CN111715198B - Magnetic fullerene nano material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides - Google Patents

Magnetic fullerene nano material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides Download PDF

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CN111715198B
CN111715198B CN202010640088.9A CN202010640088A CN111715198B CN 111715198 B CN111715198 B CN 111715198B CN 202010640088 A CN202010640088 A CN 202010640088A CN 111715198 B CN111715198 B CN 111715198B
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宋伟
周典兵
韩芳
王钰
吕亚宁
丁磊
刘宇欣
郑平
郭春丽
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Hefei Customs Technology Center
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Abstract

The invention discloses a magnetic fullerene nano material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides, wherein the preparation steps are as follows: first Fe by tetraethylorthosilicate TEOS 3 O 4 Modifying the nano particles to obtain silica-coated ferroferric oxide superparamagnetic particles, and recording the particles as Fe 3 O 4 @SiO 2 Nanoparticles; then Fe 3 O 4 @SiO 2 The nano particles react with 3-chloropropyltrimethoxysilane to obtain Fe 3 O 4 @SiO 2 @ Cl nanoparticles; finally, the fullerene C is added 60 Reacting with benzaldehyde and benzylamine to obtain 2, 5-diphenyl fullerene pyrroline, and reacting with Fe 3 O 4 @SiO 2 Reaction of @ Cl nano particles to obtain magnetic fullerene nano material, marked as Fe 3 O 4 @SiO 2 @C 60 Nanoparticles. The magnetic fullerene nano material can be used for magnetic dispersion solid phase extraction of methyl methoxyacrylate pesticides, and has the advantages of strong adsorbability, large adsorption capacity, good selectivity and easiness in elution.

Description

Magnetic fullerene nano material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides
Technical Field
The invention belongs to the technical field of enrichment, purification and detection of pesticide residues in food and environmental samples, and particularly relates to a magnetic fullerene nano material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides.
Background
Pesticide residue analysis is an analytical technique for trace components in complex mixtures. The development trend of pesticide chemical pollutant residue detection technology is that the sample dosage is less, the reagent consumption is less, and the analysis speed is fast. How to realize multi-residue analysis and ensure the recovery rate while effectively removing impurities is a difficult point of the whole pretreatment process.
The magnetic solid phase extraction technology is a novel sample pretreatment technology developed in recent years, and has some special advantages compared with the traditional solid phase extraction technology: the magnetic adsorbent can be easily separated from the sample solution by applying an external magnetic field without centrifugation or filtration; the magnetic adsorbent material is dispersed in the solution, which allows for more sufficient contact area between the sample and the magnetic adsorbent, faster mass transfer, and rapid equilibration. Fullerene (C) 60 ) As a carbon-based nano material, the carbon atom adopts sp 2 Hybridization, strong electrophilic ability, electron-deficient polyene property, and pi electron distribution in C 60 The inner and outer surfaces of the thirty-dihedral cage-shaped structure form a three-dimensional conjugated system and have stronger pi-pi conjugation effect. Due to C 60 The composite material has the advantages of large specific surface area, strong hydrophobicity, easy functional modification, good acid resistance, alkali resistance, heat resistance and chemical stability, and certain advantages when being applied to separation and enrichment of pesticide residues in foods and environments. The ferroferric oxide nano particles have superparamagnetism and are reacted with C 60 Constructing a magnetic fullerene material by reacting C 60 The adsorption performance of the method is combined with the convenient magnetic separation of the ferroferric oxide nanoparticles, the magnetic dispersion solid-phase extraction method is established, the method is applied to the enrichment and purification of pesticide residues, the pretreatment steps are simple, the method can be recycled for many times, and the analysis cost can be greatly saved.
