Diallo Mamadou S, Arasho Wondwossen, Johnson James H, Goddard William A
Materials and Process Simulation Center, Beckman Institute 139-74, California Institute of Technology, Pasadena, California 91125, USA.
Environ Sci Technol. 2008 Mar 1;42(5):1572-9. doi: 10.1021/es0715905.
Chelating agents are widely employed in many separation processes used to recover uranyl [U(VI)] from contaminated aqueous solutions. This article describes an experimental investigation of the binding of U(VI) to poly(amidoamine) [PAMAM] and poly(propyleneimine) [PPI] dendrimers in aqueous solutions. We combine fluorescence spectroscopy with bench scale ultrafiltration experiments to measure the extent of binding and fractional binding of U(VI) in aqueous solutions of these dendrimers as a function of (i) metal-ion dendrimer loading, (ii) dendrimer generation, (iii) dendrimer core and terminal group chemistry, and (iv) solution pH and competing ligands (NO3-, PO4(3-), CO3(2-), and Cl-). The overall results of this study suggest that uranyl binding to PAMAM and PPI dendrimers in aqueous solutions involves the coordination of the UO2(2+) ions with the dendrimer amine, amide, and carboxylic groups. We find significant binding of U(VI) to PAMAM dendrimers in (i) acidic solutions containing up to 1.0 M HNO3 and H3PO4 and (ii) in basic solutions containing up to 0.5 M Na2CO3. However, no binding of U(VI) by PAMAM dendrimers is observed in aqueous solutions containing 1.0 M NaCl at pH 3.0. These results strongly suggest that PAMAM and PPI dendrimers can serve as high capacity and selective chelating ligands for U(VI) in aqueous solutions.
螯合剂广泛应用于许多用于从受污染水溶液中回收铀酰[U(VI)]的分离过程。本文描述了在水溶液中U(VI)与聚(酰胺胺)[PAMAM]和聚(丙烯亚胺)[PPI]树枝状大分子结合的实验研究。我们将荧光光谱与实验室规模的超滤实验相结合,以测量在这些树枝状大分子水溶液中U(VI)的结合程度和分数结合,作为以下因素的函数:(i)金属离子与树枝状大分子的负载量,(ii)树枝状大分子的代数,(iii)树枝状大分子的核心和末端基团化学性质,以及(iv)溶液pH值和竞争配体(NO3-、PO4(3-)、CO3(2-)和Cl-)。本研究的总体结果表明,在水溶液中铀酰与PAMAM和PPI树枝状大分子的结合涉及UO2(2+)离子与树枝状大分子的胺基、酰胺基和羧基的配位。我们发现U(VI)在(i)含有高达1.0 M HNO3和H3PO4的酸性溶液以及(ii)含有高达0.5 M Na2CO3的碱性溶液中与PAMAM树枝状大分子有显著结合。然而,在pH为3.0的含有1.0 M NaCl的水溶液中未观察到PAMAM树枝状大分子对U(VI)的结合。这些结果强烈表明,PAMAM和PPI树枝状大分子可作为水溶液中U(VI)的高容量和选择性螯合配体。