chain. However, the SAXS profiles were not explained by the same model with uniform beads but with beads each consisting of a core and a shell having different electron densities. To explore the chain thickness determined form the SANS profile, scattering intensities for different combinations of d-PEG/DO, d-PEG/Mix, h-PEG/DO, and h-PEG/Mix were also examined.
熊田 高之; 元川 竜平; 大場 洋次郎; 中川 洋; 関根 由莉奈; Micheau, C.; 上田 祐生; 杉田 剛; 美留町 厚; 佐々木 未来; et al.
Journal of Applied Crystallography, 56(6), p.1776 - 1783, 2023/12
被引用回数：14 パーセンタイル：96.95(Chemistry, Multidisciplinary)既存のメイン検出器および高位置分解能フォトマル検出器に加えて新規に導入した前面検出器を組み合わせることにより、波数0.002nmから6nmにわたる散乱を3つの光学機器配置により切れ目なく測定できるようになった。またグラフィカルユーザーインターフェースの導入と併せて装置のユーザビリティが大幅に向上した。
辻 勇人*; 中畑 雅樹*; 菱田 真史*; 瀬戸 秀紀*; 元川 竜平; 井上 大傑*; 江川 泰暢*
Journal of Physical Chemistry Letters (Internet), 14(49), p.11235 - 11241, 2023/12
被引用回数：5 パーセンタイル：65.84(Chemistry, Physical)This work investigates the water-fraction dependence of the aggregation behavior of hydrophobic solutes in water-tetrahydrofuran (THF) and the elucidation of the role of THF using fluorescence microscopy, dynamic light scattering, neutron and X-ray scattering, as well as photoluminescence measurements. Based on the obtained results, the following model is proposed: hydrophobic molecules are molecularly dispersed in the low-water-content region (10-20 vol %), while they form mesoscopic particles upon increasing the water fraction to 30 vol percent. This abrupt change is due to the composition fluctuation of the water-THF binary system to form hydrophobic areas in THF, followed by THF-rich droplets where hydrophobic solutes are incorporated and form loose aggregates. Further increasing the water content prompts the desolvation of THF, which decreases the particle size and generates tight aggregates of solute molecules. This model is consistent with the luminescence behavior of the solutes and will be helpful to control the aggregation state of hydrophobic solutes in various applications.
柴田 基樹*; 中西 洋平*; 阿部 淳*; 有馬 寛*; 岩瀬 裕希*; 柴山 充弘*; 元川 竜平; 熊田 高之; 高田 慎一; 山本 勝宏*; et al.
Polymer Journal, 55(11), p.1165 - 1170, 2023/11
被引用回数：2 パーセンタイル：20.65(Polymer Science)Marine ecosystem degradation due to micro plastics is a significant environmental problem, as acknowledged by Sustainable Development Goal 14. Decomposition of plastics using near critical or supercritical water is one of the promising methods to reduce micro plastics. To attain the optimization of the method for improving environmental friendliness, it is necessary to clarify the structural change of materials during the process. We, thus, investigated the decomposition processes of polystyrene particles dispersed in deuterated water (DO) during heating under near critical or supercritical conditions by using in situ small-angle neutron scattering. Under subcritical conditions, the PS particles were swollen by DO due to increased compatibility with temperature. Near the critical point in subcritical conditions, the cleavage of PS chains in the particles occurred, so that the swollen ratio was much enhanced though the PS particles kept their shapes. In a supercritical condition, the PS particles were degraded into oil including oligomers or monomers and the phase-separated structures with styrene-rich and DO-rich regions.
熊田 高之; 中川 洋; 三浦 大輔; 関根 由莉奈; 元川 竜平; 廣井 孝介; 稲村 泰弘; 奥 隆之; 大石 一城*; 森川 利明*; et al.
Journal of Physical Chemistry Letters (Internet), 14(34), p.7638 - 7643, 2023/08
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)スピンコントラスト変調中性子小角散乱法を用いて急冷したグルコース濃厚溶液中に生成するナノアイス結晶の構造解析を行ったところ、厚さ1nm程度、半径数十nm以上の平面上の氷晶が生成していることを見出した。本結果はグルコース分子が特定の成長面に吸着することによりその面からの結晶成長を阻害していることを示す。
斉藤 拓巳*; 元川 竜平; 大窪 貴洋*; 三浦 大輔*; 熊田 高之
Environmental Science & Technology, 57(26), p.9802 - 9810, 2023/07
被引用回数：1 パーセンタイル：10.96(Engineering, Environmental)Aggregation of humic acids (HAs) were studied by small-angle neutron and X-ray scattering techniques. The combination of these techniques enables us to examine aggregation structures of heterogeneous HA particles. Two HAs with distinctive compositions were examined; a commercial HA (PAHA) and a HA extracted from deep sedimentary groundwater (HHA). While macroscopic coagulation tests showed that these HAs were stable in solutions except for HHA at pH 
6, small-angle neutron scattering (SANS) and X-ray scattering (SAXS) revealed that they formed aggregates with the sizes exceeding sub-micrometer length scale. The SAXS curves of PAHA remarkably varied with pD, whereas the SANS curves did not. With the help of theoretical fittings, it was revealed that PAHA aggregates consisted of two domains: poorly hydrated cores and well-hydrated proton-rich shells. The cores are (dis)aggregated with pD inside the aggregates of the shell. The SANS and SAXS curves of HHA resemble each other, and their intensities at low q increased with a decrease of pD, indicating the formation of homogeneous aggregates. This study revealed that distinctive aggregation behaviors exist in humic substances with heterogeneous structures like PAHA, which is invaluable for their roles in the fate of contaminants or nutrients in aqueous environments.
Micheau, C.; 上田 祐生; 元川 竜平; Bauduin, P.*; Girard, L.*; Diat, O.*
Langmuir, 39(31), p.10965 - 10977, 2023/07
被引用回数：9 パーセンタイル：73.37(Chemistry, Multidisciplinary)Understanding clay flotation mechanisms has become a major concern because of the increasing level of environmental contamination of soil and ground water by heavy metals and radionuclides. Clays are often used as sorbents for extracting metals in indirect flotation processes but can function simultaneously as defoamers. However, how foam generation and stability depend on the molecular interactions between the clays and surfactant is still controversial. In the present study, an amine polyethoxylated surfactant was used as a bifunctional surfactant that collected clay particles and acted as a foaming agent in the flotation process. The pH conditions strongly affected the surfactant physicochemical properties, allowing the clay extraction efficiency to be tuned. The interfacial recovery factor of the clays almost reached 100 percent under acidic (pH lower than 6) and neutral (pH 6-10) conditions, whereas it was negative under alkaline conditions (pH higher than 10), contrary to expectations. To elucidate the mechanisms involved in the particle flotation process for each of the pH conditions, the bulk and foam phases were analyzed. The effects of electrostatic interactions between the solutes and multiscale structure on the clay extraction behavior were investigated by electrophoretic measurements, dynamic light scattering, small-angle neutron scattering, and image analysis. Based on these results, three flotation processes were found depending on pH range: surfactant foam fractionation at pH higher than 10; clay particle foam flotation at pH 6-10; and particle froth flotation at pH lower than 6.
