CN110152632B - Magnetic COF-TpPa for enriching amide pesticides and preparation method and application thereof - Google Patents
Magnetic COF-TpPa for enriching amide pesticides and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a magnetic COF-TpPa for enriching amide pesticides and a preparation method and application thereof, belonging to the technical field of adsorption materials. The preparation method provided by the invention comprises the following steps: (1) mixing 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, aminated magnetic beads and ethanol, and carrying out a first aldehyde-amine condensation reaction to obtain aldehyde-based magnetic beads; (2) adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, and carrying out a second amidol condensation reaction to obtain magnetic COF-TpPa for enriching amide pesticides. The magnetic COF-TpPa prepared by the preparation method provided by the invention has excellent adsorbability on amide pesticides (prochloraz and tolfenpyrad), good stability, superparamagnetism and easiness in separation, and the preparation method is simple to operate and mild and controllable in reaction conditions.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a magnetic COF-TpPa for enriching amide pesticides and a preparation method and application thereof.
Background
A Covalent Organic Framework (COF) material is an Organic porous material which is connected by light elements such as C, H, B, O, N and the like through Covalent bonds, has an ordered structure and controllable functions, has the advantages of highly ordered structure, large specific surface area, good chemical stability and thermal stability and the like, and is mainly applied to the fields of photoelectricity, catalysis, gas adsorption storage, sensing and the like. The application of the covalent organic framework material in the enrichment detection of pesticide residues is only reported, and currently, no COF with good enrichment capacity for amide pesticide residues exists.
At present, the common synthetic methods of COF materials include a solvothermal synthesis method, a sound wave-assisted method, a microwave method, a mechanical grinding method, and the like, and the solvothermal synthesis method is most reported and most widely applied, and is mainly used for dissolving a precursor of a reaction in a suitable medium solution and synthesizing the precursor in a closed reaction container (such as a reaction kettle, a heat-resistant pipe, and the like) by a high-temperature high-pressure method, wherein the temperature is usually above 100 ℃ and even reaches 200 ℃. The whole process of COF synthesis by the solvothermal method is carried out in a closed reaction container, real-time observation and sampling research cannot be carried out, and the yield is generally low. In addition, some COF materials require liquid nitrogen flash freezing and flame sealing operations (e.g. Synthesis and application as a solvent for polymeric aromatic hydrocarbons, xuexing Shi, 2018) in the solvent thermal Synthesis process, and triazine COFs materials require reaction in high-temperature molten zinc chloride under severe reaction conditions. Therefore, the COF preparation method has harsh conditions and cannot be produced in large scale, which hinders the wide application of COF materials. In addition, the covalent organic framework material has the problems of poor stability and difficult separation, and further limits the application of the covalent organic framework material in the enrichment of the amide pesticide residues.
Disclosure of Invention
The magnetic COF-TpPa obtained by the preparation method provided by the invention has excellent adsorbability on amide pesticides, can be used for enriching pesticide residues, and has excellent stability, easy separation and simple preparation method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of magnetic COF-TpPa for enriching amide pesticides, which comprises the following steps:
(1) mixing 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, aminated magnetic beads and ethanol, and carrying out a first aldehyde-amine condensation reaction to obtain aldehyde-based magnetic beads;
(2) adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, and carrying out a second amidol condensation reaction to obtain magnetic COF-TpPa for enriching amide pesticides.
Preferably, in the step (1), the mass ratio of the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde to the aminated magnetic beads is 0.1-0.4: 1.
Preferably, the temperature of the first aldehyde-amine condensation reaction in the step (1) is 40-55 ℃ and the time is 1-2 h.
Preferably, the solvent in the dispersion of the aldehyde-based magnetic beads, the solution of p-phenylenediamine and the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde in the step (2) is a mixed solution of 1, 4-dioxane and trimethylbenzene, and the volume ratio of the 1, 4-dioxane to the trimethylbenzene is 1: 0.2-4.
Preferably, the mass ratio of the aminated magnetic beads in the step (1) to the p-phenylenediamine and the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde in the step (2) is 1: 0.15-0.35: 0.25-0.4.
Preferably, the temperature of the second aldehyde amine condensation reaction in the step (2) is 15-35 ℃ and the time is 1-4 d.
Preferably, after the first aldehyde-amine condensation reaction in step (1) and the second aldehyde-amine condensation reaction in step (2) are completed, magnetic separation and washing are independently further included.
