A kind of magnetic sulfonic acid functionalized cofs material and its preparation method and application

A sulfonic acid-based, functionalized technology, applied in chemical instruments and methods, separation methods, analytical materials, etc., can solve the problem of poor selective adsorption performance of aromatic amine compounds, and achieve strong electrostatic adsorption and efficient adsorption effect

Active Publication Date: 2021-01-22

ZHENGZHOU TOBACCO RES INST OF CNTC

5 Cites 0 Cited by

AI-Extracted Technical Summary

Problems solved by technology

[0006] The purpose of the present invention is to provide a magnetic sulfonic acid functionalized COFs material, th...

Abstract

The invention relates to a magnetic sulfonic functional COFs material, a preparation method and application thereof. The COFs material includes a covalent organic framework formed by Schiff base condensation reaction of 2, 4, 6-triformylphloroglucinol and 2, 5-diaminobenzenesulfonic acid, and magnetic nanoparticles for modification on the covalent organic framework, wherein the magnetic nanoparticles are amino functionalized Fe3O4/SiO2 core-shell nanoparticles. The aperture confinement effect of the COFs material can exclude adsorption of protein and other macromolecules in a urine matrix. Thesulfonic group on the COFs material has strong electrostatic adsorption effect with the amino of an aromatic amine compound, and can achieve efficient adsorption of the aromatic amine compound and prevent adsorption of an electronegative compound. The benzene ring structure on the COFs material and the benzene ring of the aromatic amine compound have strong Pi-Pi interaction. The COFs material realizes selective efficient enrichment of trace aromatic amine compound in a complex matrix.

Application Domain

Other chemical processesComponent separation +2

Technology Topic

Protein proteinSchiff base +17

Image

Examples

Experimental program(3)

Example Embodiment

[0039]Example 1

[0040]The magnetic sulfonic acid functionalized COFs material of this embodiment, such asfigure 1 As shown, the following steps are used for preparation:

[0041]Dissolve 2,4,6-triformyl pyrogallol (21.0mg) and 2,5-diaminobenzenesulfonic acid (28.2mg) in a mixed solvent of trimethylbenzene/dioxane (from 0.2mL Trimethylbenzene and 0.8mL of dioxane are mixed), add 0.1mL of 3mol/L acetic acid solution, mix at room temperature to form a uniform solution; then under nitrogen protection, add 0.02g magnetic Nanoparticles were reacted at 100°C for 72 hours. After the reaction, the black solid product was separated, washed with anhydrous dimethylformamide, anhydrous tetrahydrofuran and anhydrous acetone, and then washed with anhydrous methanol 2-3 times to complete the activation. After vacuum drying at 150°C for 12 hours, the magnetic sulfonic acid functionalized COFs material was obtained.

[0042]Applying the magnetic sulfonic acid functionalized COFs material of this embodiment to the detection of aromatic amine compounds in human urine includes the following steps:

[0043]1) Magnetic solid phase extraction: Take out the urine sample stored at -18°C and thaw it at room temperature. Take 5mL of the thawed urine sample and place it in a plastic centrifuge tube, add 1mL of concentrated hydrochloric acid solution, and treat it in a constant temperature water bath at 80°C 2h, then cool to room temperature, add 1.2mL of 10mol/L NaOH solution to neutralize the pH to 7.0, then add 10mL of 0.5mol/L, pH=7.0 ammonium acetate-ammonia buffer solution and mix well to obtain Sample solution

