A chemically robust amine-grafted Zn(ii)-based smart supramolecular gel as a regenerative platform for trace discrimination of nitro-antibiotics and assorted environmental toxins

Abstract

Smart supramolecular metallogels are fascinating reusable materials with the potential for a wide range of sustainable applications including the detection of multiple lethal pollutants. We have assembled a chemically robust triazole-containing Zn(II)-supramolecular gel (ZnGel), where the channels and surface of the gel are strategically decorated with triazole N and appended –NH₂ units that are pivotal to ZnGel's efficacy as a multi-sensory probe. ZnGel shows selective fluorescence quenching in the presence of traces of nitro-antibiotics (LOD of nitrofurantoin: 4.62 ppm) and electron-deficient nitrophenols (LOD of 4-nitrophenol: 4.18 ppm), without any prior activation. Density functional theory calculations delineate the importance of the triazole gelator in the turn-off fluorescence response of ZnGel to divergent organo-toxins and substantiate the supramolecular interactions between the ZnGel and the analytes. Significant fluorescence quenching of ZnGel ensued in the presence of a trace amount of Fe³⁺ (LOD: 6.13 ppm) over other competing metal ions, in addition to visible colorimetric changes in the ZnGel upon metal encapsulation. The quenching ability of ZnGel remains unaltered for multiple cycles toward these environmental pollutants. The noteworthy quenching efficiency is attributed to a combination of static and dynamic fluorescence quenching and resonance energy transfer, which are in harmony with the DFT predictions. Thus, ZnGel provides a platform for the development of gel-based probes for diverse applications in the future.