The invention also provides the magnetic COF-TpPa for enriching the amide pesticides, which is obtained by the preparation method in the technical scheme and has the particle size of 0.33-0.73 mu m.
The invention also provides application of the magnetic COF-TpPa for enriching the amide pesticides in the technical scheme as an amide pesticide adsorbent.
The invention provides a preparation method of magnetic COF-TpPa for enriching amide pesticides, which comprises the following steps: (1) mixing 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, aminated magnetic beads and ethanol, and carrying out a first aldehyde-amine condensation reaction to obtain aldehyde-based magnetic beads; (2) adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, and carrying out a second amidol condensation reaction to obtain magnetic COF-TpPa for enriching amide pesticides. According to the invention, through a first aldehyde-amine condensation reaction, amino on the surface of an aminated magnetic bead reacts with aldehyde group of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal, so that the 2,4, 6-trihydroxybenzene-1, 3, 5-triformal is grafted on the surface of the aminated magnetic bead to obtain an aldehyde-based magnetic bead, then a solution of p-phenylenediamine and a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal are sequentially added to perform a second aldehyde-amine condensation reaction, the polymer of the p-phenylenediamine and the 2,4, 6-trihydroxybenzene-1, 3, 5-triformal is further grafted on the surface of the aldehyde-based magnetic bead to obtain magnetic COF-TpPa for enriching amide pesticides.
The magnetic COF-TpPa for enriching the amide pesticides obtained by the preparation method provided by the invention has a good adsorption effect on the amide pesticides (prochloraz and tolfenpyrad). The aldehyde group unit and the amine group unit in the magnetic COF-TpPa for enriching the amide pesticides, which are obtained by the invention, both take benzene rings as main frames, and the aldehyde group unit contains rich hydroxyl groups, can interact with the benzene rings in the prochloraz and the tolfenpyrad through pi-pi conjugation, and interact with the amide bonds in the prochloraz and the tolfenpyrad through hydrogen bonds, so that the adsorption and enrichment of two drugs are realized. Meanwhile, the material forms a covalent organic framework polymer on the surface of the magnetic core, so that the material has a loose porous structure and has the advantages of large specific surface area and strong adsorption capacity. The adsorption experiment result shows that the adsorption rate of the magnetic COF-TpPa for enriching the amide pesticides obtained by the preparation method provided by the invention on the two pesticides reaches more than 98%; after the magnetic covalent organic framework material-TpPa is further treated by an elution solvent, the pesticide can be eluted and transferred to an elution solution, the elution rate is more than 85 percent, which indicates that the adsorption of the magnetic COF-TpPa for enriching the amide pesticide to the pesticide is a reversible adsorption process combined based on non-covalent bond acting force, and the magnetic COF-TpPa can be regenerated by using a strong elution solvent, so that the aim of repeated use is fulfilled.
In addition, the preparation method provided by the invention is simple to operate and easy to implement, does not need harsh conditions, and the obtained material has magnetism and can be separated and recovered from a solution medium directly by adopting a magnetic separation mode.
Drawings
FIG. 1 is an SEM image of magnetic COF-TpPa obtained in example 1 and used for enriching amide pesticides;
FIG. 2 FTIR chart of magnetic COF-TpPa obtained in example 1 for enriching amide pesticides.
Detailed Description
The invention provides a preparation method of magnetic COF-TpPa (COF is short for covalent organic materials, Tp is an abbreviation of Triformyl Phloroglucinol of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal, Pa is an abbreviation of p-phenylene diamine, which is an abbreviation of p-phenylene diamine) for enriching amide pesticides, which comprises the following steps:
(1) mixing 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, aminated magnetic beads and ethanol, and carrying out a first aldehyde-amine condensation reaction to obtain aldehyde-based magnetic beads;
(2) adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, and carrying out a second amidol condensation reaction to obtain magnetic COF-TpPa for enriching amide pesticides.
The method comprises the steps of mixing 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde, aminated magnetic beads and ethanol, and carrying out a first aldehyde-amine condensation reaction to obtain aldehyde-based magnetic beads. In the invention, in the first aldehyde-amine condensation reaction process, the first aldehyde-amine condensation reaction is carried out on the amino group on the surface of the aminated magnetic bead and the aldehyde group in the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde, so that the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde is connected to the aminated magnetic bead, and the aldehyde group magnetic bead with the surface rich in aldehyde groups is obtained.
