f-Block elements are critical to the technological and energy infrastructure that underpin our modern and future world; however, their production and purification rely on economically and environmentally costly solvent extraction processes. Polymeric extractants are an emerging class of materials that can improve or supplant these methods. Our group uses isothermal titration calorimetry (ITC), a technique widely used in the study of biomolecule binding, to directly determine the impact of polymer structure on the underlying binding thermodynamics and to develop rational design principles based on structure property relationships. Motivated by the need for new, organic soluble polymer extractants, recent work has focused on developing a new method for biphasic ITC that has the potential to determine the entire thermodynamic profile of an extraction in a singular experiment. Using the well-studied model system of Eu<sup>3+</sup> extraction by di-(2-ethylhexyl) phosphoric acid (DEHPA), we have been able to reliably determine the ΔG<sub>extr</sub> in a single experiment rather than a more laborious determination of the distribution coefficient. Combined with the synthesis of polymeric analogues of industrially used small–molecule extractants, this work will enable the direct comparison of key thermodynamic parameters between small–molecule and polymeric extractants and allow for the rational development of new polymer extractants.

Biphasic isothermal titration calorimetry (ITC) as a tool to develop new polymeric extractants

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