ABSTRACT
The detection of antibiotics and pesticides are of great significance since their residues threaten the health of human beings by accumulation. However, most traditional solid chemical sensors are suffer from the limitations of low sensitivity and economic practicability because of the aggregating nature and unstable of solid sensors. Herein, a new luminescent sensor 1@PMMA (1, [(ZnL)·H2O]n (H2L = 5-(4-(pyridin-4-yl)benzamido)benzene-1,3-dioic acid); PMMA = poly(methyl methacrylate)) was successfully prepared. Notably, the polymer matrix provided the chemical protection for MOF particles. The as fabricated 1@PMMA was stable in milk, honey and egg as well as exhibited strong blue emission under ultraviolet light irradiation, which can act as luminescent probe for detecting antibiotics and pesticides. More interestingly, 1@PMMA exhibited visual, real-time and recyclable detection of antibiotics ornidazole (ODZ) and pesticides 2,6-dichloro-4-nitrobenzenamine (DCN) in real food samples. This work shows that the luminescent MOF-based mixed matrix membranes could be applied as good candidates for sensing analytes in practical application.
Subject(s)
Anti-Bacterial Agents , Food Contamination , Metal-Organic Frameworks , Pesticides , Anti-Bacterial Agents/analysis , Metal-Organic Frameworks/chemistry , Pesticides/analysis , Food Contamination/analysis , Zinc/analysis , Zinc/chemistry , Polymethyl Methacrylate/chemistry , Milk/chemistry , Luminescent Measurements/methods , Honey/analysis , Animals , Eggs/analysis , Membranes, Artificial , Food Analysis/methods , Limit of DetectionABSTRACT
The effective detection of Al3+ and antibiotics pollutants is crucial for environmental protection and human health due to their high toxicity and nondegradability, but it is still currently challenging. In this work, a methyl-decorated acylamide-containing dicarboxylate ligand H2L was elaborately designed and successfully synthesized, which was further employed to react with Zn(ii) ions and dpe ligands to construct a new luminescent Zn-MOF, namely {[Zn(L)(dpe)]·DMF·3H2O} n (1). X-ray crystallography reveals that MOF 1 is a 3D 8-fold [4 + 4] interpenetrated diamondoid framework with isolated DMF and water molecules in the pores, in which the uncoordinated acylamide groups are found and facilitate the Zn-MOF to recognize analyte molecules. The activated solvent-free MOF sample (denoted as 1a) exhibits excellent water stability and good luminescent performance. The luminescence sensing experiments show that 1a could behave as a bi-responsive chemical sensor for "turn-on" and "turn-off" luminescent detection of Al3+ and SNT in aqueous media, respectively. The sensing mechanisms have also been discussed. Furthermore, MOF 1a was successfully applied to the effective determination of Al3+ and SNT in real water samples. This represents, to our knowledge, the first example of a MOF material for "turn-on" and "turn-off" luminescent detection of Al3+ and SNT in water, which will promote the practical application of water-stable luminescent MOF sensors in monitoring metal ions and antibiotics pollutants in the environmental water matrices.