In the present invention, the particle size of the aminated magnetic bead is preferably 0.148 to 0.720. mu.m. The source of the aminated magnetic beads is not particularly limited, and the aminated magnetic beads can be directly prepared from commercially available products or self-made products; in the present example, the aminated Magnetic beads were prepared according to the Prior art "Removal of Acidic intermediates in Multi-peptides Analysis of fluids Using Modified Magnetic Nanoparticles primer to Determination of via Ultra-HPLC-MS/MS, Microchip Acta,2015,182(15): 2521-2528".
In the present invention, the mass ratio of the 2,4, 6-trihydroxybenzene-1, 3, 5-triformal to the aminated magnetic beads in the first aldehyde-amine condensation reaction is preferably 0.1 to 0.4:1, and more preferably 0.12 to 0.3.
In the invention, the dosage ratio of the aminated magnetic beads to ethanol is preferably 1g: 200-350 mL.
The invention has no special limitation on the mixing sequence of the aminated magnetic beads, the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde and the ethanol, and can obtain uniformly dispersed mixed solution. In the embodiment of the invention, preferably, the aminated magnetic beads and the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde are respectively dispersed or dissolved in ethanol, and then the dispersion liquid of the aminated magnetic beads and the solution of the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde are mixed, and the mixing sequence can fully and uniformly mix the aminated magnetic beads and the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde, so as to be beneficial to obtaining uniform reaction products subsequently; the dosage ratio of the aminated magnetic beads to the ethanol in the aminated magnetic bead dispersion liquid is preferably 1g: 60-80 mL, and more preferably 1g: 65-70 mL; the concentration of the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde in the solution of the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde is preferably 0.8-1.5 mg/mL. The manner of dispersing and dissolving is not particularly limited in the present invention, and uniform dispersion and solution can be obtained, and in the embodiment of the present invention, the manner of dispersing and dissolving is preferably an ultrasonic manner. In the embodiment of the present invention, the dispersion of the aminated magnetic beads and the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde are preferably mixed by stirring.
In the invention, the temperature of the first aldehyde-amine condensation reaction is preferably 40-55 ℃, and more preferably 45-50 ℃; the time of the first aldehyde-amine condensation reaction is preferably 1-2 h.
After the first aldol condensation reaction is complete, the present invention preferably also includes magnetic separation and washing.
According to the invention, the reaction liquid obtained by the first aldehyde-amine condensation reaction is preferably cooled to room temperature, and then is subjected to magnetic separation and washing. The cooling rate is not particularly limited in the present invention, and cooling at room temperature is sufficient.
In the present invention, the magnetic separation is preferably performed by separating the obtained aldehyde-based magnetic beads by means of an additional magnet.
In the present invention, the solvent used for the washing is preferably ethanol; the washing mode is preferably soaking washing, and the washing process is preferably assisted by ultrasound; the time of each washing is preferably 3-7 min; the washing frequency is preferably 3-5 times; the dosage of the solvent used for each washing is preferably 100-200 mL/1g of aminated magnetic beads.
After the aldehyde-based magnetic beads are obtained, adding a solution of p-phenylenediamine to a dispersion solution of the aldehyde-based magnetic beads, then adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde, and carrying out a second aldehyde-amine condensation reaction to obtain the magnetic COF-TpPa for enriching the amide pesticides. In the invention, a solution of p-phenylenediamine is added into the dispersion liquid of the aldehyde-based magnetic beads, the p-phenylenediamine and aldehyde groups on the surfaces of the aldehyde-based magnetic beads are subjected to an aldehyde-amine condensation reaction, the p-phenylenediamine is grafted on the surfaces of the aldehyde-based magnetic beads to enable the surfaces of the magnetic beads to be rich in amino groups, and then a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal is added, so that the reaction is more favorably carried out in the direction of generating COF-TpPa.
In the invention, the dispersion liquid of the aldehyde-based magnetic beads, the solution of p-phenylenediamine and the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde are preferably prepared by an ultrasonic method.
In the invention, the solvent in the dispersion liquid of the aldehyde-based magnetic beads, the solution of p-phenylenediamine and the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde in the second aldehyde-amine condensation reaction is preferably a mixed solution of 1, 4-dioxane and trimethylbenzene, and the volume ratio of the 1, 4-dioxane to the trimethylbenzene is preferably 1: 0.2-4.
