CN111495332B - Magnetic adsorption material and application thereof in detection of benzoylurea insecticides - Google Patents
Magnetic adsorption material and application thereof in detection of benzoylurea insecticides Download PDFInfo
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Abstract
The invention provides a magnetic adsorption material and application thereof in the detection of benzoylurea insecticides, belonging to the technical field of nano materials and pesticide detection and analysis. The invention prepares a magnetic covalent organic framework material (NH) 2 ‑Fe 3 O 4 @ COFs), tests prove that the material can be used as a high-efficiency magnetic solid-phase extraction material to be applied to detection and analysis of benzoylurea insecticides in tea beverages, on the basis, a novel method for analyzing 6 benzoylurea insecticides in tea beverages by magnetic solid-phase extraction-liquid chromatography-tandem mass spectrometry is established, the method is good in reproducibility, wide in linear range, high in recovery rate, low in detection limit and capable of meeting detection requirements, and rapid analysis and determination of trace benzoylurea insecticides in tea beverages can be achieved, so that the material has good practical application value.
Description
Technical Field
The invention belongs to the technical field of detection and analysis of nano materials and pesticides, and particularly relates to a magnetic adsorption material and application thereof in detection of benzoylurea insecticides.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Benzoyl urea insecticides are known as third-generation insecticides or novel insect control agents, and are widely used in the pest control of tea trees in recent years due to their broad-spectrum and high-efficiency insecticidal activity. The benzoyl urea pesticide residue can cause damage to human health through a food chain, so that the establishment of the detection method of the benzoyl urea residue in the tea and the beverage thereof has very important significance.
Currently, liquid chromatography-tandem mass spectrometry has become the most effective method for detecting benzoylurea insecticides. Tea beverage matrices are complex and samples must be pre-processed before performing liquid chromatography-tandem mass spectrometry. Magnetic solid phase extraction is a novel solid phase extraction technology based on magnetic nano materials developed in recent years. The technology avoids the complicated column passing operation of the traditional solid phase extraction, and has the advantages of short extraction time, high recovery rate, high enrichment factor, low solvent consumption and the like. The inventor finds that the core part of the technology is the magnetic adsorption material, so that the continuous development of a novel magnetic solid phase extraction adsorption material has very important significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a magnetic adsorption material and application thereof in the detection of benzoylurea insecticides. The invention successfully prepares the magnetic covalent organic framework material (NH) 2 -Fe 3 O 4 @ COFs), through experimental verification, the material can be used as a high-efficiency magnetic solid-phase extraction material to be applied to detection and analysis of benzoylurea insecticides in tea beverages, has the advantages of small adsorbent dosage, short extraction time, high magnetic separation speed and the like, and has good practical application value.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:
in a first aspect of the present invention, a magnetic absorption material is provided, wherein the magnetic absorption material is NH 2 -Fe 3 O 4 @ COFs, the preparation method comprises: synthesis of NH 2 -Fe 3 O 4 (ii) a Based on NH by room temperature 2 -Fe 3 O 4 Synthesis of NH 2 -Fe 3 O 4 @COFs。
In a second aspect of the invention, the magnetic adsorption material is provided for use as a magnetic solid phase extraction adsorbent.
Specifically, the application comprises the detection and analysis of the benzoylurea insecticides in the tea beverage.
In a third aspect of the invention, there is provided a method for detecting a benzoylurea insecticide in a tea beverage, the method comprising: with the above NH 2 -Fe 3 O 4 @ COFs is used as a magnetic solid phase extraction adsorbent to carry out magnetic solid phase extraction on a sample to be detected; detection analysis was performed using liquid chromatography-tandem mass spectrometry.
The beneficial technical effects of one or more technical schemes are as follows:
the technical scheme successfully prepares the novel magnetic NH by utilizing a mild and simple room temperature method 2 -Fe 3 O 4 @ COFs materials. Amino-functionalized Fe 3 O 4 The magnetic microspheres are covalently connected with the COFs framework, so that the material has excellent magnetism and high specific surface area. Reacting NH 2 -Fe 3 O 4 The @ COFs is used as the adsorbent for magnetic solid phase extraction to extract benzoylurea insecticides in tea beverages, and compared with other food sample pretreatment methods based on the adsorption principle, the method is simpler and more convenient, wherein the obvious advantages are that the adsorbent dosage is less, the extraction time is obviously shortened, and the magnetic separation speed is higherFast, separation can be completed within 10 seconds.