[0044]Transfer the sample solution to a 50mL beaker, add 100μL of D7-1-aminonaphthalene (concentration of 50ng/mL) and D9-4-aminobiphenyl (concentration of 10ng/mL) mixed internal standard solution, and 100mg magnetic sulfonic acid group After the functionalized COFs material is magnetically stirred for 30 minutes, place the magnet on the outer wall of one side of the beaker to separate the adsorbed magnetic sulfonic acid-based functionalized COFs material from the solution. Pour the solution in the beaker; remove the magnet and add 10 mL to the beaker Wash with water, magnetically stir for 10 minutes, use the magnet again to achieve phase separation, pour out the washing water; add 10 mL of elution solvent (diluted by methanol to concentrated ammonia water, the concentration of concentrated ammonia water is 28wt%; elution) The concentration of ammonia in the solvent is 5wt%). After magnetic stirring for 10 minutes, use a magnet to achieve phase separation. Pour to collect the eluent; concentrate the eluent to 0.1mL and use it as the solution to be tested.figure 2Shown

[0045]2) HPLC-MS/MS analysis: use the internal standard method to establish the standard working curve of each target compound, put the test solution into the HPLC-MS/MS instrument for analysis, and substitute the detection data into the standard working curve to calculate the 1-amino group in the sample The concentration of naphthalene, 2-aminonaphthalene, 3-aminobiphenyl and 4-aminobiphenyl.

[0046]In step 2), the chromatographic conditions of HPLC-MS/MS analysis are: the column is Waters C18 (100mm×2.1mmi.d., 2.7μm), the column temperature: 30℃; the mobile phase A is an aqueous solution containing 0.1% formic acid , Mobile phase B is acetonitrile solution containing 0.1% formic acid; gradient elution is adopted, and the conditions are as follows: 0-3min, 100% A0% B; 3.1-16.0min, 75% A25% B; 16.1-20min, 0% A100% B; 20.1-25.0min, 100% A; injection volume 10μL; flow rate 200μL/min.

[0047]Mass spectrometry conditions are: ion source: electrospray ionization source (ESI); scanning method: positive ion scanning; detection method: multi-reaction monitoring MRM; electrospray voltage: 5500V; curtain air pressure: 30psi; auxiliary gas 1 pressure: 70psi; auxiliary Gas 2 pressure: 70psi; ion source temperature: 500°C; see Table 1 for quantitative ion pair, qualitative ion pair, residence time, collision energy (CE) and declustering voltage (DP) of each compound.

[0048]Table 1 Quantitative ion pair, qualitative ion pair, residence time, collision energy and declustering voltage of each compound

[0049]

[0050]Table 2 shows the linear equation, correlation coefficient, detection limit and quantification limit of each aromatic amine compound with 3 times the signal-to-noise ratio (S/N) as the detection limit and 10 times the S/N as the quantification limit.

[0051]Table 2 Linear equation, correlation coefficient, detection limit and quantification limit of aromatic amine compounds

[0052]

[0053]The same urine sample was tested in parallel for 6 times in one day and measured in 5 days. The relative standard deviation (RSD) of the measurement results indicates the intra-day and inter-day precision of the method. At the same time, the spike recovery experiment was performed. The results are shown in the table 3 shown.

[0054]Table 3 The intra-day precision, intra-day precision and recovery rate of the method of Example 1

[0055]

[0056]It can be seen from the results in Table 3 that this method has good precision and high recovery rate of standard addition, and is suitable for the detection of aromatic amine metabolites in human urine.

[0057]Urine samples of 5 smokers and 2 non-smokers were collected, and the method in Example 1 was used to analyze the 1-aminonaphthalene, 2-aminonaphthalene, 3-aminobiphenyl, and 4-aminobiphenyl in the urine samples. The metabolites were subjected to magnetic solid phase extraction and HPLC-MS/MS analysis. The results are shown in Table 4.

[0058]Table 4 Analysis of urine samples of smokers and non-smokers (pg/mL)

[0059]

[0060]It can be seen that the method of Example 1 can conveniently detect the content of metabolites of 1-aminonaphthalene, 2-aminonaphthalene, 3-aminobiphenyl and 4-aminobiphenyl in human urine. The detection process is simple and precise. In Table 4, the content of aromatic amine metabolites in the urine of smokers is significantly higher than that of non-smokers. The purification treatment solution obtained by using this magnetic solid phase extraction technology can also lay a foundation for the follow-up study of aromatic amine compounds. Good foundation.