In the invention, the ratio of the amount of the solvent in the dispersion of the aldehyde-based magnetic beads to the amount of the aminated magnetic beads is preferably 60-85 mL:1 g.
In the invention, the concentration of the solution of p-phenylenediamine is preferably 0.002-0.004 g/mL.
In the invention, the concentration of the solution of the 2,4, 6-trihydroxybenzene-1, 3, 5-triformal is preferably 0.0015-0.003 g/mL.
In the invention, the mass ratio of the aminated magnetic beads to p-phenylenediamine in the condensation reaction of second aldehyde amine is preferably 1: 0.15-0.35, and more preferably 1: 0.2-0.3.
In the invention, the mass ratio of the aminated magnetic beads to the 2,4, 6-trihydroxybenzene-1, 3, 5-triformal in the condensation reaction of the second aldehyde amine is preferably 1: 0.25-0.4.
In the present invention, the solution of p-phenylenediamine is preferably slowly added to the dispersion of the aldehyde-based magnetic beads, and then the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal is slowly added. In the present invention, the slow addition is advantageous to further promote the reaction toward the formation of COF-TpPa.
The pressure of the second aldehyde amine condensation reaction is not particularly limited, and the normal pressure condition is adopted.
In the invention, the temperature of the second aldehyde amine condensation reaction is preferably 15-35 ℃; the time of the second aldehyde amine condensation reaction is preferably 1-4 d; the time for the second aldehyde amine condensation reaction is preferably started when the addition of the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde is completed.
After the second aldehyde amine condensation reaction is completed, the present invention preferably further comprises magnetic separation and washing. In the present invention, the solvent used for the washing is preferably ethanol; the washing mode is preferably soaking washing, and the washing process is preferably assisted by ultrasound; the time of each washing is preferably 3-7 min; the washing frequency is preferably 3-5 times; the dosage of the solvent used for each washing is preferably 80-300 mL/1g of aminated magnetic beads.
In the present invention, the stirring state is preferably maintained during the first and second aldehyde-amine condensation reactions.
The invention also provides the magnetic COF-TpPa for enriching the amide pesticides, which is obtained by the preparation method in the technical scheme and has the particle size of 0.33-0.73 mu m.
In the magnetic COF-TpPa for enriching the amide pesticides, 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde and aminated magnetic beads are connected through imine bonds, p-phenylenediamine and 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde are also connected through imine bonds, and structural change cannot occur under the condition that water and common organic solvents such as acetonitrile, methanol and a small amount of acid are added, so that the magnetic COF-TpPa provided by the invention has excellent stability in water and organic solvents, and is suitable for the adsorption process in liquid media.
The invention also provides the application of the magnetic COF-TpPa for enriching the amide pesticides in the technical scheme as the amide pesticide adsorbent; in the present invention, the amide pesticide is preferably at least one of prochloraz and tolfenpyrad.
The specific use method of the pesticide adsorbent is not particularly limited, and the conventional use method of the pesticide adsorbent can be adopted.
The following examples are provided to illustrate the magnetic COF-TpPa for enriching amide pesticides and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 0.05g of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde with 50mL of ethanol, and performing ultrasonic homogenization to obtain a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde; mixing 0.3g of aminated magnetic beads (the particle size is 0.148-0.720 mu m) with 20mL of ethanol, and uniformly performing ultrasonic treatment to obtain a dispersion liquid of the aminated magnetic beads; mixing the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde with the dispersion liquid of aminated magnetic beads, and reacting at 40 ℃ for 1 h; after the reaction is finished, cooling the temperature to room temperature, separating out the aldehyde magnetic beads in a way of adding a magnet, soaking and washing for 3 times (40-50 mL each time) by using ethanol, and clarifying the washing liquid by using ultrasound while soaking to obtain aldehyde magnetic beads;
mixing the aldehyde magnetic beads with 25mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a dispersion liquid of the aldehyde magnetic beads; mixing 0.07g of p-phenylenediamine with 25mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a solution of the p-phenylenediamine; mixing 0.1g of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal with 50mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal; slowly adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then slowly adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde, and stirring for reaction at 25 ℃ for 3 d; after the reaction is finished, separating out the magnetic COF-TpPa by adding a magnet, pouring out the reaction solution, soaking and washing for 3 times (100 mL each time) by using ethanol, and simultaneously soaking and assisting with ultrasound, and finally clarifying the washing solution to obtain the magnetic COF-TpPa for enriching the amide pesticides.