Disclosure of Invention
In order to overcome the defects of complicated operation steps, long time consumption, difficult recycling of an adsorbent and the like of the traditional solid-phase pretreatment method, the invention provides a magnetic fullerene nano-material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides, so as to realize high-selectivity adsorption, separation and detection of methyl methoxyacrylate pesticides such as azoxystrobin, pyraclostrobin, trifloxystrobin, fenpyroximate and the like in a detected sample.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention discloses a preparation method of a magnetic fullerene nano-material, which is characterized by comprising the following steps: first Fe by tetraethylorthosilicate TEOS 3 O 4 Modifying the nano particles to obtain silicon dioxide coated ferroferric oxide superparamagnetic particles, and marking the particles as Fe 3 O 4 @SiO 2 Nanoparticles; then Fe 3 O 4 @SiO 2 The nano particles react with 3-chloropropyltrimethoxysilane to obtain Fe 3 O 4 @SiO 2 @ Cl nanoparticles; finally, the fullerene C is added 60 Reacting with benzaldehyde and benzylamine to obtain 2, 5-diphenyl fullerene pyrroline, and reacting with Fe 3 O 4 @SiO 2 Reaction of @ Cl nano particles to obtain magnetic fullerene nano material, marked as Fe 3 O 4 @SiO 2 @C 60 Nanoparticles.
The synthetic route of the invention is as follows:
Figure BDA0002570677850000021
the preparation method of the magnetic fullerene nano-material specifically comprises the following steps:
step 1, adding Fe 3 O 4 Dispersing the nanoparticles in isopropanol water solution, ultrasonically dispersing for 15min, introducing nitrogen, transferring to room temperature, and stirring; then adding ammonia water with the mass concentration of 26%, stirring for 5min, adding tetraethyl orthosilicate, heating to 45 ℃, and stirring for 12h; magnetically separating the product, washing and drying to obtain Fe 3 O 4 @SiO 2 Nanoparticles; the cleaning is preferably performed by sequentially using deionized water and ethanol; the drying is carried out for 12h under vacuum at 60 ℃.
Step 2, mixing the Fe 3 O 4 @SiO 2 Dissolving the nanoparticles in toluene, introducing nitrogen gas, and stirring at room temperature for 30min; then triethylamine and 3-chloropropyltris addedHeating methoxysilane to 110 ℃, and continuing to react for 24 hours; cooling to room temperature, magnetically separating the product, washing and drying to obtain Fe 3 O 4 @SiO 2 @ Cl nanoparticles; the cleaning is preferably performed by sequentially using deionized water and ethanol; the drying is carried out for 12h under vacuum at 60 ℃.
Step 3, adding C 60 Adding benzaldehyde and benzylamine into o-dichlorobenzene, and dissolving by ultrasonic waves; then reacting for 6 hours at the temperature of 160 ℃ with stirring; cooling to room temperature, filtering out insoluble impurities through silica gel, and performing rotary evaporation under a vacuum condition until the insoluble impurities are dry; and dissolving the obtained residue by using carbon disulfide, and leaching the residue by using carbon disulfide and toluene through a silica gel column to obtain the 2, 5-diphenyl fullerene pyrroline.
Step 4, adding Fe 3 O 4 @SiO 2 Dissolving the @ Cl nano particles in toluene, introducing a nitrogen gas chamber, and stirring at a high temperature for 30min; then adding triethylamine and 2, 5-diphenyl fullerene pyrroline, continuing to react for 4 hours at room temperature, and then heating to 110 ℃ for reaction for 12 hours; stopping reaction, cooling to room temperature, cleaning and drying to obtain the target product Fe 3 O 4 @SiO 2 @C 60 Nanoparticles. The cleaning is preferably performed by sequentially using toluene, ethanol water solution and ethanol; the drying is carried out for 12h under vacuum at 60 ℃.
Preferably, in step 1 and step 2, fe 3 O 4 The dosage ratio of the nano particles, isopropanol, water, ammonia water, tetraethyl orthosilicate, toluene, triethylamine and 3-chloropropyltrimethoxysilane is 1g:100mL of: 8mL of: 10mL of: 8mL of: 100mL of: 1mL:2mL.
Preferably, in step 3, C 60 The dosage ratio of benzaldehyde, benzylamine and o-dichlorobenzene is 0.5mmol:2.5mmol:2.5mmol:60mL.
Preferably, in step 4, fe 3 O 4 @SiO 2 The dosage ratio of the @ Cl nano particles to the toluene to the triethylamine to the 2, 5-diphenyl fullerene pyrroline is 2g:80mL of: 1mL of: 1g.
