Reversible Calcium(II)-Ion Binding through an Apparent pKa Shift of Thermosensitive Block-Copolymer Micelles

Angew Chem Int Ed Engl. 2015 Nov 16;54(47):14085-9. doi: 10.1002/anie.201505351. Epub 2015 Sep 25.

Abstract

There is an increasing need for smart materials capable of removing multivalent ions from aqueous streams without the inconvenience of brine regeneration as in ion-exchange processes. Herein, we present a thermoresponsive micellar system consisting of polystyrene-poly(methoxy diethyleneglycol acrylate) block copolymer surfactants modified with carboxylic acid end groups (PS-PMDEGA-COOH) that can be used to switch between the adsorption and desorption of divalent calcium(II) cations by a mild temperature trigger, thus providing a new type of thermoregenerable ion-adsorbing materials. The switch of calcium(II)-binding capacity is demonstrated to result from a shift in the pKa value of the carboxylic acid groups by the collapse and redissolution of the PMDEGA block and the associated change in local polarity.

Keywords: calcium(II) binding; responsive polymers; self-assembly; smart materials; thermoreponsive polymers.