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筋田 涼太*; 青木 裕之; 竹中 幹人*; 大内 誠*; 寺島 崇矢*
ACS Macro Letters (Internet), 13(6), p.747 - 753, 2024/06
Herein, we report the water-assisted self-assembly of alternating copolymers bearing imidazolium cations and hydrophobic groups to create water-compatible and nanostructured materials. The copolymers efficiently absorbed water into the cationic segments from the outer environments, depending on the relative humidity. The absorbed water serves as hydrophilic molecules to modulate the weight fraction of hydrophilic/hydrophobic units in the samples. Thus, the morphologies and domain spacing of the nanostructures can be controlled by not only the side chains, but also the amount of absorbed water. The self-assembly of the cationic copolymers, developed herein, afforded universal access to various morphologies, including lamella, gyroid, and cylinder, in addition to the precision control of the domain spacing at the 0.01 nm level.
O/HO vapor generator for contrast-variation neutron scattering有馬 寛*; 高田 慎一; 笠井 聡*; 大内 啓一*; 森川 利明*; 宮田 登*; 宮崎 司*; 青木 裕之; 岩瀬 裕希*; 廣井 孝介; et al.
Journal of Applied Crystallography, 56(6), p.1802 - 1812, 2023/12
被引用回数：0 パーセンタイル：0.02(Chemistry, Multidisciplinary)The contrast-variation technique in neutron scattering experiments plays a pivotal role in distinguishing partial structures within multi-component complexes, facilitating the elucidation of distinct sample constituents. This differentiation is achieved using different isotopes, namely hydrogen and deuterium, which possess varying neutron scattering characteristics. This study presents a novel vapor generator designed for neutron scattering experiments, enabling continuous control of the DO/HO ratio of the vapor. This feature is especially useful for contrast-variation studies. The generator features two saturators and four mass flow controllers, allowing for the rapid and independent generation of DO/HO vapors. Additionally, the incorporation of the two-temperature method ensures accurate dew point control within a margin of 
0.2
Cdp. This setup proves useful for conducting time-resolved experiments and can accelerate research on functional polymers, such as polymer electrolyte membranes for fuel cells, where water potential assumes critical importance.
筋田 涼太*; 今井 彩帆里*; 大内 誠*; 青木 裕之; 寺島 崇矢*
Macromolecules, 56(23), p.9738 - 9749, 2023/12
被引用回数：0 パーセンタイル：0.00(Polymer Science)Constructing ordered ionic nanostructures into bulk polymers and thin films is an important technique to create functional materials, such as polyelectrolytes and proton- and ion-conducting materials, for various applications. Herein, we report microphase separation of cationic homopolymers bearing alkyl ammonium bromides to create sub-4 nm lamellar materials, where an ionic phase is alternatingly layered with a hydrophobic alkyl phase and serves as a channel for water intercalation. We prepared cationic homopolymers with linear or branched alkyl pendants (octyl or 2-ethylhexyl group: C8-eicosyl or 2-octyldodecyl group: C20) via the free radical polymerization of 2-(dimethylamino)ethyl acrylate (DMAEA), followed by the quaternization of the polyDMAEA with corresponding alkyl bromides. The homopolymers carrying linear hexadecyl, octadecyl, and eicosyl groups were crystalline at room temperature, whereas the others were amorphous. The homopolymers bearing linear alkyl pendants longer than the decyl group or branched alkyl pendants larger than the 2-butyloctyl group formed lamellar structures by the self-assembly of the side chains. The domain spacing can be controlled between 2.5 and 3.7 nm by tuning the pendant structures and are smaller than that formed by the corresponding random copolymers. A cationic homopolymer bearing crystalline octadecyl groups maintained lamellar structures up to 
210 
C far beyond the melting temperature (50 C). The cationic homopolymer further formed a multilayered lamellar thin film on a silicon substrate, in which the cationic layers absorbed water under humid conditions and reversibly released the water therefrom in a N gas atmosphere.
今井 彩帆里*; 荒川 勝利*; 中西 洋平*; 竹中 幹人*; 青木 裕之; 大内 誠*; 寺島 崇矢*
Macromolecules, 55(20), p.9113 - 9125, 2022/10
被引用回数：3 パーセンタイル：34.93(Polymer Science)Microphase separation of copolymers is a key technique to produce polymer bulk materials or thin films with ordered nanostructures for applications in various research fields including nanotechnologies, electronic devices, among many others. Herein, we report water-assisted microphase separation of amphiphilic random copolymers bearing quaternary ammonium cations and hydrophobic alkyl or oleyl groups in the solid state and the thin films. We investigated the effects of sample preparation protocols and the hydrophobic pendants (a butyl group: C4 - octadecyl or oleyl group: C18), composition, and molecular weight of the copolymers on the microphase separation behavior. By annealing under humid conditions, the copolymers bearing alkyl groups longer than an octyl group (C8) formed sub-5 nm lamellar structures comprising cationic layers and hydrophobic layers. Water hardly remained in the resulting lamellar materials under ambient conditions. The domain spacing was controlled between 3.7 and 5.3 nm by tuning the length of the hydrophobic pendants and composition and was independent of the molecular weight and molecular weight distribution. The cationic random copolymers carrying amorphous hydrophobic pendants provided transparent or translucent polymer materials containing small lamellar structures. The random copolymers further formed multilayered lamellar thin films on silicon substrates by spin-coating the copolymer solutions, followed by a humid annealing process. The layered lamellae were directly observed as terrace structures with about 4-5 nm steps by atomic force microscopy.
