アミノカルボン酸を配位子とするキレート樹脂の高機能化設計  [in Japanese] Design for Functionalization of Chelating Resins Having Aminocarboxylic Acids as Ligands  [in Japanese]

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Abstract

アミノカルボン酸型キレート樹脂における錯形成能,吸脱着速度及び元素選択性の改善を目指し,各設計因子の捕捉特性への影響を精査した.基材樹脂の親水化及びスペーサを介して配位子の導入により,配位子本来の錯安定度定数の序列と一致した捕捉特性が得られた.この知見を基に,カルボキシメチル化ポリエチレンイミンを配位子とするキレート樹脂を開発した.多座配位が可能な官能基構造の採用により捕捉可能pH範囲を拡大すると共に,アルカリ土類金属元素を捕捉しないという特徴的な捕捉機能を達成した.このキレート樹脂を環境水や尿中の金属元素の固相抽出に適用したところ,アルカリ金属元素及びアルカリ土類金属元素の妨害を受けずに対象金属元素を効率良く抽出可能であった.また,カルボキシメチル化ポリエチレンイミンをレーヨンと混合紡糸した繊維状金属元素吸着剤も開発し,上記特徴的捕捉機能が繊維状金属元素吸着剤においても発現することを確認した.

The design factors for chelating resins were evaluated in detail using a chromatographic method to improve the complexation abilities, the adsorption/desorption equilibrium and element selectivities on chelating resins. The adsorption properties on the chelating resins were drastically improved by adopting a hydrophilic base matrix and a spacer arm. A good correlation was obtained between the retention factors of rare-earth elements and the stability constants of the ligand on the chelating group immobilized. In consideration of these results, novel polyaminocarboxylic acid-type chelating resins were designed. They were synthesized by partial carboxymethylation of oligo-/polyethyleneimine that was immobilized onto the hydrophilic base matrix. Further, an unique element exclusion mechanism was added by introducing positive sites into the ligands. Consequently, the adsorption pH range was expanded by introducing ligands having a multidentate ligand, and alkaline and alkaline earth elements were scarcely retained. On the other hand, the recoveries under acidic conditions for molybdenum and vanadium, which form oxo-acid in water, were reinforced by the ion-exchange interaction with the positive site. These chelating resins were applied to the solid-phase extraction of trace metal elements in environmental water and biological fluid, and the target metal elements could be effectively extracted without any interferences of coexisting elements, such as alkaline and alkaline earth elements. Furthermore, chelate fiber was developed by a wet-spining method mixed with rayon and a macromolecule polyaminocarboxylic acid compound. However, despite the mixed spining into rayon, the element adsorption characteristics on the polyaminocarboxylic acid-type chelating fiber mentioned above was completely preserved. These chelating materials having unique element adsorption characteristics in this studies will contribute to improving of the measurement accuracy and precision in the element analyses.

Journal

  • BUNSEKI KAGAKU

    BUNSEKI KAGAKU 64(11), 811-819, 2015

    The Japan Society for Analytical Chemistry

Codes

  • NII Article ID (NAID)
    130005129313
  • NII NACSIS-CAT ID (NCID)
    AN00222633
  • Text Lang
    JPN
  • ISSN
    0525-1931
  • NDL Article ID
    026916805
  • NDL Call No.
    Z17-9
  • Data Source
    NDL  J-STAGE 
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