The magnetic fullerene nano material prepared by the invention can be used as a magnetic dispersion solid phase extraction adsorbent for magnetic dispersion solid phase extraction of methoxy methyl acrylate pesticides in water samples or fruit and vegetable samples, and comprises the following steps:
step 1, extraction
The water sample extraction method comprises the following steps: sucking 1mL of water sample to be detected into a 15mL pointed-bottom centrifuge tube, adding 9mL of ultrapure water, uniformly mixing, adding 30mg of the magnetic fullerene nano material, and performing oscillation extraction for 20min; gathering the magnetic fullerene nano-material to the bottom by using a magnet, and pouring all the solution;
the fruit and vegetable sample extraction method comprises the following steps: weighing 2g of fruit and vegetable samples to be detected, putting the fruit and vegetable samples into a 50mL plastic centrifuge tube, adding 20mL acetonitrile, and homogenizing and extracting for 1min at 15000r/min on a high-speed tissue triturator; centrifuging at 10000r/min for 5min, sucking 1mL of supernatant into a 15mL pointed-bottom centrifuge tube, adding 9mL of ultrapure water, mixing uniformly, adding 30mg of the magnetic fullerene nano material, and performing oscillation extraction for 20min; gathering the magnetic fullerene nano-material to the bottom by using a magnet, and pouring all the solution;
step 2, elution
Adding 1mL of ethyl acetate solution into a centrifugal tube in which the magnetic fullerene nano material is positioned, and carrying out desorption by vortex for 1min; transferring the clear liquid into a new centrifugal tube after magnetic separation by a magnet;
the desorption operation is repeated for 2 times, all desorption solutions are combined and collected in a test tube, and then the magnetic dispersion solid-phase extraction of the methoxy methyl acrylate pesticides in the water sample or the fruit and vegetable sample is completed;
step 3, detecting
The obtained analytic solution can be used for UHPLC-MS/MS analysis, so that the concentration of the methoxy methyl acrylate pesticide in the water sample to be detected can be determined.
Compared with the prior art, the invention has the beneficial effects that:
the magnetic fullerene nano material (Fe) synthesized by the invention 3 O 4 @SiO 2 @C 60 Nano particles) has strong adsorbability to methyl methoxyacrylate pesticides, large adsorption capacity, good selectivity and easy elution, can be used for magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides, has the advantages of quick method, repeatedly usable materials and saved sample pretreatment time and cost. The method is sensitive and has high accuracy by combining UHPLC-MS/MS analysis。
Drawings
FIG. 1 shows Fe obtained in example 1 of the present invention 3 O 4 @SiO 2 @C 60 Scanning electron micrographs of nanoparticles.
FIG. 2 shows Fe in example 1 of the present invention 3 O 4 Nanoparticles, fe 3 O 4 @SiO 2 Nanoparticles, C 60 And Fe 3 O 4 @SiO 2 @C 60 Infrared spectrum of the nanoparticles.
