Hydroxy-Containing Covalent Organic Framework Combined with Nickel Ferrite as a Platform for the Recognition and Capture of Bisphenols

A hydroxy-containing
covalent organic framework (COF) was successfully
obtained via a simple nitrogen-purge synthetic procedure for the first
time. The COF favored a serrated AA-stacking arrangement, which enhanced
the stability compared with common AA or AB arrangements. To validate
the potential of the COF in environmental applications, we decorated
the COF onto NiFe2O4 and used the NiFe2O4@COF nanocomposite for magnetic solid-phase extraction
of trace bisphenols (BPs). The parameters affecting extraction efficiencies
were systematically optimized. Under the optimum extraction conditions,
calibration plots showed good linearity (5.0–1.0 × 103 ng mL–1) for six BPs, and limits of detection
varied from 0.14 to 0.73 ng mL–1. Molecular polarity
indexes and molecular dynamics simulations revealed why the COF could
efficiently recognize and capture BPs. An adsorption mechanism related
to the interaction between BP clusters and the COF was discovered.
Ecotoxicological assessment of BPs further unraveled the significance
of the developed method for the timely tracking of the concentration,
distribution, and migration of BPs in environmental media.

首次通过一种简便的氮气净化合成方法成功制备了一种含羟基的共价有机框架（COF）。该COF倾向于采用锯齿状的AA堆叠排列，与常见的AA或AB排列相比，这种排列增强了其稳定性。为了验证COF在环境应用中的潜力，我们将其装饰在NiFe2O4表面，并利用NiFe2O4@COF纳米复合材料进行磁固相萃取微量双酚（BPs）。系统地优化了影响萃取效率的参数。在最佳萃取条件下，校准曲线显示了六种BPs的良好线性关系（5.0–1.0 × 103 ng mL–1），检测限介于0.14至0.73 ng mL–1之间。分子极性指数和分子动力学模拟揭示了COF能够高效识别和捕获BPs的原因。一种与双酚（BP）簇与COF之间相互作用的吸附机制被发现。双酚的生态毒性评估进一步揭示了所开发方法对于及时追踪环境介质中BPs的浓度、分布和迁移的重要性。