Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
Chemistry. 2011 Feb 7;17(6):1818-27. doi: 10.1002/chem.201002372. Epub 2011 Jan 5.
Seven water-soluble, tetradentate bis(3-hydroxy-N-methyl-pyridin-2-one) (bis-Me-3,2-HOPO) ligands were synthesized that vary only in linker geometry and rigidity. Solution-phase thermodynamic measurements were conducted between pH 1.6 and pH 9.0 to determine the effects of these variations on proton and uranyl cation affinity. Proton affinity decreases by introduction of the solubilizing triethylene glycol group as compared to unsubstituted reference ligands. Uranyl affinity was found to follow no discernable trends with incremental geometric modification. The butyl-linked 4 li-Me-3,2-HOPO ligand exhibited the highest uranyl affinity, consistent with prior in vivo decorporation results. Of the rigidly-linked ligands, the o-phenylene linker imparted the best uranyl affinity to the bis-Me-3,2-HOPO ligand platform.
七种水溶性、四齿双（3-羟基-N-甲基-2-吡啶酮）（双-Me-3,2-HOPO）配体被合成，这些配体仅在连接体的几何形状和刚性上有所不同。在 pH 值 1.6 到 9.0 之间进行了溶液相热力学测量，以确定这些变化对质子和铀酰阳离子亲和力的影响。与未取代的参考配体相比，引入增溶的三乙二醇基团会降低质子亲和力。发现铀酰亲和力随着几何结构的增量修饰没有明显的趋势。带有丁基连接的 4 li-Me-3,2-HOPO 配体表现出最高的铀酰亲和力，与先前的体内去毒化结果一致。在刚性连接的配体中，邻苯二酚连接体赋予双-Me-3,2-HOPO 配体平台最佳的铀酰亲和力。