FIG. 3 is a liquid chromatography triple quadrupole tandem mass spectrometry chromatogram of azoxystrobin (azoxystrobin), pyraclostrobin (pyraclostatin), trifloxystrobin (Trifloxystrobin), and fenpyroximate (fenpyroximate) of the present invention.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
This example prepares Fe as follows 3 O 4 @SiO 2 @C 60 Nanoparticle:
step 1, adding 1g of Fe 3 O 4 Dispersing the nano particles in 100mL of isopropanol and 8mL of water, ultrasonically dispersing for 15min, introducing nitrogen, transferring to room temperature, and stirring; then adding 10mL of ammonia water with the mass concentration of 26%, stirring for 5min, adding 8mL of tetraethyl orthosilicate, heating to 45 ℃, and stirring for 12h; magnetically separating the product, sequentially washing with deionized water and ethanol, and vacuum drying at 60 deg.C for 12 hr to obtain Fe 3 O 4 @SiO 2 Nanoparticles;
step 2, synthesizing the Fe synthesized in the step 1 3 O 4 @SiO 2 Dissolving the nano particles in 100mL of toluene, introducing a nitrogen gas, and stirring for 30min at a constant temperature; then adding 1mL of triethylamine and 2mL of 3-chloropropyltrimethoxysilane, heating to 110 ℃, and continuing to react for 24 hours; cooling to room temperature, magnetically separating the product, sequentially washing with deionized water and ethanol, and vacuum drying at 60 deg.C for 12 hr to obtain Fe 3 O 4 @SiO 2 @ Cl nanoparticles;
step 3, adding C 60 (360mg, 0.5 mmol), benzaldehyde (2.5 mmol) and benzylamine (2.5 mmol) are added into 60mL o-dichlorobenzene and dissolved by ultrasound; then reacting for 6 hours at the temperature of 160 ℃ with stirring; cooling to room temperature, filtering out insoluble impurities through silica gel, and performing rotary evaporation under a vacuum condition until the insoluble impurities are dry; dissolving the obtained residue with carbon disulfide, and eluting with carbon disulfide and toluene through a silica gel column to obtain 2, 5-diphenyl fullerene pyrroline;
step 4, adding 2g of Fe 3 O 4 @SiO 2 Dissolving the @ Cl nano particles in 80mL of toluene, introducing a nitrogen gas, and stirring at a room temperature for 30min; then adding 1mL of triethylamine and 1g of 2, 5-diphenyl fullerene pyrroline, continuing to react for 4 hours at room temperature, and then heating to 110 ℃ for reaction for 12 hours; stopping reaction, cooling to room temperature, sequentially washing with toluene, ethanol water solution and ethanol, and drying at 60 ℃ under vacuum for 12h to obtain the target product Fe 3 O 4 @SiO 2 @C 60 Nanoparticles.
FIG. 1 shows Fe obtained in this example 3 O 4 @SiO 2 @C 60 Scanning electron micrographs of nanoparticles. FIG. 2 shows Fe in this example 3 O 4 Nanoparticles, fe 3 O 4 @SiO 2 Nanoparticles, C 60 And Fe 3 O 4 @SiO 2 @C 60 Infrared spectrum of the nanoparticles.
Example 2
This example prepares Fe as follows 3 O 4 @SiO 2 @C 60 Nanoparticle:
step 1, 2g of Fe 3 O 4 Dispersing the nano particles in 200mL of isopropanol and 16mL of water, ultrasonically dispersing for 15min, introducing nitrogen, transferring to room temperature, and stirring; then adding 20mL of ammonia water with the mass concentration of 26%, stirring for 5min, adding 16mL of tetraethyl orthosilicate, heating to 45 ℃, and stirring for 12h; magnetically separating the product, sequentially washing with deionized water and ethanol, and vacuum drying at 60 deg.C for 12 hr to obtain Fe 3 O 4 @SiO 2 Nanoparticles;
step 2, synthesizing the Fe synthesized in the step 1 3 O 4 @SiO 2 Dissolving the nano particles in 200mL of toluene, introducing a nitrogen gas, and stirring for 30min at a constant temperature; then adding 2mL of triethylamine and 4mL of 3-chloropropyltrimethoxysilane, heating to 110 ℃, and continuing to react for 24h; cooling to room temperature, magnetically separating the product, sequentially washing with deionized water and ethanol, and vacuum drying at 60 deg.C for 12 hr to obtain Fe 3 O 4 @SiO 2 @ Cl nanoparticles;
step 3, adding C 60 (720mg, 1mmol), benzaldehyde (5 mmol) and benzylamine (5 mmol) were added to 120mL of o-dichlorobenzene and dissolved by ultrasonic; then reacting for 6 hours at the temperature of 160 ℃ with stirring; cooling to room temperature, filtering out insoluble impurities through silica gel, and performing rotary evaporation under a vacuum condition until the insoluble impurities are dry; dissolving the obtained residue with carbon disulfide, and eluting with carbon disulfide and toluene through a silica gel column to obtain 2, 5-diphenyl fullerene pyrroline;
step 4, adding 4g of Fe 3 O 4 @SiO 2 Dissolving the @ Cl nano particles in 160mL of toluene, introducing a nitrogen gas, and stirring at a room temperature for 30min; then adding 2mL of triethylamine and 2g of 2, 5-diphenyl fullerene pyrroline, continuing to react for 4 hours at room temperature, and then heating to 110 ℃ for reaction for 12 hours; stopping reaction, cooling to room temperature, sequentially cleaning with toluene, ethanol water solution and ethanol, and drying at 60 ℃ for 12h in vacuum to obtain the target product Fe 3 O 4 @SiO 2 @C 60 Nanoparticles.