The magnetic COF-TpPa for enriching the amide pesticides obtained in the example is characterized by a scanning electron microscope, and the result is shown in FIG. 1. The particle size of the magnetic COF-TpPa for enriching the amide pesticides obtained in the embodiment is 0.330-0.730 μm, which is larger than that of the aminated magnetic bead, and thus, other monomers are grafted on the surface of the aminated magnetic bead.
The magnetic COF-TpPa for enriching the amide pesticides obtained in the example is characterized by an infrared spectrogram, and the result is shown in FIG. 2. 1577cm in the figure-1、1242cm-1、561cm-1The characteristic peaks of the respective C-C, C-N and Fe-O bonds appear, which indicate the formation of imine bonds on the one hand and also the magnetic Fe on the other hand3O4COF-TpPa is formed on the surface of the microsphere.
Example 2
Mixing 0.05g of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde with 60mL of ethanol, and performing ultrasonic homogenization to obtain a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde; mixing 0.4g of aminated magnetic beads (the particle size is 0.148-0.720 mu m) with 25mL of ethanol, and uniformly performing ultrasonic treatment to obtain a dispersion liquid of the aminated magnetic beads; mixing the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde with the dispersion liquid of aminated magnetic beads, and reacting at 50 ℃ for 1 h; after the reaction is finished, cooling the temperature to room temperature, separating out the aldehyde magnetic beads in a way of adding a magnet, soaking and washing the aldehyde magnetic beads for 3 times (50 mL each time) by using ethanol, and clarifying the washing liquid by using ultrasound while soaking to obtain the aldehyde magnetic beads;
mixing the aldehyde magnetic beads with 25mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a dispersion liquid of the aldehyde magnetic beads; mixing 0.09g of p-phenylenediamine with 30mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a solution of the p-phenylenediamine; mixing 0.12g of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal with 60mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal; slowly adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then slowly adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde, and stirring for reaction at 25 ℃ for 3 d; after the reaction is finished, separating out the magnetic COF-TpPa by adding a magnet, pouring out the reaction solution, soaking and washing for 3 times (80 mL each time) by using ethanol, and simultaneously soaking and assisting with ultrasound, and finally clarifying the washing solution to obtain the magnetic COF-TpPa for enriching the amide pesticides.
The particle size of the magnetic COF-TpPa for enriching the amide pesticides obtained in the embodiment is 0.330-0.630 μm, which is larger than that of the aminated magnetic bead, and thus, other monomers are grafted on the surface of the aminated magnetic bead.
Example 3
Mixing 0.1g of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde with 80mL of ethanol, and performing ultrasonic homogenization to obtain a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde; mixing 0.3g of aminated magnetic beads (the particle size is 0.148-0.720 mu m) with 20mL of ethanol, and uniformly performing ultrasonic treatment to obtain a dispersion liquid of the aminated magnetic beads; mixing the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde with the dispersion liquid of aminated magnetic beads, and reacting at 50 ℃ for 1 h; after the reaction is finished, cooling the temperature to room temperature, separating out the aldehyde magnetic beads in a way of adding a magnet, soaking and washing the aldehyde magnetic beads for 3 times (30 mL each time) by using ethanol, and clarifying the washing liquid by using ultrasound while soaking to obtain the aldehyde magnetic beads;
mixing the aldehyde magnetic beads with 20mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a dispersion liquid of the aldehyde magnetic beads; mixing 0.07g of p-phenylenediamine with 30mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a solution of the p-phenylenediamine; mixing 0.09g of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal with 55mL of mixed solvent (obtained by mixing 1, 4-dioxane and trimethylbenzene in a volume ratio of 1: 1), and performing ultrasonic homogenization to obtain a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-triformal; slowly adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then slowly adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde, and stirring for reaction at 25 ℃ for 3 d; after the reaction is finished, separating out the magnetic COF-TpPa by adding a magnet, pouring out the reaction solution, soaking and washing for 3 times (80 mL each time) by using ethanol, and simultaneously soaking and assisting with ultrasound, and finally clarifying the washing solution to obtain the magnetic COF-TpPa for enriching the amide pesticides.
The particle size of the magnetic COF-TpPa for enriching the amide pesticides obtained in the embodiment is 0.430-0.730 μm, which is larger than that of the aminated magnetic bead, and thus, other monomers are grafted on the surface of the aminated magnetic bead.