Example Embodiment

[0061]Example 2

[0062]The magnetic sulfonic acid group functionalized COFs material of this embodiment is prepared using the following steps:

[0063]Dissolve 2,4,6-triformyl pyrogallol (11.0mg) and 2,5-diaminobenzenesulfonic acid (18.2mg) in a mixed solvent of trimethylbenzene/dioxane (from 0.2mL Trimethylbenzene and 0.6mL of dioxane are mixed), add 0.1mL of 3mol/L acetic acid solution, mix at room temperature to form a homogeneous solution; then under nitrogen protection, add 0.02g magnetic Nanoparticles were reacted at 90°C for 80 hours. After the reaction, the black solid product was separated, washed with anhydrous dimethylformamide, anhydrous tetrahydrofuran, and anhydrous acetone in sequence, and then washed with anhydrous methanol for 2-3 times to complete the activation. After vacuum drying at 150°C for 12 hours, the magnetic sulfonic acid functionalized COFs material was obtained.

Example Embodiment

[0064]Example 3

[0065]The magnetic sulfonic acid group functionalized COFs material of this embodiment is prepared using the following steps:

[0066]Dissolve 2,4,6-triformyl pyrogallol (28.0mg) and 2,5-diaminobenzenesulfonic acid (40.0mg) in a mixed solvent of trimethylbenzene/dioxane (from 0.2mL Trimethylbenzene and 1.2mL of dioxane are mixed), add 0.1mL of 3mol/L acetic acid solution, mix at room temperature to form a uniform solution; then under nitrogen protection, add 0.04g magnetic Nanoparticles were reacted at 120°C for 60 hours. After the reaction, the black solid product was separated, washed with anhydrous dimethylformamide, anhydrous tetrahydrofuran, and anhydrous acetone, and then washed with anhydrous methanol 2-3 times to complete the activation. After vacuum drying at 150°C for 12 hours, the magnetic sulfonic acid functionalized COFs material was obtained.

[0067]In other embodiments of the magnetic sulfonic acid-based functionalized COFs material of the present invention, the amount of 2,4,6-triformylpyrogallol, 2,5-diaminobenzenesulfonic acid, magnetic nanoparticles and catalyst acetic acid, The specific Schiff base condensation reaction conditions can be adjusted adaptively within the scope of the present invention, and COFs materials with equivalent performance can be obtained.

PUM

Description & Claims & Application Information

We can also present the details of the Description, Claims and Application information to help users get a comprehensive understanding of the technical details of the patent, such as background art, summary of invention, brief description of drawings, description of embodiments, and other original content. On the other hand, users can also determine the specific scope of protection of the technology through the list of claims; as well as understand the changes in the life cycle of the technology with the presentation of the patent timeline. Login to view more.

Classification and recommendation of technical efficacy words

Efficient adsorption

A kind of magnetic sulfonic acid functionalized cofs material and its preparation method and application

AI-Extracted Technical Summary

Problems solved by technology

Abstract

Image

Examples

Example Embodiment

Example Embodiment

Example Embodiment

PUM

Description & Claims & Application Information

Similar technology patents

Preparation method of MnO2/chitosan carbon/cellulose aerogel urea-formaldehyde resin adhesive additive

Environment-friendly fluff removing machine for spinning

Method for detecting content of caffeine in tea leaves

Preparation method of hyperbranched polyester modified silver ion-loaded diatomite

Method and device for cooperative treatment of waste gas and wastewater from automobile repair factories

Classification and recommendation of technical efficacy words

Method for preparing Ti4+ supported hydroxyapatite nano powder absorbing disinfection material

Preparation method and application method of adsorbent for treating reactive dye wastewater

Preparation method of MnO2/chitosan carbon/cellulose aerogel urea-formaldehyde resin adhesive additive

Preparation method of hyperbranched polyester modified silver ion-loaded diatomite

Method and device for cooperative treatment of waste gas and wastewater from automobile repair factories