Determination Of Adsorption Performance And Degradation Of Quinolone Antibiotics By Imprinted Materials

In this paper,metal organic frameworks ZIF-8/67,ZIF-67 and MIL-88A were used as carriers,combined with molecular imprinted polymers.Surface Molecular Imprinted Polymers（SMIPs）were synthesized by different template molecules.The prepared polymers were used as the sorbent of solid phase extraction column.The columns were optimized for the determination of quinolone antibiotics in water environment by high performance liquid chromatography（HPLC）.A method for the detection of quinolone antibiotics was established that verified by linear relationship,labeling and recovery experiment,and applied to actual water samples.A new 172 nm xenon excimer lamp oxygen generator was used to degrade quinolone antibiotics.The conditions were optimized and the mechanism of degradation was studied.It mainly includes the following four parts:1.Surface molecular imprinted polymers（ZIF-8/67@SMIPs）were synthesized by precipitation polymerization,using Bimetallic zeolite imidazolate framework ZIF-8/67 as support material and ciprofloxacin as template molecule.The successful synthesis of the carrier and polymers was confirmed by various characterization methods.The adsorption capacity of ZIF-8/67@SMIPs was determined to be 10.45μg mg^-1 at a concentration of 30μg m L^-1 by isothermal adsorption experiment.The imprinted materials were used as the packing material of the SPE column,and the parameters of the self-made column were optimized and5%methanol-water（V/V）was selected as the loading solvent and 0.1%formic acid-80%acetonitrile water（V/V）as the elution solvent with an elution volume of 4 m L.The capacity of the self-made column under optimized conditions was 150μg,which could be reused 6times.The recovery of ciprofloxacin was in the range of 88.34%～111.97%with the relative standard deviations（RSD）ranging from 3.23%to 5.72%at three concentrations of 10μg m L^-1,20μg m L^-1 and 30μg m L^-1 by the spiked recovery experiments.The limit of detection（LOD）of the method in matrix was 2.59 ng m L^-1 and the limit of quantification（LOQ）was 8.65 ng m L^-1.The developed method could be successfully used for the determination of quinolone antibiotics in aqueous environment.2.Surface molecular imprinted polymers（ZIF-67@SMIPs）were synthesized by using ZIF-67 as supporting material and enrofloxacin as template molecule.The successful synthesis of the carrier and polymers was confirmed by various characterization methods.The adsorption capacity of the polymers was determined at 9.02μg mg^-1 when enrofloxacin was30μg m L^-1.ZIF-67@SMIPs was used as the solid phase extraction column filler,and the parameters of the self-made column were optimized.The sample solvent was 5%methanol-water（V/V）,the elution solvent was 0.1%formic acid-methanol（V/V）with an elution volume of 4 m L.The column capacity was verified to be 510μg,which could be reused for 7 times with the optimized conditions.In the matrix,the LOD was 1.44 ng m L^-1,and the LOQ was4.79 ng m L^-1.The recoveries for enrofloxacin were 84.16%～100.68%,83.79%～95.17%and84.57%～98.43%,respectively at the spiked concentrations of 10μg m L^-1,20μg m L^-1 and 30μg m L^-1 and the RSD was 4.46%to 7.35%.The established method was used to detect the lake water and the sewage from the aquaculture plant.It was proved that the developed method could be applied to the determination of quinolone antibiotics in aqueous environment.3.Surface molecularly imprinted polymers（MIL-88A@SMIPs）were synthesized with MIL-88A as the carrier,quercetin as the dummy template for sparfloxacin,MAA as the functional monomer.The adsorption rate and isothermal adsorption experiments on the polymer showed that the adsorption of SMIPs on sparfloxacin reached equilibrium at 15 min,and the adsorption capacity was 4.8μg mg^-1 when sparfloxacin concentration was 30μg m L^-1.The polymers were used as SPE column filler,and the parameters were optimized.The elution volume was 2 m L with 0.1%formic acid and methanol（V/V）.It was verified that the column capacity was 80μg which could be reused for 7 times.In the matrix,the LOD was 6.8ng m L^-1,and the LOQ was 22.68 ng m L^-1.The recovery of sparfloxacin was in the range of87.04%～107.44%with RSD ranging from 3.87%to 4.67%at 3μg m L^-1,15μg m L^-1 and 30μg m L^-1.The developed method was applied to the pretreatment and detection of actual water samples.4.The 172 nm xenon excimer lamp oxygen generator was used to degrade quinolone antibiotics.It was found that the NO_x content produced by 172 nm xenon excimer lamp oxygen generator was much lower than that of the dielectric barrier discharge ozonator.The degradation conditions of 172 nm xenon excimolecular lamp oxygen generator was optimized.The results showed that the gaseous form of activated oxygen had superior performance with degradation rates in the range of 78.67%to 95.93%.After exploring the degradation temperature and initial concentration of the target,it was concluded that the degradation rates of three quinolone antibiotics were the best at 2℃,which were 70.63%,100%and 90.77%,respectively,while the initial concentration of the target had little influence on the degradation effect.The experimental results showed that 172 nm xenon excimer lamp oxygen generator has excellent performance in the field of quinolone antibiotic degradation and could be used in real life.