Fe obtained in this example 3 O 4 @SiO 2 @C 60 The morphology and properties of the nanoparticles are similar to those of example 1.
Example 3 application example
Fe obtained in the above examples 3 O 4 @SiO 2 The @ Cl nano particle can be used as a magnetic dispersion solid phase extraction adsorbent for magnetic dispersion solid phase extraction of methoxy methyl acrylate pesticides in a water sample or a fruit and vegetable sample, and is combined with UHPLC-MS/MS analysis, so that the concentration of the methoxy methyl acrylate pesticides in the water sample or the fruit and vegetable sample to be detected is determined. The method comprises the following specific steps:
step 1, extraction
The method for extracting the environmental water sample comprises the following steps: 1mL of water sample to be detected is absorbed into a 15mL pointed-bottom centrifuge tube, 9mL of ultrapure water is added and mixed evenly, 30mg of the magnetic fullerene nano-material obtained in the previous embodiment is added, and oscillation extraction is carried out for 20min; gathering the magnetic fullerene nano material to the bottom by using a magnet, and pouring all the solution;
the fruit and vegetable sample extraction method comprises the following steps: weighing 2g of fruit and vegetable samples to be detected, putting the fruit and vegetable samples into a 50mL plastic centrifuge tube, adding 20mL acetonitrile, and homogenizing and extracting for 1min at 15000r/min on a high-speed tissue triturator; centrifuging at 10000r/min for 5min, sucking 1mL of supernatant into a 15mL pointed-bottom centrifuge tube, adding 9mL of ultrapure water, mixing uniformly, adding 30mg of the magnetic fullerene nano material obtained in the embodiment, and performing oscillation extraction for 20min; gathering the magnetic fullerene nano-material to the bottom by using a magnet, and pouring all the solution;
step 2, elution
Adding 1mL of ethyl acetate solution into a centrifugal tube in which the magnetic fullerene nano material is positioned, and carrying out desorption by vortex for 1min; transferring the clear liquid into a new centrifuge tube after magnetic separation by a magnet;
the desorption operation is repeated for 2 times, all desorption solutions are combined and collected in a test tube, and then the magnetic dispersion solid-phase extraction of the methoxy methyl acrylate pesticides in the water sample or the fruit and vegetable sample is completed;
step 3, detection
The obtained analytic solution can be used for UHPLC-MS/MS analysis, so that the concentration of the methoxy methyl acrylate pesticide in a water sample to be detected can be determined. The specific conditions are as follows:
(1) The desorption solution was blown dry with nitrogen and then made to volume through a 0.22 μm organic phase filter with 1mL of the initial mobile phase for UHPLC-MS/MS analysis.
(2) Liquid chromatography conditions: a column of ZORBAX Eclipse Plus C18 (2.1 mm. Times.50mm, 1.8 μm); mobile phase: the A phase was 0.05% (V/V) formic acid-water solution, and the B phase was acetonitrile. Flow rate: 0.3mL/min; column temperature: 40 ℃; the sample size was 10. Mu.L.
(3) Gradient elution procedure: 0min,5% of B;0.3min,5% by weight of B;2.5min,40% by volume B;6.5min,80% by volume B;8.5min,80% by volume B;8.51min,5% by weight of B;10min,5% B.
(4) Mass spectrum conditions: an ion source: electrospray ionization source (ESI), positive ion mode, ion source temperature 300 deg.C, electrospray voltage 4000V, atomizing gas pressure 40psi, drying gas temperature 300 deg.C, drying gas flow rate 10L/min, capillary voltage 3000V. MRM (multiple reaction monitoring) multiple reaction monitoring mode: the qualitative ion pair, quantitative ion pair, residence time, fragmentation voltage (FP) and collisional gas voltage (CE) are shown in Table 1.
