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上田 祐生; 小林 徹; 中村 聡志; 伴 康俊; 金田 結依; 生田目 望; Micheau, C.; 徳永 紘平; 中部 倫太郎; 金子 政志*; et al.
Langmuir, 42(1), p.1613 - 1626, 2026/01
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)溶媒抽出系における金属イオンの選択性を支配する構造要因の理解は、高レベル放射性廃棄物の分離変換プロセスを高度化する上で極めて重要である。本研究では、代表的なランタニドとしてランタン(La)とネオジム(Nd)を対象に、ニトリロトリアセトアミド(NTAamide)抽出剤のアルキル側鎖分岐度が抽出挙動に及ぼす影響を系統的に調査した。分子量は同一だがアルキル分岐度の異なる4種類の抽出剤(いずれもアミド鎖の1本が炭素数8)を用い、硝酸濃度に対する分配比を測定した。さらに、LaおよびNdの局所配位構造を拡張X線吸収微細構造(EXAFS)で解析し、有機相における超分子的凝集挙動を小角中性子散乱(SANS)で評価した。その結果、EXAFS解析から、LaおよびNdの内圏配位環境はアルキル分岐度の影響をほとんど受けないことが明らかとなった。一方、SANS解析からは、分岐の少ない抽出剤ほど低硝酸濃度で大きな凝集体を形成し、特にNdにおいては凝集体形成が抽出を促進し、難溶性錯体の沈殿を防いでいることが示された。これらの結果は、アルキル分岐度が超分子的凝集挙動を強く制御し、それが抽出挙動を支配していることを示している。本研究は、ランタニドおよびアクチニドの溶媒抽出において、選択性向上のための新しい設計概念として「ナノスケール構造制御」の可能性を示すものである。
柴田 基樹*; 竹中 幹人*; 元川 竜平; 熊田 高之; 上田 祐生; 宮崎 司*; 中西 洋平*; 阿部 淳*; 岩瀬 裕希*; 柴山 充弘*; et al.
Polymer, 340, p.129203_1 - 129203_7, 2025/12
被引用回数：0 パーセンタイル：0.00(Polymer Science)The development of effective plastic degradation methods is crucial to address environmental pollution. Hydrothermal liquefaction using near-critical water is a promising technology, but the fundamental dissolution and decomposition mechanisms remain poorly understood. This study investigates the thermodynamics of a polystyrene (PS)/water system under near-critical conditions to elucidate this mechanism. We performed in situ small-angle neutron scattering (SANS) to observe the swelling of PS particles in deuterated water (D
O) at various temperatures under pressures of 10 MPa and 25 MPa. By applying the 
(FHS) theory to the swelling data, We quantitatively determined the Flory-Huggins interaction parameter as a function of temperature and pressure by applying the FHS theory to the swelling data. Based on these results, we constructed a phase diagram of the PS/DO system. The diagram reveals that miscibility increases with increasing pressure. This work provides a thermodynamical properties of water solutions of polymers under near-critical conditions for optimizing industrial hydrothermal recycling processes.
吉田 美里*; 新井 健悟*; 中川 大輝*; 堀川 喜樹*; 岩瀬 裕希*; 熊田 高之; 元川 竜平; 四方 俊之*
Biomacromolecules, 26(11), p.8332 - 8342, 2025/11
被引用回数：0 パーセンタイル：0.00(Biochemistry & Molecular Biology)Structure and conformation of hydroxypropylmethyl cellulose (HpMC) samples (DS = 1.8 and MS = 0.15) with narrow molar mass distributions of Mw/Mn 
1.3 at Mw of 210, 310 and 440 kg/mol dissolved in aqueous solution were investigated using static light scattering (SLS) and small angle neutron scattering (SANS) techniques to cover a wide scattering vector (q) range. The q dependencies of the concentration-reduced excess Rayleigh ratios via SLS at the extrapolated zero-concentration were smoothly linked with those of the concentration reduced excess scattering intensities via SANS using the same factor for all the HpMC samples. The linked scattering intensity curves were reasonably described with the form factor of monodisperse rod particles. Moreover, broad interference scattering peaks possibly exist at q= 0.042 nm
in the linked scattering curves, suggesting the presence of a periodicity of ~150 nm in the rod-like particles formed by HpMC molecules.
