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首页> 外文期刊>Chemistry: A European journal >Bifunctional Cyclam-Based Ligands with Phosphorus Acid Pendant Moieties for Radiocopper Separation: Thermodynamic and Kinetic Studies
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Bifunctional Cyclam-Based Ligands with Phosphorus Acid Pendant Moieties for Radiocopper Separation: Thermodynamic and Kinetic Studies

机译：双功能环基的配体与磷酸侧链的放射性铜分离：热力学和动力学研究

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摘要

Two macrocyclic ligands based on cyclam with trans-disposed N-methyl and N-(4-aminobenzyl) substituents as well as two methylphosphinic (H(2)L1) or methylphosphonic (H(4)L2) acid pendant arms were synthesised and investigated in solution. The ligands form stable complexes with transition metal ions. Both ligands show high thermodynamic selectivity for divalent copper over nickel(II) and zinc(II)K(CuL) is larger than K(Ni/ZnL) by about seven orders of magnitude. Complexation is significantly faster for the phosphonate ligand H(4)L2, probably due to the stronger coordination ability of the more basic phosphonate groups, which efficiently bind the metal ion in an out-of-cage complex and thus accelerate its in-cage binding. The rate of Cu-II complexation by the phosphinate ligand H(2)L1 is comparable to that of cyclam itself and its derivatives with non-coordinating substituents. Acid-assisted decomplexation of the copper(II) complexes is relatively fast ((1/2)=44 and 42s in 1M aq. HClO4 at 25 degrees C for H(2)L1 and H(4)L2, respectively). This combination of properties is convenient for selective copper removal/purification. Thus, the title ligands were employed in the preparation of ion-selective resins for radiocopper(II) separation. Glycidyl methacrylate copolymer beads were modified with the ligands through a diazotisation reaction. The separation ability of the modified polymers was tested with cold copper(II) and non-carrier-added Cu-64 in the presence of a large excess of both nickel(II) and zinc(II). The experiments exhibited high overall separation efficiency leading to 60-70% recovery of radiocopper with high selectivity over the other metal ions, which were originally present in 900-fold molar excess. The results showed that chelating resins with properly tuned selectivity of their complexing moieties can be employed for radiocopper separation.
机译：合成并研究了两个基于环素的大环配体，它们具有转置的N-甲基和N-（4-氨基苄基）取代基以及两个甲基次膦酸（H（2）L1）或甲基膦酸（H（4）L2）酸侧链在解决方案中。配体与过渡金属离子形成稳定的络合物。两种配体对二价铜在镍（II）和锌（II）K（CuL）上的热力学选择性都高，比K（Ni / ZnL）大七个数量级。膦酸酯配体H（4）L2的络合显着更快，这可能是由于更碱性的膦酸酯基团具有更强的配位能力，可以有效地结合笼外复合物中的金属离子，从而加速其在笼内的结合。次膦酸酯配体H（2）L1的Cu-II络合速率可与Cyclam本身及其具有非配位取代基的衍生物相媲美。铜（II）配合物的酸辅助解络速度相对较快（分别在25°C的H（2）L1和H（4）L2的1M HClO4水溶液中（1/2）= 44和42s）。这些特性的组合方便了选择性铜的去除/纯化。因此，标题配体用于制备用于放射性铜（II）分离的离子选择性树脂。甲基丙烯酸缩水甘油酯共聚物珠通过重氮化反应用配体改性。在大量过量的镍（II）和锌（II）的存在下，用冷铜（II）和未添加载体的Cu-64测试了改性聚合物的分离能力。实验显示出较高的总分离效率，导致放射性铜的回收率达到60-70％，并且与其他金属离子相比具有较高的选择性，而其他金属离子最初的摩尔过量为900倍。结果表明，可以通过适当调节其络合部分的选择性螯合树脂来进行放射性铜的分离。

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