Recyclable macromolecular thermogels for Hg(II) detection and separation via sol-gel transition in complex aqueous environments

Abstract

The sensitive detection and quantitative separation of toxic heavy metal ions in aqueous media are of great importance. In this study, a thermogelling poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) (PCL-PEG-PCL) triblock copolymer (P1) was synthesized, and difluoroboron dipyrromethene (BODIPY) fluorophore integrated with thiosemicarbazide units was attached to the chain ends of P1 through consecutive post-polymerization modifications, leading to P4. P4 exhibited rapid and selective detection of Hg(II) in 100% aqueous media via turn-on fluorescence emission with a limit of detection (LOD) of as low as 0.461 μM. This turn-on emission behavior is attributed to the suppression of C?N isomerization caused by the formation of a coordination complex between P4 and Hg(II) ions. The selective and quantitative removal of Hg(II) among various metal ions was achieved by trapping chelated Hg(II) ions inside the dehydrated P4 gel via thermo-controlled sol-gel-dehydrated gel transitions. Treating the Hg(II) ion-trapped dehydrated gels with sodium sulfide (Na2S) in acetone/water at room temperature led to HgS precipitates, and P4 in solution was dried and recycled. This recyclable thermoresponsive macromolecular probe is promising for not only Hg(II) detection but also its separation and removal from complex aqueous environments.