Abstract:

Ribavirin （RBV） is a broad-spectrum antiviral drug. It is widely used to treat various viral infections. However， its entry into water bodies can cause serious harm to both the ecological environment and human health. Thus， there is an urgent need for a simple and efficient method to detect RBV for detection purposes. In this study， a two-dimensional ZIF material （ZIF-L） served as the matrix， RBV as the template molecule， and 3-aminophenylboronic acid （APBA） as the functional monomer， using its self-polymerization ability to form a molecularly imprinted layer on the surface of ZIF-L. Imprinted cavities were created using a MeOH-HAc （1∶1， volume ratio） eluent to disrupt the interaction between RBV and APBA， yielding ZIF-L-based boronate affinity molecularly imprinted polymers （ZIF@B-MIPs）. Non-imprinted materials （ZIF@B-NIPs） were prepared identically without RBV. ZIF@B-MIPs features dynamic recognition sites formed through pH-responsive boronate ester bonds. This enabled synergistic recognition based on the template molecule’s “shape memory” and “chemical bonding”. Scanning electron microscopy （SEM） and Fourier-transform infrared spectroscopy （FT-IR） were employed to characterize the morphology and functional groups of the material. Notably， new FT-IR peaks emerged for ZIF@B-MIPs at 1 381 cm^-1 （B-O vibration） versus ZIF-L， confirming APBA polymerization. This indicates that the polymerization of APBA onto the surface of ZIF-L was successful. The synthesis and adsorption conditions were optimized. The results showed that， with a ZIF-L dosage of 100 mg， the optimal amount of the self-polymerizing reagent APBA was 100 mg. A self-polymerization time of 5 h was sufficient to form an appropriately thick imprinted layer. At pH 8.5， the stability of the polymer network was maintained while the imprinting effect and mass transfer efficiency were maximized. The post-elution re-adsorption capacity retention rate reached 96.8%， balancing elution efficiency with structural integrity. A RBV mass concentration of 60 mg/L was selected for the experimental requirements. After optimization， the saturation adsorption capacity of ZIF@B-MIPs for RBV reached 21.43 mg/g. The imprinting factor （IF） was 5.32. The material’s performance was assessed through adsorption and reusability experiments. The results indicated that the material possesses good specificity and selective recognition ability. It also exhibits a rapid adsorption rate and good reusability. The adsorption experiment results showed that the adsorption kinetics followed the pseudo-second-order model （R²=0.995 3）. Adsorption equilibrium was achieved within 15 min. The adsorption process of RBV by the adsorbent involves chemisorption. The Langmuir isotherm adsorption model （R²=0.982 5） fitted the experimental data better. This indicates that the adsorption of RBV by ZIF@B-MIPs likely involves monolayer adsorption. In mixed solutions of RBV and three interfering substances （lamivudine，uridine，inosine） with mass concentration ratios of 1∶1 and 1∶10， the adsorption capacity of RBV by ZIF@B-MIPs remained high. The interfering substances had minimal impact on the adsorption performance. The reusability experiment results showed that the material retained 93.6% of its initial adsorption capacity after six adsorption-desorption cycles. The reproducibility of ZIF@B-MIPs was investigated using six batches of adsorbents. The adsorption capacity for RBV ranged from 19.41 to 20.73 mg/g. This indicates that the material also possesses good reproducibility. In the detection of actual environmental water samples， the method exhibited excellent applicability. The recoveries of RBV in environmental water samples at three spiked levels （30， 50， 60 mg/L） were 83.8%-94.5% （RSD<2.1%）. The detection system constructed in conjunction with high performance liquid chromatography （HPLC） demonstrated a good linear relationship in the range of 0.05 to 100 mg/L （R²=0.991 6）. The limit of detection was 0.038 mg/L （S/N=3）， and limit of quantification was 0.081 mg/L （S/N=10）. The ZIF@B-MIPs-HPLC technology was successfully applied to the efficient adsorption， enrichment， and detection of RBV in drinking water sources. It holds potential for applications in the fields of human health and environmental protection. This technology offers a new strategy for the rapid detection of trace antiviral drugs in environmental samples.

Key words: ribavirin （RBV）, molecularly imprinted polymers （MIPs）, adsorption, high performance liquid chromatography （HPLC）