CN-122017095-A - Solid-phase microextraction probe based on COF@copolymerization microsphere/MXene coating and preparation method and application thereof

Abstract

The invention belongs to the technical field of food detection, and particularly relates to a solid-phase microextraction probe based on a COF@copolymerization microsphere/MXene coating, and a preparation method and application thereof. The solid-phase microextraction probe is obtained by carrying out amination treatment on a support carrier to obtain an aminated support carrier, then loading a reaction monomer and a polymer skeleton on the surface of the aminated support carrier, and then adding 2, 6-dialdehyde-1, 5-dihydroxynaphthalene (DHNDA), MXene and glacial acetic acid for in-situ assembly, so that the extraction efficiency of the probe on organophosphorus pesticides is improved through a COF@copolymerization microsphere/MXene coating, and the high-selectivity and high-sensitivity detection on the organophosphorus pesticides in tea samples are realized.

Inventors

• CHEN QUANSHENG
• Hua Meifang
• CHEN XIAOMEI
• FANG YUWEN

Assignees

• 集美大学

Dates

Publication Date

20260512

Application Date

20260327

Claims (10)

1. 1. The preparation method of the solid-phase microextraction probe based on the COF@copolymerization microsphere/MXene coating is characterized by comprising the following steps of: carrying out amination treatment on the support carrier to obtain an aminated support carrier; Immersing the aminated support carrier in a solution containing a reaction monomer and a polymer skeleton, loading the reaction monomer and the polymer skeleton on the surface of the aminated support carrier, and then adding 2, 6-dialdehyde-1, 5-dihydroxynaphthalene, MXene and glacial acetic acid for in-situ assembly reaction to obtain the solid-phase microextraction probe; The reaction monomer is 1,3, 5-tri (4-aminophenyl) benzene; The polymer skeleton is DVB-NVP.
2. 2. The method according to claim 1, wherein the amination step comprises immersing the support in a mixed solution of 3-aminopropyl triethoxysilane, ethanol and water, and reacting to obtain the aminated support.
3. 3. The preparation method according to claim 2, wherein the volume ratio of 3-aminopropyl triethoxysilane, ethanol and water in the mixed solution is 3-4:3-4:1-2; and/or the reaction time is 1-2 h.
4. 4. The method according to claim 1, wherein the concentration of the reactive monomer in the solution containing the reactive monomer and the polymer skeleton is 0.05 to 0.1 mmol/L, the concentration of the polymer skeleton is 6 to 8. Mu.g/mL, and the solvent is 1, 4-dioxane and 1,3, 5-trimethylbenzene in a volume ratio of 1 to 2:4 to 8.
5. 5. The method according to claim 1, wherein the step of supporting the reaction monomer and the polymer skeleton comprises preheating 20 to 30 min at 50 to 70 ℃ after ultrasonic and vibration treatment.
6. 6. The method according to claim 1, wherein in the step of in-situ assembly reaction, the addition amount of 2, 6-dialdehyde-1, 5-dihydroxynaphthalene is 0.05 to 0.1 mmol/L, the addition amount of MXene is 0.5 to 1.0 mg/mL, and the addition amount of glacial acetic acid is 1 to 2 mmol/L; and/or the temperature of the in-situ assembly reaction is 60-80 ℃ and the time is 5-6 h; and/or, the MXene is Ti 3 C 2 T x MXene.
7. 7. The preparation method of the DVB-NVP, according to claim 1, is characterized in that the preparation method of the DVB-NVP comprises the steps of dissolving divinylbenzene and vinyl pyrrolidone monomers in acetonitrile, and carrying out ultrasonic treatment under a nitrogen atmosphere to obtain the DVB-NVP, wherein the volume ratio of the divinylbenzene to the vinyl pyrrolidone to the acetonitrile is 4-6:4-5:10-20, and the ultrasonic treatment time is 10-30 min.
8. 8. A solid phase microextraction probe based on cof@co-microsphere/MXene coating, characterized in that it is prepared by the preparation method according to any one of claims 1-7.
9. 9. Use of a solid phase microextraction probe based on cof@co-microsphere/MXene coating according to claim 8 for detecting residual organophosphorus pesticide.
10. 10. A method of detecting OPPs, comprising the steps of: S1, sample pretreatment, namely accurately weighing 5-10 g samples to be tested, adding ultrapure water, sealing and soaking 1-3 h to obtain a sample solution to be tested; S2, establishing a standard curve, namely performing solid-phase microextraction on a series of organophosphorus pesticide standard solutions with known concentrations by using the solid-phase microextraction probe according to claim 8, and then analyzing by using a gas chromatograph-flame luminosity detector; s3, sample detection, namely immersing the solid-phase microextraction probe into the sample solution to be detected obtained in the step S1, extracting at 25-30 ℃ for 20-40 min, and simultaneously assisting in the extraction by magnetic stirring in the solution; S4, calculating the concentration, namely substituting the peak area measured in the step S3 into the quantitative prediction model established in the step S2, and calculating the specific concentration of the organophosphorus pesticide in the sample to be measured.

