Ligand Design Principle for Molecular Recognition and the Application to Separation Chemistry

分子识别配体设计原理及其在分离化学中的应用

• 批准号: 07454201
• 负责人: MATSUI Masakazu
• 金额: $ 4.99万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454201/
• 关键词: molecular recognition; selective complex formation; bite size; beta-diketones; polypyrazolyl borate; solvent extraction; separation chemistry; イオンサイズ認識; 配位子間の歪み; 配位子内の歪み; 分離機能; 配位子設計

Ion size recognition with conventional organic ligands was proved to be governed by several factors. The first is based on the distance between the donor atoms, that is, the bite size. Bite size in a 6-membered ring such as beta-diketone also governs not only the selectivity, but the acidity of the ligand. The second factor governing ion size recognition is the chelate ring rigidity. The third is the unstabilization of chelates based on the inter ligand contact, which is caused by bulky terminal group of the ligand.The application of the three requirments to the separation of rare earth and Group 13 metal ions was performed : The efficient extraction-separation of each metal ion in Group 13 by bulky 4-substituted acylpyrazolones confirms the validity of the factors on the role of the bite size and steric factors. The above results thus have proved the possibility of designing ligands of high selectivity for target metal ions by controlling the bite size of the ligand and/or creating intra- and interligand contacts.

传统有机配体对离子大小的识别受到多种因素的影响。第一种是基于施主原子之间的距离，也就是咬合大小。6元环(如β-二酮)中的咬合大小不仅控制着配体的选择性，而且还决定着配体的酸性。影响离子尺寸识别的第二个因素是螯合环的刚性。三是由于配体末端基团较大，导致配体间接触形成的络合物不稳定，将这三个条件应用于稀土离子和第13族金属离子的分离：4-取代基团大的4-取代吡唑酮对第13族金属离子的有效萃取分离证实了影响稀土离子的大小和空间因素的有效性。因此，上述结果证明了通过控制配体的咬合大小和/或建立配体内和配体间的接触来设计对目标金属离子具有高选择性的配体的可能性。

项目成果

Quyen Thi Hanh Le: "Highly Acidic Extractant, 4-Benzolyl-3-phenyl-5-isoxazolone : The Svnergistic Extraction of Alkaline Earth and Alkali Metals Combined with Trioctylphosphine Oxide or Bis (diphenylphosphinyl) methane" Bull. Chem. Soc. Jpn.68. 2867-2873

Quyen Thi Hanh Le：“高酸性萃取剂 4-苯甲基-3-苯基-5-异恶唑酮：与三辛基氧化膦或双（二苯基膦基）甲烷结合对碱土和碱金属的协同萃取”公报。

Quyen Thi Hanh Le: "Decisive Role of a Phenyl Group at the α-position of Benzoylacetone in the Solvent Extraction of Al^<3+> and In^<3+>" J. Chem. Soc., Chem. Commun.2271-2272 (1995)

Quyen Thi Hanh Le：“苯甲酰丙酮 α 位上的苯基在 Al^<3+> 和 In^<3+> 溶剂萃取中的决定性作用”J. Chem.，Chem.2271。 -2272 (1995)

松井正和: "イオンサイズ認識のための配位子設計" 分析化学. 45. 209-223 (1996)

Masakazu Matsui：“离子大小识别的配体设计”分析化学 45. 209-223 (1996)。

Osamu Shirai: "Ion Transfer through a Liquid Membrane or a Bilayer Lipid Membrane in the Presence of Sufficient Electrolytes" J. Electroanal. Chem.389. 61-70 (1995)

Osamu Shirai：“在存在足够电解质的情况下通过液膜或双层脂质膜的离子转移”J. Electroanal。

藤野 治: "ICP質量分析法によるアパタイト鉱物中の希土類元素、トリウムおよびウランの定量" 日本化学会誌. 7. 650-655 (1996)

Osamu Fujino：“通过 ICP 质谱法测定磷灰石矿物中的稀土元素、钍和铀”日本化学学会杂志 7. 650-655 (1996)。