On the basis, the technical scheme establishes a new method for analyzing 6 benzoylurea insecticides in the tea beverage by combining magnetic solid phase extraction-liquid chromatography-tandem mass spectrometry, the method has good reproducibility, wide linear range and high recovery rate, the detection limit is low, the detection requirement can be met, and the rapid analysis and determination of trace benzoylurea insecticides in the tea beverage can be realized, so that the method has good practical application value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings according to the provided drawings without creative efforts.
FIG. 1 shows NH in example 1 of the present invention 2 -Fe 3 O 4 And NH 2 -Fe 3 O 4 A profile of @ COFs; (a) an infrared spectrum; (b) an X-ray diffraction pattern; (c) nitrogen adsorption and desorption isotherms and pore size distribution maps; (d) hysteresis curve.
FIG. 2 is a typical chromatogram of 6 benzoylurea insecticides in a tea beverage according to example 1 of the present invention; (a) Blank sample, (b) adding 50ng L of label -1 ，(c)250ng L -1 ，(d)500ng L -1 (ii) a The pesticide composition comprises (1) chlorfluazuron, (2) triflumuron, (3) hexaflumuron, (4) teflubenzuron, (5) novaluron and (6) lufenuron.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As mentioned above, the continuous development of new magnetic solid phase extraction adsorption materials is of great significance. Covalent organic framework materials (COFs) are novel nano materials, are completely composed of light elements, have the characteristics of low framework density, large specific surface area, high porosity, uniform pore size distribution, controllable pore size, rich organic monomer types, flexible and various synthesis methods, functionalized surface chemical properties, high chemical stability and the like, and have wide application prospects in sample pretreatment. In view of the above, the present invention develops a magnetic covalent organic framework material NH 2 -Fe 3 O 4 @ COFs, and is used as a magnetic solid phase extraction adsorbent for detecting and analyzing the content of benzoylurea insecticides in tea beverages.
In one embodiment of the present invention, a magnetic absorption material is provided, wherein the magnetic absorption material is NH 2 -Fe 3 O 4 @ COFs, the preparation method comprises: synthesis of NH 2 -Fe 3 O 4 (ii) a Based on NH by room temperature 2 -Fe 3 O 4 Synthesis of NH 2 -Fe 3 O 4 @COFs。
In still another embodiment of the present invention, the NH 2 -Fe 3 O 4 The synthesis method comprises the following steps:
adding ferric trichloride, sodium acetate and hexamethylene diamine into ethylene glycol, and carrying out hydrothermal reaction to obtain NH 2 -Fe 3 O 4 ；
In another embodiment of the invention, the mass ratio of ferric trichloride, sodium acetate and hexamethylenediamine is 1-5; preferably 1;
in another embodiment of the present invention, the hydrothermal reaction conditions are specifically: reacting for 3 to 8 hours at 180 to 220 ℃, preferably for 6 hours at 200 ℃.
In another embodiment of the present invention, the synthesis method further comprises: after the reaction is finished, water and ethanol are used for alternately washing for 2-3 times, black precipitate is obtained through magnetic separation, and the black precipitate is obtained through drying.
In another embodiment of the present invention, the drying method is specifically vacuum drying at 50 ℃ for 12h.
In yet another embodiment of the present invention, the room temperature method is based on NH 2 -Fe 3 O 4 Synthesis of NH 2 -Fe 3 O 4 The specific method of @ COFs comprises the following steps:
reacting NH 2 -Fe 3 O 4 Adding 2, 5-dimethoxybenzene-1, 4-dimethyl aldehyde (DMTA) into the mixed solution of 1, 4-dioxane and mesitylene for dispersion, adding an acetic acid solution for reaction, then adding the mixed solution of 1,3, 5-tri (4-aminophenyl) benzene (TAPB) dispersed in 1, 4-dioxane and mesitylene into the solution, and reacting at room temperature to obtain the product.
In still another embodiment of the present invention, the NH 2 -Fe 3 O 4 The mass ratio of the DMTA to the DMTA is 1-5; preferably 4. In the present invention, NH is controlled by optimization 2 -Fe 3 O 4 The addition amount of the magnetic COFs material improves the yield of the magnetic COFs material, enhances the magnetism of the product and shortens the subsequent magnetic separation time.
In another embodiment of the present invention, the above synthesis method further comprises: after the reaction is finished, obtaining brown precipitate, separating the precipitate by magnetic force, and washing with methanol to remove impurities; drying to obtain the product.
In another embodiment of the present invention, the drying method is specifically vacuum drying at 60 ℃ for 12h.
In another embodiment of the present invention, the magnetic adsorbent is used as a magnetic solid phase extraction adsorbent.