戸田 賀奈子*; 元川 竜平; 斉藤 拓巳*
Journal of Physical Chemistry C, 129(36), p.16261 - 16271, 2025/09
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)The development of the nano-scale pore size distribution of metakaolin-based geopolymers (MKGPs) was evaluated by the application of the small-angle neutron scattering (SANS), followed by the polydisperse spherical (PDSP) model application, where the modelled outputs were then deconvoluted by bimodal log-normal distribution fitting. Small pores, with a log-normal distribution modal value of 2.5 nm, immediately formed after mixing, with a decrement in the pore volume as a function of time. Larger pore size distribution with log-normal distribution modal values larger than 4nm, required an induction period, indicating the larger pore size distribution evolution corresponds to the pores as aluminosilicate cluster gel interstices. The nano-scale pore size distribution development varied by the curing temperature and the type of activators, which were evaluated in this study. The initial pore evolution of the MKGPs may be the critical step in determining the nano-sized porosity of the MKGPs, which characterizes the diffusive property of the material, such as the De of HDO.
渡邉 拓*; 前島 結衣*; 上田 祐生; 元川 竜平; 高畠 愛*; 武田 真一*; 不動寺 浩*; 岸川 圭希*; 桑折 道済*
Langmuir, 41(34), p.22762 - 22773, 2025/09
被引用回数：1 パーセンタイル：0.00(Chemistry, Multidisciplinary)メラニン粒子の集合構造、つまりメラニンポリドーパミン(PDA)層で被覆されたコロイド粒子は、鮮やかな構造色を作り出す。PDA層の厚さは粒子の配列や光学特性に影響を与えるが、その根本的なメカニズムについては議論が続いている。我々は、PDAの水膨潤特性が、溶液中でのこれらの粒子の分散と凝集を支配する重要な要因であることを実証した。乾燥状態と湿潤状態の詳細な比較から、PDA層は水分子を容易に吸収し、厚い層では著しい膨潤を引き起こすことが明らかになった。PDA層の膨潤は、粒子が水中で分散したままか、部分的に凝集したままかを決定し、最終的には水が蒸発した後の乾燥状態での粒子配列を制御した。これらの知見は、コロイド粒子の自己組織化に関する洞察を提供し、周期的な粒子秩序を調整する戦略を提供する。この特徴は、光学技術やセンシング技術における様々な応用にとって極めて重要である。
Guerinoni, E.*; Zemb, T.*; 元川 竜平; 上田 祐生; 青柳 登; Pellet-Rostaing, S.*; Dourdain, S.*
Journal of Physical Chemistry B, 129(32), p.8210 - 8217, 2025/08
被引用回数：0 パーセンタイル：0.00(Biophysics)Liquid-liquid extraction of uranium involves an acidic aqueous phase in contact with an oil phase containing aliphatic amines and a linear alkane. Excess electrolyte in the oil phase leads to a third phase, hindering metal ion extraction and stripping. We determine the largest admissible extractant concentration (LOC) before macroscopic phase separation. Using small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS), we analyze the microstructure of the phases. In all aliphatic diluents, the third phase consists of weak water-in-oil (w/o) aggregates with interdigitated hydrocarbon chains. Even after centrifugation, SANS detects residual deuterated solvent molecules. A fraction of these w/o aggregates contains uranium(VI) cations (U-loaded aggregates), which exhibit stronger attractive interactions than unloaded aggregates. This leads to the segregation of U-loaded aggregates into large clusters, detected as a Porod-type decay in SAXSbut absent in SANS at a low q-values.
-butadiene) reinforced by carbon blackWatanabe, Yuki*; 熊川 大幹*; Karitani, Shu*; 井上 正志*; 岩蕗 仁*; 中西 洋平*; 柴田 基樹*; 元川 竜平; 杉田 剛; 上田 祐生; et al.
Macromolecules, 58(16), p.8641 - 8648, 2025/08
被引用回数：0 パーセンタイル：0.00(Polymer Science)We investigated how the particle size of carbon black (CB) affects the reinforcement of CB to vulcanized poly(styrene-co-butadiene) (SBR) in the glassy region. When the average diameter of CB d is larger than 100 nm, the enhancement of modulus can be expressed by the Eshelby/Mori-Tanaka model, which agrees with the results obtained for an SBR/silica system. On the other hand, at d 100nm, the volume fraction dependence of the enhancement becomes stronger than the theory's prediction. The scattering studies on the SBR/CB systems revealed that the aggregates of CB at d 100nm consist of densely packed CB, while the aggregates of CB at d 
100nm exhibit branch structures. At d 100nm, the voids or the occluded region in the packed CB increase the volume fraction, resulting in a stronger volume fraction dependence of the enhancement.