Application example 1
The adsorption performance of the magnetic COF-TpPa for enriching the amide pesticides obtained in example 1 on the amide pesticides is detected by the following method:
(1) preparing a pesticide aqueous solution by using a pesticide mixture standard with the concentration of 5ppm, wherein the concentration of each pesticide in the pesticide aqueous solution is 50 ppb;
(2) measuring 5mL of the pesticide aqueous solution, putting the pesticide aqueous solution into a 10mL centrifugal tube, putting 30mg of the magnetic COF-TpPa obtained in the example 1 into the centrifugal tube, and performing vortex for 10min to ensure that the material is fully tumbled in the centrifugal tube to adsorb the pesticide;
(3) fixing magnetic COF-TpPa on the side wall of a centrifuge tube by means of an external magnet, and then taking 1mL of supernatant to pass through a membrane and putting the supernatant into a sample injection vial;
(4) discarding the rest supernatant, keeping the material in a centrifuge tube, adding 5mL acetonitrile, and ultrasonically eluting for 5 min;
(5) fixing the material on the side wall of a centrifuge tube in a way of adding a magnet, then taking 1mL of supernatant acetonitrile solution to pass through a membrane, and putting the solution into a sample injection vial;
(6) respectively setting pesticide aqueous solution contrast and pesticide acetonitrile solution contrast with the concentration of each pesticide of 50ppb, and respectively taking 1mL of the solution to pass through a membrane and putting the solution into a sample injection vial;
(7) detection analysis was performed using LC-MS/MS.
The data are collated, and the percentage content of the pesticide left in the pesticide aqueous solution (marked as "unadsorbed pesticide amount") and the percentage content of the pesticide eluted by the magnetic COF-TpPa after the pesticide is adsorbed (marked as "eluted pesticide amount" in terms of the percentage content of the control of the pesticide acetonitrile solution) are calculated, and the results are shown in table 1:
table 1 results of adsorption performance of magnetic COF-TpPa for enrichment of amide-based pesticides obtained in example 1 on 2 amide-based pesticides
The data in table 1 show that the magnetic COF-TpPa for enriching the amide pesticides provided by the invention has excellent adsorption performance on prochloraz and tolfenpyrad, the adsorption rate (namely 1-unadsorbed pesticide amount) is over 98%, and meanwhile, the magnetic COF-TpPa after adsorbing the pesticides is eluted, the pesticide amount is over 85% and is close to the theoretical adsorption amount of the magnetic COF-TpPa, so that the pesticide on the magnetic COF-TpPa is easy to elute, and the eluted magnetic COF-TpPa has high recovery degree and can be reused.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of magnetic COF-TpPa for enriching amide pesticides comprises the following steps:
(1) mixing 2,4, 6-trihydroxybenzene-1, 3, 5-triformol, aminated magnetic beads and ethanol, and carrying out a first aldehyde-amine condensation reaction to obtain aldehyde-based magnetic beads; the temperature of the first aldehyde-amine condensation reaction is 40-55 ℃, and the time is 1-2 h;
(2) adding a solution of p-phenylenediamine into the dispersion liquid of the aldehyde-based magnetic beads, then adding a solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde, and carrying out a second amidol condensation reaction to obtain magnetic COF-TpPa for enriching amide pesticides;
and (3) performing condensation reaction on the second aldehyde amine in the step (2) at the temperature of 15-35 ℃ for 1-4 days.
2. The method according to claim 1, wherein the mass ratio of the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde to the aminated magnetic beads in step (1) is 0.1 to 0.4: 1.
3. The method according to claim 1, wherein the solvent in the dispersion of the aldehyde-based magnetic beads, the solution of p-phenylenediamine, and the solution of 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde in step (2) is a mixture of 1, 4-dioxane and trimethylbenzene, and the volume ratio of 1, 4-dioxane to trimethylbenzene is 1: 0.2-4.
4. The method according to claim 1, wherein the mass ratio of the aminated magnetic beads in the step (1) to the p-phenylenediamine and the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde in the step (2) is 1: 0.15-0.35: 0.25-0.4.
5. The method according to claim 1, wherein the steps of (1) and (2) are carried out separately by magnetic separation and washing.
6. The magnetic COF-TpPa for enriching the amide pesticides obtained by the preparation method of any one of claims 1 to 5 has a particle size of 0.33 to 0.73 μm.
7. The use of the magnetic COF-TpPa for enriching amide pesticides as claimed in claim 6 as an amide pesticide adsorbent.
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