Role of Alkyl Chain Branching in the Self-Assembly of Nitrilotriacetamide-Based Lanthanide Extractants

Ueda, Yuki   ; Kobayashi, Toru ; Nakamura, Satoshi  ; Ban, Yasutoshi  ; Kaneta, Yui ; Nabatame, Nozomi; Micheau, C.; Tokunaga, Kohei   ; Nakabe, Rintaro; Kaneko, Masashi*; Motokawa, Ryuhei   

Understanding the structural factors governing the metal ions selectivity of solvent extraction systems is crucial for developing advanced processes for partitioning and transmutation of high-level radioactive waste. Here, we systematically investigated the effect of alkyl side-chain branching in nitrilotriacetamide (NTAamide) extractants on the extraction of lanthanum (La) and neodymium (Nd), chosen as representative lanthanides. Four extractants having each eight carbon atoms as one of the amide chains with identical molecular weights but different degrees of alkyl branching were examined. Distribution ratios were measured as a function of HNO concentration, and the local coordination structures of La and Nd were analyzed by extended X-ray absorption fine structure (EXAFS), while supramolecular aggregation in the organic phase was characterized by small-angle neutron scattering (SANS). EXAFS analysis revealed that the inner-sphere coordination environment of La and Nd was essentially unaffected by the degree of alkyl branching. In contrast, SANS results showed that extractants with fewer branched alkyl groups formed larger aggregates at low HNO concentrations, particularly in the case of Nd, where aggregation was found to facilitate extraction and prevent precipitation of poorly soluble complexes. These findings demonstrate that alkyl branching strongly influences supramolecular aggregation, which in turn governs extraction behavior. This work highlights the potential of nanoscale structural control as a new design concept for improving selectivity in lanthanide and actinide solvent extraction systems.