Fabrication of stable multivariate metal-organic frameworks with excellent adsorption performance toward bisphenols from environmental samples

As a type of environmental endocrine disrupting chemicals, bisphenols (BPs) have a certain embryonic toxicity and teratogenicity, which can significantly increase the risks of breast cancer, prostate cancer, leukemia and other cancers. In this work, stable multivariate metal-organic frameworks (UiO-66-NH₂/TCPP_x) were synthesized via in situ one-pot method and used as miniaturized dispersive solid-phase extraction (dμSPE) sorbents for extraction of trace BPs from environmental samples. The phase purity, crystal morphology and physical properties of UiO-66-NH₂/TCPP_x samples were varied by adjusting the mass ratio of TCPP. The extraction performance of UiO-66-NH₂/TCPP_x samples were investigated and UiO-66-NH₂/TCPP_1.0 exhibited the highest adsorption efficiency. Besides, UiO-66-NH₂/TCPP_1.0 possessed excellent recycling stability for the adsorption and desorption of BPs more than 20 cycles. The experimental parameters including amount of adsorbent, adsorption time, sample solution pH, temperature, desorption time and desorption solvents which affecting the efficiency of dμSPE were studied, respectively. Good linearity (R² > 0.9992) in range of 0.1–200 ng mL⁻¹ was obtained. The detection limits (S/N = 3) and quantification limits (S/N = 10) were achieved at 0.03–0.08 ng mL⁻¹ and 0.1–0.5 ng mL⁻¹, respectively. The relative standard deviations (RSDs) of intra-day and inter-day ranged from 2.5 to 5.5% and 1.1–6.8%. Enrichment factors were calculated in the range of 303–338. The obtained recoveries of bisphenol F (BPF), bisphenol A (BPA), bisphenol B (BPB) and bisphenol AF (BPAF) were 81.26–91.03% (RSDs = 0.96–6.47%), 82.2–97.27% (RSDs = 0.45–6.15%), 87.56–97.26% (RSDs = 1.1–6.22%) and 82.2–100.8% (RSDs = 0.46–4.07%). The UiO-66-NH₂/TCPP_1.0 can be employed as potential dμSPE sorbents for the enrichment of trace BPs in the environmental samples.