关键词: 开管-毛细管电色谱, 共价有机骨架材料, 环境内分泌干扰物, 硝基苯酚

Abstract:

As a class of new porous crystalline materials, covalent organic frameworks (COFs) are attracting the attention of a large number of scientists. Because of their large specific surface area, low density, high stability, and tunable pore size, COFs have been widely applied in many fields, including analytical chemistry. Open-tubular capillary electrochromatography (OT-CEC) is a mode of capillary electrochromatography. In recent years, a variety of materials such as porous organic frameworks have been used as the stationary phase for OT-CEC to overcome the disadvantages of low phase ratio and column capacity, thereby improving the separation efficiency. However, there are a few reports on the use of COFs as the stationary phase to improve the separation efficiency of OT-CEC. Environmental endocrine disruptors (EEDs) are a large class of exogenous chemicals that can disturb the effect of the normal endocrine substances and adversely affect the endocrine and reproductive systems of human beings. Considering the widespread existence of EEDs and the disadvantages of existing detection methods (e. g., gas chromatography-mass spectrometry and high performance liquid chromatography-mass spectrometry), such as complicated operation and large sample consumption, it is necessary to develop new methods for the separation and determination of EEDs in complex samples. OT-CEC is a good choice in this regard because of its low sample dosage, simple operation, and high analytical speed. Accordingly, a two-dimensional azine-linked covalent organic framework (ACOF-1) with a large surface area and small pore size was synthesized according to the reference method. Then, an ACOF-1-coated capillary was fabricated using ACOF-1 as the stationary phase, via covalent bonding, and used as the separation channel to establish a new OT-CEC method for the separation and detection of nitrophenol EEDs. X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM) were used to characterize the synthesized ACOF-1 and the ACOF-1-coated capillary. The peak pattern in the XRD spectrum confirmed the successful synthesis of ACOF-1. The absorption peaks in the FT-IR spectrum and the morphology of the inner wall seen in the SEM images also demonstrated that the ACOF-1-coated capillary was fabricated successfully. A series of experiments were carried out to investigate the effects of the organic additive (methanol) content, pH, and concentration of the borate buffer on the resolution, migration time, and peak shape. Based on the results, the optimal separation conditions for the four nitrophenol analytes were 15 mmol/L borate (pH 9.20) with 10% (v/v) methanol. Under the optimum conditions, 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2, 4-dinitrophenol (DNP), and 2, 4, 6-trinitrophenol (TNP) could be baseline separated within 20 min by the established OT-CEC method. The linear range for 2-NP and 4-NP was 10-500 mg/L, while that for DNP and TNP was 20-1000 mg/L. The determination coefficients (R²) were greater than 0.99. For the four analytes, the limits of detection and limits of quantitation were in the ranges of 0.13-0.23 mg/L and 0.45-0.60 mg/L, respectively. The intraday, interday, and column-to-column relative standard deviations (RSDs) of the migration time and peak area were less than 9.4%. These results revealed that the established method has good repeatability and high stability, thus being suitable for the separation and detection of nitrophenol EEDs. The mechanism studies revealed that the pore size of ACOF-1 was the main factor influencing the separation behavior of each analyte. This work demonstrated the feasibility of using capillary electrochromatography with COFs as the stationary phase for the separation and detection of EEDs. Future research will continue to focus on the preparation of COF-coated capillaries and their application to OT-CEC separation and determination of EEDs.

Key words: open-tubular capillary electrochromatography (OT-CEC), covalent organic frameworks, environmental endocrine disruptors, nitrophenols