TABLE 1 Multi-reaction monitoring mode (MRM) parameters for pesticides
Figure BDA0002570677850000061
In order to verify the sensitivity and accuracy of the method, the magnetic fullerene nano-material obtained in the embodiment 1 is used for extracting, eluting and detecting the standard solution of azoxystrobin, pyraclostrobin, trifloxystrobin and fenpyroximate with the known concentration of 0.001mg/L according to the method, and the extraction, elution and detection are repeated for 6 times, so that the recovery rates of 4 pesticides are all higher than 80%, and the indoor precision is less than 6%. The method comprises the steps of respectively adding 3 levels of azoxystrobin, pyraclostrobin, trifloxystrobin and fenpyroximate pesticides to an apple sample without methoxy methyl acrylate pesticides at 0.01mg/kg, 0.05mg/kg and 0.10mg/kg, carrying out recovery determination, repeating each level for 6 times, extracting, eluting and detecting by using the magnetic fullerene nano-material obtained in the embodiment 1 according to the method, wherein the results are shown in table 2, the recovery rates of 4 pesticides are higher than 60%, the indoor precision is less than 10%, and the detection methodology requirements are met.
Table 2 mean recovery and precision (n = 6) for 4 pesticides
Figure BDA0002570677850000062
Figure BDA0002570677850000071
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. The application of the magnetic fullerene nano material in the magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides is characterized in that the preparation method of the magnetic fullerene nano material comprises the following steps: first Fe by tetraethylorthosilicate TEOS 3 O 4 Modifying the nano particles to obtain silicon dioxide coated ferroferric oxide superparamagnetic particles, and marking the particles as Fe 3 O 4 @SiO 2 Nanoparticles; then Fe 3 O 4 @SiO 2 The nano particles react with 3-chloropropyltrimethoxysilane to obtain Fe 3 O 4 @SiO 2 @ Cl nanoparticles; finally, fullerene C is added 60 Reacting with benzaldehyde and benzylamine to obtain 2, 5-diphenyl fullerene pyrroline, and reacting with Fe 3 O 4 @SiO 2 Reaction of @ Cl nano particles to obtain magnetic fullerene nano material, marked as Fe 3 O 4 @SiO 2 @C 60 Nanoparticles.
2. Use according to claim 1, characterized in that: in the magnetic dispersion solid-phase extraction of methoxy methyl acrylate pesticides in a water sample or a fruit and vegetable sample, the magnetic fullerene nano material plays a role as a magnetic dispersion solid-phase extraction adsorbent.
3. The application of the magnetic fullerene nano-material as claimed in claim 1 or 2, wherein when the magnetic fullerene nano-material is used for magnetic dispersion solid phase extraction of methoxy methyl acrylate pesticides in a water sample, the method comprises the following steps:
step 1, extraction
Sucking 1mL of water sample to be detected into a 15mL pointed-bottom centrifuge tube, adding 9mL of ultrapure water, uniformly mixing, adding 30mg of the magnetic fullerene nano material, and performing oscillation extraction for 20min; gathering the magnetic fullerene nano-material to the bottom by using a magnet, and pouring all the solution;
step 2, elution
Adding 1mL of ethyl acetate solution into a centrifugal tube in which the magnetic fullerene nano material is positioned, and carrying out desorption by vortex for 1min; transferring the clear liquid into a new centrifugal tube after magnetic separation by a magnet;
the desorption operation is repeated for 2 times, all desorption solution is merged and collected in a test tube, and then the magnetic dispersion solid-phase extraction of the methoxy methyl acrylate pesticide in the water sample is completed;
step 3, detection
The obtained desorption solution is used for UHPLC-MS/MS analysis, so that the concentration of the methoxy methyl acrylate pesticide in the water sample to be detected is determined.
