Nanocellulose hydrogels formed via crystalline transformation from cellulose I to II and subsequent freeze cross-linking reaction

Sekine, Yurina; Nankawa, Takuya; Hiroi, Kosuke; Oba, Yojiro*; Nagakawa, Yoshiyasu*; Sugita, Tsuyoshi; Shibayama, Yuki; Ikeda-Fukazawa, Tomoko*

Carbohydrate Polymers, 327, p.121538_1 - 121538_11, 2024/03

https://doi.org/10.1016/j.carbpol.2023.121538

We describe non-toxic, tough nanocellulose (NC) hydrogels formed from chemically unmodified NC by cellulose crystalline transformation and subsequent freeze cross-linking reaction. Using low-concentration NaOH and freezing together induced the crystalline transformation of NC from cellulose I to II via freeze concentration. After the crystalline transformation, cross-linking between the NC and CA in the freeze concentration layer (FCL) provided a strong NC network structure, forming NC hydrogels with high mechanical strength. The freeze-cross-linked NC hydrogel easily retained powder adsorbents in its inner space by mixing the NC-NaOH sol and the powder, and the hydrogel showed high removal efficiency for heavy metals. The results highlight the versatility of chemically unmodified celluloses in developing functional materials, suggest possible practical applications.

Conversion of clay minerals to photocatalysts for Cr reduction and salicylic acid decomposition

Sugita, Tsuyoshi; Mori, Masanobu*; Shimoyama, Iwao

Applied Clay Science, 243, p.107074_1 - 107074_8, 2023/10

https://doi.org/10.1016/j.clay.2023.107074

We have investigated the conversion of biotite, a subgroup of clay minerals, into photocatalysts by heat treatment with CaCl. The reaction products obtained after heat treatment were examined in terms of composition, structure, and photocatalytic activity against Cr and salicylic acid (SA). When mixtures of biotite and CaCl were heated at temperatures up to 600C, the biotite crystal structure was retained, whereas a phase transformation from biotite to octahedral wadalite crystals occurred upon heating to 700C. The photocatalytic reduction rate of Cr per unit surface area and the photocatalytic degradation efficiency of SA increased significantly with increasing treatment temperature. Even the samples that retained the biotite structure after heat treatment displayed some photocatalytic activity, suggesting that this method may also be suitable for preparing photocatalysts from other common natural materials.

Microscopic structural changes during the freeze cross-linking reaction in carboxymethyl cellulose nanofiber hydrogels

Miura, Daisuke*; Sekine, Yurina; Nankawa, Takuya; Sugita, Tsuyoshi; Oba, Yojiro; Hiroi, Kosuke; Ozawa, Tatsuhiko

Carbohydrate Polymer Technologies and Applications (Internet), 4, p.100251_1 - 100251_9, 2022/12

https://doi.org/10.1016/j.carpta.2022.100251

The reaction mechanism of carboxymethyl cellulose nanofiber (CMCF) hydrogel formed by freeze-crosslinking was investigated. We succeeded in observing the hierarchical structural changes during the freeze-crosslinking reaction. Freeze-crosslinked CMCF hydrogels exhibited a characteristic hierarchical alignment structure from the angstrom to micrometer scale that differed from normal cross-linked CMCF hydrogels produced by a conventional method without freezing. It was shown that the characteristic hierarchical structure contributes the excellent mechanical properties of freeze-crosslinked CMCF hydrogels.

Carbonated nanohydroxyapatite from bone waste and its potential as a super adsorbent for removal of toxic ions

Sekine, Yurina; Nankawa, Takuya; Yamada, Teppei*; Matsumura, Daiju; Nemoto, Yoshihiro*; Takeguchi, Masaki*; Sugita, Tsuyoshi; Shimoyama, Iwao; Kozai, Naofumi; Morooka, Satoshi

Journal of Environmental Chemical Engineering, 9(2), p.105114_1 - 105114_12, 2021/04

https://doi.org/10.1016/j.jece.2021.105114

Remediating toxic ion contamination is crucial for protecting human health and the environment. This study aimed to provide a powerful strategy for effectively utilizing bone waste from the food production and preparation industries for removal of toxic ions. Here, we show that immersing pig bone in NaHCO solution produced a carbonated nanohydroxyapatites (C-NHAP). The C-NHAP exhibited high adsorptivity for Sr, Cd, Pb, and Cu. The strontium adsorptivity was about 250 and 4,500 times higher than that of normal bone and synthetic HAP, respectively. The C-NHAP is an eco-friendly, high-performance material that is simple to prepare and should be useful for tackling problems of food waste disposal and environmental pollution.

Eco-friendly carboxymethyl cellulose nanofiber hydrogels prepared via freeze cross-linking and their applications

Sekine, Yurina; Nankawa, Takuya; Yunoki, Shunji*; Sugita, Tsuyoshi; Nakagawa, Hiroshi; Yamada, Teppei*

ACS Applied Polymer Materials (Internet), 2(12), p.5482 - 5491, 2020/12

https://doi.org/10.1021/acsapm.0c00831

We developed a cross-linking method using freeze concentration and used it to synthesize a new type of carboxymethyl cellulose nanofiber (CMCF) hydrogel with high compressive strength ( 80 MPa) and high compressive recoverability. The hydrogels were prepared by adding an aqueous solution of citric acid (CA) to a frozen CMCF sol and then thawing the sol. The reaction between the freeze-concentrated CMCF and CA created a rigid porous structure that reflected the ice crystal structure. Their cross-linked structure has a high stability to compressive stress. Bentonite was immobilized on a CMCF hydrogel by adding bentonite to the CMCF sol before freeze cross-linking. The CMCF-bentonite hydrogel showed high adsorptivity for chemical dyes. The physically cross-linked CMCF hydrogels are non-toxic, metal-free, and simple to prepare, and thus they may be useful as sustainable materials in various fields.