In another embodiment of the present invention, the application comprises detecting and analyzing the benzoylurea insecticides in the tea beverage. The magnetic adsorption material prepared by the invention is very suitable for detecting trace and trace benzoyl urea insecticides in tea beverages, and can be repeatedly used for many times, thereby further reducing the detection cost.
In another embodiment of the present invention, there is provided a method for detecting benzoylurea insecticides in tea beverages, comprising: with the above NH 2 -Fe 3 O 4 @ COFs is used as a magnetic solid phase extraction adsorbent to carry out magnetic solid phase extraction on a sample to be detected; detection analysis was performed using liquid chromatography-tandem mass spectrometry.
In another embodiment of the present invention, in the magnetic solid phase extraction, the extraction conditions are specifically: the pH is 2 to 10, preferably weakly acidic, and more preferably 6.
In another embodiment of the present invention, the mass-to-volume ratio of the magnetic solid phase extraction adsorbent, the sample solution and the analysis solution is 5 to 20mg:10-50ml: 1-5 ml; preferably 10mg:40ml:3ml.
In yet another embodiment of the present invention, the resolving solution comprises methanol, acetonitrile, acetone, and n-hexane; methanol is preferred.
By controlling the parameter conditions, the dosage of the adsorbent can be obviously reduced, the extraction time is shortened, and the magnetic separation speed is accelerated.
In yet another embodiment of the present invention, the liquid chromatography conditions are C18 column: 2.1mm × 100mm,2.6 μm; mobile phase: phase A is 0.5mM ammonium acetate water, phase B is acetonitrile; gradient elution procedure: 0-7min, B phase rising from 50% to 85%,7-10min, B phase falling from 85% to 50%; flow rate: 0.4mL min-1; column temperature: 25 ℃; sample introduction amount: 10 μ L.
In yet another embodiment of the present invention, the mass spectrometry conditions are ion spray voltage: -4500V; source temperature: 500 ℃; curtain gas: 40psi; inlet voltage (EP): -10V; collision cell exit voltage: -13V; atomizer gas and turbine gas pressure: 50psi; the ion source gas 1 (GS 1) and the ion source gas 2 (GS 2) are both 50psi. Both the collision gas and the atomizing gas are nitrogen. The scanning mode adopts a multi-reaction monitoring mode.
In yet another embodiment of the present invention, the benzoylurea insecticides include, but are not limited to, chlorfluazuron, triflumuron, hexaflumuron, teflubenzuron, novaluron and lufenuron.
The present invention will be further described with reference to the following examples. The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Based on the embodiments of the present invention, those skilled in the art can change the present invention without making any creative changes.
Example 1
1 experimental part
1.1 Synthesis of the magnetically adsorbing Material
NH 2 -Fe 3 O 4 The synthesis of (2): accurately weighing 1.0g FeCl 3 ·6H 2 O,4.0g of anhydrous sodium acetate and 3.6g of hexamethylenediamine are added into 30ml of ethylene glycol, ultrasonic dispersion is carried out until a transparent solution is obtained, the transparent solution is transferred into a 50ml reaction kettle and reacts for 6 hours at 200 ℃, deionized water and ethanol are alternately washed for three times, and black precipitate is obtained through external magnetic separation. Vacuum drying at 50 deg.C for 12h to obtain NH 2 -Fe 3 O 4 。
Magnetic adsorbent (NH) 2 -Fe 3 O 4 @ COFs) at room temperature: in a 25ml round-bottom flask, 40mgNH was accurately weighed 2 -Fe 3 O 4 And 96mg2, 5-dimethoxybenzene-1, 4-Dimethylaldehyde (DMTA), 2.0ml of 1, 4-dioxane and 2.0ml of mesitylene were added, and after ultrasonic dispersion for 10min, 1.0ml of a 3M acetic acid solution was added dropwise. Ultrasonic reaction for 10min, a mixture of 1,3, 5-tris (4-aminophenyl) benzene (TAPB, 112 mg) dispersed in 2.0ml of 1, 4-dioxane and 2.0ml of mesitylene was added to the above solution, and reacted at room temperature for 20min to obtain a brown precipitate, which was separated by external magnetic force and washed several times with methanol to remove impurities. Vacuum drying at 60 deg.C for 12h to obtain NH 2 -Fe 3 O 4 @COFs。
1.2 conditions of liquid chromatography-tandem Mass Spectrometry
Liquid chromatography conditions C18 column: 2.1mm × 100mm,2.6 μm; mobile phase: phase A is 0.5mM ammonium acetate water, phase B is acetonitrile; gradient elution procedure: 0-7min, B phase rising from 50% to 85%,7-10min, B phase falling from 85% to 50%; flow rate: 0.4mL min -1 (ii) a Column temperature:25 ℃; sample introduction amount: 10 μ L.