Description

Solid-phase microextraction probe based on COF@copolymerization microsphere/MXene coating and preparation method and application thereof Technical Field The invention belongs to the technical field of food detection, and particularly relates to a solid-phase microextraction probe based on a COF@copolymerization microsphere/MXene coating, and a preparation method and application thereof. Background Long-term ingestion of tea leaves containing organophosphorus pesticides (OPPs) may cause various respiratory, cardiovascular and autoimmune diseases in humans, thereby raising a great deal of attention to OPPs residues in tea leaves. Hot water brewing is a traditional way of drinking tea. When tea is made, OPPs of tea leaves can be leached into tea soup, and even though nonpolar OPPs which is characterized by high octanol-water distribution coefficient logarithm (logKow) has low solubility in water, toxicity and threat to human health are not ignored. The analytical method of OPPs residues is generally dependent on chromatographic techniques, whereas sample pretreatment plays a critical role in chromatographic analysis. Among the numerous pretreatment technologies, the immersion solid phase microextraction detection (DI-SPME) technology has the advantages of low consumption of adsorption materials and samples, high enrichment factors, simple operation, less consumption of organic solvents, no need of complex equipment and the like, and plays an important role in OPPs residue detection. This technique immerses the adsorption coating directly into the sample solution, such that the contact surface between the adsorption coating and the analyte is increased. This feature not only improves the extraction efficiency of the analyte, but also shortens the time required for extraction. However, the SPME coating preparation methods currently employed mainly include materials and support carriers (SSWs) that are bonded by physical adhesion or electrochemical polymerization. Due to the lack of stable chemical bonding between the materials and SSWs, the coating stripping phenomenon is easy to occur, and the extraction efficiency is further affected. Thus, there is a need to research and develop more robust coating preparation methods to improve the reliability and reproducibility of SPME probes in OPPs assays. Disclosure of Invention The invention aims to provide a solid-phase microextraction probe based on a COF@copolymerization microsphere/MXene coating, a preparation method and application thereof, and particularly provides a pretreatment method of the solid-phase microextraction probe based on the COF@copolymerization microsphere/MXene coating, which is used for detecting the residue of organophosphorus pesticides in tea so as to solve the problems in the prior art and realize rapid and specific detection of OPPs pollution in the tea. In order to achieve the above object, the present invention provides the following solutions: The invention provides a preparation method of a solid-phase microextraction probe based on a COF@copolymerization microsphere/MXene coating, which comprises the following steps: carrying out amination treatment on the support carrier (SSWs) to obtain an aminated support carrier (SSW-NH 2); Immersing the aminated support carrier in a solution containing a reaction monomer and a polymer skeleton, loading the reaction monomer and the polymer skeleton on the surface of the aminated support carrier, and then adding 2, 6-dialdehyde-1, 5-dihydroxynaphthalene (DHNDA), MXene and glacial acetic acid to carry out in-situ assembly reaction to obtain the solid-phase microextraction probe (COF TAPB-DHNDA @DVB-NVP/MXene solid-phase coating probe); the reaction monomer is 1,3, 5-tri (4-aminophenyl) benzene (TAPB); The polymer skeleton is DVB-NVP. Further, the amination treatment step comprises the steps of immersing the support carrier in a mixed solution of 3-aminopropyl triethoxysilane (APTES), ethanol and water for reaction to obtain the aminated support carrier. Optionally, the volume ratio of 3-aminopropyl triethoxysilane (APTES), ethanol and water in the mixed solution is 3-4:3-4:1-2. Alternatively, the reaction time is 1-2 h. Further, the concentration of the reaction monomer in the solution containing the reaction monomer and the polymer skeleton is 0.05-0.1 mmol/L, the concentration of the polymer skeleton is 6-8 mug/mL, and the solvent is 1, 4-dioxane and 1,3, 5-trimethylbenzene with the volume ratio of 1-2:4-8. Further, the step of supporting the reaction monomer and the polymer skeleton is that after ultrasonic and vibration treatment, the reaction monomer and the polymer skeleton are preheated at 50-70 ℃ for 20-30 min. Further, in the step of in-situ assembly reaction, the addition amount of 2, 6-dialdehyde-1, 5-dihydroxynaphthalene is 0.05-0.1 mmol/L, the addition amount of MXene is 0.5-1.0 mg/mL, and the addition amount of glacial acetic acid is 1-2 mmol/L. Further, the MXene is Ti 3C2Tx MXene. Fur