河合 優作*; Park, J.*; 元川 竜平; 以倉 崚平*; 村山 駿介*; 山岡 賢司*; 藤井 義久*; 池本 夕佳*; 田中 賢*; 松葉 豪*; et al.
ACS Applied Polymer Materials (Internet), 7(12), p.7767 - 7776, 2025/06
被引用回数：1 パーセンタイル：49.37(Materials Science, Multidisciplinary)The material properties of polymeric materials in aqueous environments are significantly influenced by water content. It is widely recognized that polymeric materials become more brittle with increased water content. However, the specific relationship between hydration levels and polymer chains has not been fully elucidated, leaving many uncertainties. Conversely, intermediate water (IMW), which refers to adsorbed water, plays an active role in influencing the biocompatibility and antifouling properties of these materials. In this study, we examined the correlation between IMW and toughness (Gf) / Youngs modulus (E). We synthesized dual cross-network (DC) elastomers through the bulk copolymerization of cyclodextrin (CD) monomers and vinyl monomers in the presence of movable cross-linked elastomers. The resulting DC elastomers exhibited both high Gf and high E. We used poly(2-methoxyethyl acrylate) (PMEA) as the primary polymer and poly(N,N-dimethyl acrylamide) (PDMAA) as the secondary polymer. The DC materials were formulated as DC(MEA-DMAA)(100-w:w)(Wc), where w and Wc represent the weight percentage of the secondary polymer (PDMAA) and the water content, respectively. The mechanical properties of the DC materials mostly decreased with increasing amounts of the secondary polymer. However, DC(MEA-DMAA)(90:10)(22), which contained 10 wt percent of PDMAA, exhibited the highest Gf and E among all samples. Differential scanning calorimetry (DSC) measurements indicated the presence of IMW in DC(MEA-DMAA)(90:10)(22). We propose that the IMW in this sample facilitates the formation of crosslinks between polymer chains and water molecules, contributing to the observed enhancements in E and Gf.
-nonyl N,N-dimethylammonio)-propyl sulfate, present in isotropic solutions above its upper critical solution temperature丹治 珠緒*; 楠 裕翔*; 中川 太一; 高瀬 つぎ子*; 上田 祐生; 元川 竜平; Hinze, W. L.*; 高貝 慶隆*
Langmuir, 41(21), p.13184 - 13191, 2025/06
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)The thermosensitive zwitterionic surfactant, C
APSO
, in solution displays a liquid-liquid miscibility gap exhibiting an upper critical solution temperature (UCST) in contrast to the lower critical temperature as is characteristic of nonionic surfactants. In this study, the micellar and aggregational properties of this surfactant in its homogeneous isotropic one phase region above the UCST was examined using surface tension and small-angle neutron scattering (SANS) measurements. The critical micelle concentration (CMC) of CAPSO was determined in both HO and DO at 40 and 70
C as well as the cloud point temperature determined over a surfactant concentration range of 0.05-0.70 M. The CMC values were in the range of 48-55 mM (40C) and 61-65 mM (70C), respectively. The SANS data was analyzed using a core-shell model in which the CAPSO is represented by a nonyl hydrophobic core and polar [(N,N-dimethylammonio)-propylsulfate] headgroup shell. Results revealed that the CAPSO micelle aggregates are spherical in shape with a core diameter of 2.56 nm and shell thickness of 2.28 nm and an aggregation number of 30 at 40C. The data at 70C indicated that the aggregates were slightly larger in size, i.e., core diameter of 2.70 nm and shell thickness of 2.52 nm with an aggregation number of 35. At a fixed surfactant concentration, the aggregation number and size slightly decreased with a decrease in temperature from 70 to 40C.
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, 18(10), p.e202402034_1 - e202402034_13, 2025/05
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.; 元川 竜平
ファインケミカル, 54(5), p.53 - 60, 2025/05
持続可能な社会を実現するためには金属資源のリサイクルが重要である。高濃度の金属イオンを取り扱う抽出操作では、プロセスの安全な運転を阻害する油相の相分離(第三相の生成)が長年の課題であった。本稿では、フルオラス化合物の強力な疎水性を利用した、第三相を生成させない新たな抽出系開発におけるこれまでの成果をまとめた。
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。
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：2 パーセンタイル：25.21(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：2 パーセンタイル：25.21(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：9 パーセンタイル：91.92(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：5 パーセンタイル：69.50(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：6 パーセンタイル：59.68(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：4 パーセンタイル：60.55(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.
