α-Aminobisphosphonate Copolymers Based on Poly(ε-caprolactone)s and Poly(ethylene glycol): A New Opportunity for Actinide Complexation.

Original α-aminobisphosphonate-based copolymers were synthesized and successfully used for actinide complexation. For this purpose, poly(α-chloro-ε-caprolactone- co -ε-caprolactone)- b -poly(ethylene glycol)- b -poly(α-chloro-ε-caprolactone- co -ε-caprolactone) copolymers were first prepared by ring-opening copolymerization of ε-caprolactone (εCL) and α-chloro-ε-caprolactone using poly(ethylene glycol) (PEG) as a macro-initiator and tin(II) octanoate as a catalyst. The chloride functions were then converted to azide moieties by chemical modification, and finally α-aminobisphosphonate alkyne ligand (TzBP) was grafted using click chemistry, to afford well-defined poly(αTzBPεCL- co -εCL)- b -PEG- b -poly(αTzBPεCL- co -εCL) copolymers. Three copolymers, showing different α-aminobisphosphonate group ratios, were prepared (7, 18, and 38%), namely, CP8, CP9, and CP10, respectively. They were characterized by 1 H and 31 P NMR and size exclusion chromatography. Sorption properties of these copolymers were evaluated by isothermal titration calorimetry (ITC) with neodymium [Nd(III)] and cerium [Ce(III)] cations, used as surrogates of actinides, especially uranium and plutonium, respectively. ITC enabled the determination of the full thermodynamic profile and the calculation of the complete set of thermodynamic parameter (Δ H , T Δ S , and Δ G ), with the K a constant and the n stoichiometry. The results showed that the number of cations sorbed by the functional copolymers logically increased with the number of bisphosphonate functions borne by the macromolecular chain, independently of the complexed cation. Additionally, CP9 and CP10 copolymers showed higher sorption capacities [21.4 and 34.0 mg·g -1 for Nd(III) and 9.6 and 14.3 mg·g -1 for Ce(III), respectively] than most of the systems previously described in the literature. CP9 also showed a highest binding constant (7000 M -1 ). These copolymers, based on non-toxic and biocompatible poly(ε-caprolactone) and PEG, are of great interest for external body decontamination of actinides as they combine high number of complexing groups, thus leading to great decontamination efficiency, and limited diffusion through the skin due to their high-molecular weight, thus avoiding additional possible internal contamination.