4. The application of the magnetic fullerene nano-material as claimed in claim 1 or 2, wherein when the magnetic fullerene nano-material is used for magnetic dispersion solid phase extraction of methoxy methyl acrylate pesticides in fruit and vegetable samples, the method comprises the following steps:
step 1, extraction
Weighing 2g of fruit and vegetable samples to be detected, putting the fruit and vegetable samples into a 50mL plastic centrifuge tube, adding 20mL acetonitrile, and homogenizing and extracting for 1min at 15000r/min on a high-speed tissue triturator; centrifuging at 10000r/min for 5min, sucking 1mL of supernatant into a 15mL pointed-bottom centrifuge tube, adding 9mL of ultrapure water, mixing uniformly, adding 30mg of the magnetic fullerene nano material, and performing oscillation extraction for 20min; gathering the magnetic fullerene nano-material to the bottom by using a magnet, and pouring all the solution;
step 2, elution
Adding 1mL of ethyl acetate solution into a centrifugal tube in which the magnetic fullerene nano material is positioned, and carrying out desorption by vortex for 1min; transferring the clear liquid into a new centrifuge tube after magnetic separation by a magnet;
the desorption operation is repeated for 2 times, all desorption solutions are combined and collected in a test tube, and then the magnetic dispersion solid-phase extraction of the methoxy methyl acrylate pesticides in the fruit and vegetable samples is completed;
step 3, detecting
The obtained desorption solution is used for UHPLC-MS/MS analysis, so that the concentration of the methoxy methyl acrylate pesticide in the water sample to be detected is determined.
5. Use according to claim 1, characterized in that: the preparation method of the magnetic fullerene nano-material specifically comprises the following steps:
step 1, adding Fe 3 O 4 Dispersing the nanoparticles in isopropanol water solution, ultrasonically dispersing for 15min, introducing nitrogen, cooling to room temperature, and stirring; then adding ammonia water with the mass concentration of 26%, stirring for 5min, adding tetraethyl orthosilicate, heating to 45 ℃, and stirring for 12h; magnetically separating the product, washing and drying to obtain Fe 3 O 4 @SiO 2 Nanoparticles;
step 2, mixing the Fe 3 O 4 @SiO 2 Dissolving the nanoparticles in toluene, introducing nitrogen gas, and stirring at room temperature for 30min; adding triethylamine and 3-chloropropyltrimethoxysilane, heating to 110 ℃, and continuing to react for 24 hours; cooling to room temperature, magnetically separating the product, washing and drying to obtain Fe 3 O 4 @SiO 2 @ Cl nanoparticles;
step 3, adding C 60 Adding benzaldehyde and benzylamine into o-dichlorobenzene, and dissolving by ultrasonic waves; then reacting for 6 hours at the temperature of 160 ℃ with stirring; cooling to room temperature, filtering out insoluble impurities through silica gel, and performing rotary evaporation under a vacuum condition until the insoluble impurities are dry; dissolving the obtained residue with carbon disulfide, and eluting with carbon disulfide and toluene through a silica gel column to obtain 2, 5-diphenyl fullerene pyrroline;
step 4, adding Fe 3 O 4 @SiO 2 Dissolving the @ Cl nano particles in toluene, introducing a nitrogen gas chamber, and stirring at a high temperature for 30min; adding triethylamine and 2, 5-diphenyl fullerene pyrroline, continuing to react for 4 hours at room temperature, and then heating to 110 ℃ for reaction for 12 hours; stopping reaction, cooling to room temperature, cleaning and drying to obtain the target product Fe 3 O 4 @SiO 2 @C 60 Nanoparticles.
6. Use according to claim 5, characterized in that: in step 1 and step 2, fe 3 O 4 The dosage ratio of the nano particles, isopropanol, water, ammonia water, tetraethyl orthosilicate, toluene, triethylamine and 3-chloropropyltrimethoxysilane is 1g:100mL of: 8mL of: 10mL of: 8mL of: 100mL of: 1mL of: 2mL.
7. Use according to claim 5, characterized in thatCharacterized in that: in step 3, C 60 The dosage ratio of benzaldehyde, benzylamine and o-dichlorobenzene is 0.5mmol:2.5mmol:2.5mmol:60mL.
8. Use according to claim 5, characterized in that: in step 4, fe 3 O 4 @SiO 2 The dosage ratio of the @ Cl nano particles, the toluene, the triethylamine and the 2, 5-diphenyl fullerene pyrroline is 2g:80mL of: 1mL of: 1g of the total weight of the composition.
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