Ikami, Takaya*; Watanabe, Yuki*; 小川 紘輝*; 竹中 幹人*; 山田 悟史*; 大内 誠*; 青木 裕之; 寺島 崇矢*
ACS Macro Letters (Internet), 10(12), p.1524 - 1528, 2021/12
被引用回数：8 パーセンタイル：50.84(Polymer Science)Making ordered nanostructures in polymers and their thin films is an important technique to produce functional materials. Herein, we report instant yet precise self-assembly systems of amphiphilic random copolymers to build multilayered lamellar structures in bulk materials and thin films. Random copolymers bearing octadecyl groups and hydroxyethyl groups induced crystallization-driven microphase separation via simple evaporation from the solutions to form lamellar structures in the solid state. The domain spacing was controlled in the range between 3.1 and 4.2 nm at the 0.1 nm level by tuning copolymer composition. Interestingly, just by spin-coating the polymer solutions onto silicon substrates, the copolymers autonomously formed thin films consisting of multilayered lamellar structures, where amorphous/hydrophilic parts and crystalline octadecyl domains are alternatingly layered from a silicon substrate to the air/polymer interface at regular intervals. The lamellar domain spacing was tunable by selecting hydrophilic pendants.
宮崎 司*; 宮田 登*; 有馬 寛*; 吉良 弘*; 大内 啓一*; 笠井 聡*; 津村 佳弘*; 青木 裕之
Langmuir, 37(32), p.9873 - 9882, 2021/08
被引用回数：5 パーセンタイル：35.86(Chemistry, Multidisciplinary)We investigated the structure of the crystalline adsorption layer of poly(vinyl alcohol) (PVA) in hot water by neutron reflectivity in two cases: when the adsorption layer is exposed on the substrate by leaching the upper bulk layer and when it is deeply embedded between a relatively thick PVA film and substrate. In both cases, the PVA adsorption layer consists of three layers on the Si substrate. The bottom layer, consisting of amorphous chains that are strongly constrained on the substrate, is not swollen even in hot water at 90C. The middle layer, consisting of amorphous chains that are much more mobile compared with those in the bottom layer, has no freedom to assume a crystalline form. Only the molecular chains in the top layer are crystallizable in the adsorption layer, leading to a heterogeneous layered structure in the film thickness direction. This layered structure is attributed to the crystallizable chains of PVA during the formation of the adsorption layer driven by hydrogen bonding. However, the structure and dynamics in the adsorption layer may differ in both cases because the molecular chains in the vicinity of the surface seem to be affected by surface effects even in the adsorption layer.
有馬 寛*; 宮田 登*; 吉田 鉄生*; 笠井 聡*; 大内 啓一*; Zhang, S.*; 宮崎 司*; 青木 裕之
Review of Scientific Instruments, 91(10), p.104103_1 - 104103_7, 2020/10
被引用回数：9 パーセンタイル：54.35(Instruments & Instrumentation)We developed a novel humidity control system for neutron reflectivity measurements based on the two-way gas-flow method that can generate up to 85% relative humidity (RH) within a temperature range of 5-85C. The system consists of a gas-flow-type humidity generator and a thermostatic sample chamber, each of which can independently control the temperature. The key features include rapid humidity response and long stable operation time. The humidity reaches equilibrium within 2 to 5 min during the humidity change, and the system exhibited acceptable stability over a three-day, nonstop experimental measurement duration, with a precision of 1% RH at 85C and 85% RH. The sample chamber is capable of measuring substrate samples with dimensions of up to 2-in. in diameter and 5-mm in thickness. We demonstrate the reflectivity data measured at a pulsed neutron facility, MLF BL17, in the Japan Proton Accelerator Research Complex. The combined use of this system with neutrons permits in situ, time-resolved studies of the swelling process of polyvinyl alcohol and adhesive materials.
Gd核異性体の寿命測定浅井 雅人; 林 裕晃*; 長 明彦; 佐藤 哲也; 乙川 義憲; 長江 大輔; 塚田 和明; 宮下 裕次*; 大内 裕之*; 泉 さやか*; et al.
no journal, ,
崩壊で励起される長寿命核異性体の半減期を、全吸収検出器を用いて測定する方法を新たに開発し、
Gd及び
GdのKアイソマーの半減期を初めて決定した。原子力機構タンデム加速器に設置されたオンライン同位体分離装置ISOLを用いて、短寿命中性子過剰核Eu及びEuを合成・分離し、Euの崩壊で放出される線や
線を全吸収測定した。検出された事象ごとに時間情報を付加して記録することで、100
秒以上の寿命を持つ核異性体の寿命測定を可能にした。