Mass spectrum conditions ion spray voltage: -4500V; source temperature: 500 ℃; curtain gas: 40psi; inlet voltage (EP): -10V; collision cell exit voltage: -13V; atomizer gas and turbine gas pressure: 50psi; the ion source gas 1 (GS 1) and the ion source gas 2 (GS 2) are both 50psi. Both the collision gas and the atomizing gas are nitrogen. The scanning mode adopts a multi-reaction monitoring mode.
1.3 sample Collection and processing
Four primary taste tea beverages were purchased from local supermarkets, sample # 1, sample # 2, sample # 3 and sample # 4. As the purchased original tea drink is clear and transparent liquid in appearance, the filtration treatment is not needed. To reduce interference of other substances such as pigments, the sample concentration was diluted three times and the pH was adjusted to 6.0. The samples to be tested were stored in brown glass bottles at 4 ℃ until use.
1.5 magnetic solid phase extraction Process
Weighing 10mgNH 2 -Fe 3 O 4 @ COFs was added to 40ml of the solution to be tested, vortexed and shaken at room temperature for 10min, the mixture was separated by external magnetic force, the magnetic adsorbent was collected, 3ml of methanol was added, and ultrasonic analysis was performed for 1min. After the desorption solution is dried by nitrogen at 40 ℃, 0.5ml of water/acetonitrile solution (1, 1 v). The recovered adsorbent was washed with 3ml of methanol and water, respectively, and then used in the next experiment.
2 results and discussion
2.1NH 2 -Fe 3 O 4 Synthesis of @ COFs
In the experiment, NH 2 -Fe 3 O 4 @ COFs is synthesized using a simple and rapid room temperature method. The experiment optimizes the key parameter NH 2 -Fe 3 O 4 And (4) using the amount. When NH of the reaction system 2 -Fe 3 O 4 When the addition amount is 20mg, the generated magnetic COFs material is less, the magnetic separation time is longer (30 s), and the magnetism is weaker; increase of NH 2 -Fe 3 O 4 By 40mg, the time for magnetic separation is significantly shortened (10 s) and the magnetic properties are significantly enhanced. However, NH continues to increase 2 -Fe 3 O 4 Addition amount of (2) (60 mg), NH after reaction 2 -Fe 3 O 4 A residue appears. Thus, NH in the experiment 2 -Fe 3 O 4 The amount of (B) is selected to be 40mg.
2.2NH 2 -Fe 3 O 4 Characterization of @ COFs
COFs，NH 2 -Fe 3 O 4 And NH 2 -Fe 3 O 4 The infrared spectrum of @ COFs is shown in FIG. 1a, at NH 2 -Fe 3 O 4 The spectrum of @ COFs, 1615cm -1 And 1587cm -1 The absorption peaks of C = N and C = C, respectively, are consistent with the characteristic absorption peaks in the non-magnetic COFs spectra, indicating that schiff base reaction has occurred between the monomers and a covalent organic framework structure is formed. Furthermore, NH 2 -Fe 3 O 4 @ COFs spectrogram of 569cm -1 Fe-O absorption peak and NH of 2 -Fe 3 O 4 Identity, NH 2 -Fe 3 O 4 1482and 872cm in spectrogram -1 Characteristic absorption peak, indicating Fe 3 O 4 The surface has been functionally modified with amino groups. Thus, the results of the infrared spectroscopy data indicate that NH was successfully synthesized by covalent attachment 2 -Fe 3 O 4 @COFs。
NH 2 -Fe 3 O 4 The @ COFs diffraction peaks (2 θ =2.78,4.80,5.57,7.39, 30.1, 35.3 and 62.5 °) confirm that it has a very good crystalline structure (as in fig. 1 b). NH (NH) 2 -Fe 3 O 4 @ COFs having a specific surface area of 140.2m 2 g -1 (FIG. 1 c), pore volume 0.21cm 3 g -1 。NH 2 -Fe 3 O 4 @ COFs and NH 2 -Fe 3 O 4 The magnetization values of the magnetic particles are respectively 58.2emu g -1 And 94.2emu g -1 The results show that both have good superparamagnetism, and rapid separation can be realized.
2.3 optimization of magnetic solid-phase extraction conditions
NH 2 -Fe 3 O 4 @ COFs is used as magnetic solid phase extraction adsorbent and is combined with liquid chromatography-tandem mass spectrometry to measure 6 benzaldehydes in tea beverageUreides as insecticides. The extraction conditions (adsorbent amount, extraction time, sample volume and pH) and desorption conditions (type and volume of eluent) were optimized for optimal experimental parameters. Work Using the recovery of 6 benzoylurea insecticides to evaluate NH 2 -Fe 3 O 4 The extraction effect of the @ COFs material on the benzoylurea insecticides.