Extraction performance of a fluorous phosphate for Zr(IV) from HNO solution; Comparison with tri--butyl phosphate

Ueda, Yuki; Kikuchi, Kei; Sugita, Tsuyoshi; Motokawa, Ryuhei

Solvent Extraction and Ion Exchange, 37(5), p.347 - 359, 2019/07

https://doi.org/10.1080/07366299.2019.1638015

We have newly-designed fluorous phosphate(TFP) for the effective Zr(IV) ion extractant as an alternative extractant against the conventional organic phosphate, tri--butyl phosphate(TBP). Zr(IV) ion extraction system using the TBP has many problems such as the formation of the third phase during liquid-liquid extraction. Here, we develop the fluorous extraction system based on the TFP-perfluorohexane for the Zr(IV) ion extraction to improve the Zr(IV) ion extraction system with an effective extractability and without the third phase formation. Our main findings were that the significant high extraction performance of the TFP for Zr(IV) ion as compared with TBP, and the origins of the high extraction performance of the TFP are related to the water and HNO contents in the fluorous phase and the stability of the complex, Zr(No)(TFP).

Extraction ability of 4-benzoyl-3-phenyl-5-isoxazolone towards 4f-ions into ionic and molecular media

Atanassova, M.*; Okamura, Hiroyuki; Eguchi, Ayano; Ueda, Yuki; Sugita, Tsuyoshi; Shimojo, Kojiro

Analytical Sciences, 34(8), p.973 - 978, 2018/08

https://doi.org/10.2116/analsci.18P166

The distribution constants of 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) and deprotonated one (PBI) between hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([CCim][TfN]) and aqueous phases were determined, together with the acid-dissociation constant of HPBI. The solvent extraction of three selected lanthanoid ions (La, Eu, and Lu) with HPBI from aqueous nitrate phase into [CCim][TfN] has been investigated. Application of the ionic liquid as the extracting phase greatly enhanced the extraction performance of HPBI for lanthanoid ions compared with that in the chloroform system. The composition of the extracted species was established to be anionic tetrakis entities, Ln(PBI), for light, middle, and heavy lanthanoid ions in an ionic environment.

Enhanced aqueous adsorption and photodecomposition of anionic organic target by amino group-modified TiO as anionic adsorptive photocatalyst

Sugita, Tsuyoshi; Kobayashi, Kenichi*; Kobayashi, Kentaro*; Yamazaki, Taiki*; Fujii, Kengo*; Itabashi, Hideyuki*; Mori, Masanobu*

Journal of Photochemistry and Photobiology A; Chemistry, 356, p.71 - 80, 2018/04

https://doi.org/10.1016/j.jphotochem.2017.12.025

Photocatalysts shows high redox property only by light irradiation. However, the reaction performance is lowered in aqueous phase due to the low contact efficiency between catalyst and targets. In this study, to enhance aqueous adsorption and photodecomposition of anionic organic target, we developed an amino functional-based spacer (3-[2-(2- aminoethylamino)ethylamino]propyl-trimethoxysilane, DETA), and used it to modify TiO. The modified catalyst with positively charged amino groups could enhance the adsorption and photodecomposition of anionic organic targets.

Pretreatment method in FIA by solvent extraction and the application possibility of novel solvent extraction method

Sugita, Tsuyoshi

Journal of Flow Injection Analysis, 33(1), p.39 - 40, 2016/06

http://jafia.kyushu-u.ac.jp/japanese/jfia/contents/33_1/HP/JFIA33(1)(2016)PP.39.pdf

A novel solvent extraction way, emulsion flow (EF) method, has been developed at JAEA. EF method achieves both good emulsion formation and quick phase separation only by solution sending. In this report, I referred Flow Injection Analysis (FIA) using solvent extraction as a preprocessing technique and introduced an outline of the EF method as such. Furthermore, I mentioned the application possibility of the EF method to the preprocessing in FIA with its advantage for extracting and concentrating a trace component from a large-volume sample.

Horonobe Underground Research Laboratory Project; Research and development plan (H22-H26)

Iwatsuki, Teruki; Sato, Haruo; Nohara, Tsuyoshi; Tanai, Kenji; Sugita, Yutaka; Amano, Kenji; Yabuuchi, Satoshi; Oyama, Takuya; Amano, Yuki; Yokota, Hideharu; et al.

JAEA-Research 2011-009, 73 Pages, 2011/06

JAEA-Research-2011-009.pdf:4.41MB

The research and development plan in Horonobe Underground Research Laboratory are summarized according to the 2nd Midterm Plan till 2014 fiscal year of JAEA. In this midterm, galleries and the infrastructures for the research and development up to the depth of 350 m are constructed by Private Financial Initiative (PFI). Additionally Phase 3: Operation phase at the galleries begins in parallel to Phase 2: Construction phase. In these phases various research and development including collaboration with other institutes are conducted at the galleries. Generallic applicable techniques on the subject of the investigation of geological environment, facility construction in deep underground and the reliability of geological deposal are developed during the phase. The feasibility and reliance of various technologies concerning geological disposal is demonstrated by widely opening the outcome to the public in the society.