In this experiment, the effect of four different addition levels (5, 10, 15 and 20 mg) on the recovery of 6 benzoylurea insecticides was investigated. The experimental results show that: when the dosage of the adsorbent is 5mg, the recovery rate of the florfenicol is higher than 80 percent. When the dosage of the adsorbent is 10mg, the recovery rate of the 6 benzoyl urea insecticides is improved along with the dosage of the adsorbent; however, the recovery remained stable during the increase in adsorbent dosage from 10mg to 20 mg. Therefore, 10mgNH was chosen in the following experiments 2 -Fe 3 O 4 @ COFs as adsorbents.
The effect of adsorption time on recovery within 5-40min was investigated. The experimental data show that when the adsorption time is 10min, the recovery rate of the 6 benzoyl urea insecticides reaches the peak value; within 10-40min, the recovery rate is not obviously changed. Therefore, the adsorption time for this experiment was determined to be 10min.
Methanol, acetonitrile, acetone and n-hexane were chosen as resolving solutions for the experiment. The experimental result shows that in the 4 solvents, the elution performance of methanol and acetone on 6 benzoyl urea insecticides is better than that of acetonitrile, and the elution capability of n-hexane is the lowest. Therefore, methanol was selected as the analytical solution in the experiment. In addition, the volume of the methanol is optimized in the experiment, when the volume of the analysis solution is gradually increased from 1ml to 3ml, the recovery rate of the 6 benzoylurea insecticides is gradually increased, the volume of the methanol is continuously increased, and the recovery rate is kept unchanged. Therefore, the volume of methanol was finally determined to be 3ml.
The influence of different sample pH values (2-10) on the extraction efficiency of 6 benzoyl urea insecticides is researched in the experiment. The experimental results show that the recovery rate gradually increases when the pH value increases from 2 to 6, and the recovery rate is highest when the pH value is 6, and the recovery rate decreases along with the increase of the pH value of the solution. Thus, the pH of the sample solution was selected to be 6.
In the present invention, the effect of five different sample volumes (10ml, 20ml,30ml,40ml, 50ml) on the recovery rate of 6 benzoylurea insecticides was studied. The experimental results show that with the same amount of adsorbent and other factors, the recovery of 6 benzoylurea insecticides (0.01 μ g) decreased with increasing sample volume, and the time for magnetic separation was found to increase with increasing sample volume. Therefore, in order to secure the extraction effect and save the separation time, the experiment determined the volume of the sample solution to be 40ml.
Finally, the optimal conditions of the magnetic solid phase extraction are determined as follows: the dosage of the adsorbent is 10mg, the adsorption time is 10min, the analytical solution is 3ml of methanol, the pH value of the sample solution is 6, and the volume of the sample solution is 40ml.
2.4NH 2 -Fe 3 O 4 Study on number of times of recycling of @ COFs
NH 2 -Fe 3 O 4 @ COFs is used as a magnetic solid phase extraction adsorbent, and the number of times of recycling is studied in the experiment. The recovery rate of 6 benzoyl urea insecticides is 80-110% in the previous 9 circulation tests, but the recovery rate of novaluron and lufenuron is reduced to below 80% after the 10 th circulation. Thus, the adsorbent NH was present in this experiment 2 -Fe 3 O 4 @ COFs are cyclically used 9 times.
2.5 methodological parameters
The experimental data show that the concentration of 6 benzoyl urea insecticides is 10-1000 ng L -1 Has a good linear relationship in the concentration range of (A), R 2 Is 0.9977-0.9999. The detection limit is 0.06-1.65 ngL when the signal-to-noise ratio S/N =3 is measured -1 (ii) a The quantitative limit of the method is 0.19-5.49 ng L by using the S/N =10 of the signal-to-noise ratio -1 . The relative standard deviations between daytime (n = 5) and daytime (n = 5) are 2.0 to 6.4% and 2.3 to 6.2%, respectively.
2.6 method applications
To verify the applicability of the new method, 4 primary taste tea beverages were selected for analysis. The content of hexaflumuron, novaluron and lufenuron in sample 1 was 11.1, 11.9 and 7.1ng L, respectively -1 (ii) a Sample(s)2 the content of hexaflumuron and lufenuron is 21.5 ng L and 15.2ng L respectively -1 (ii) a The lufenuron content in sample 3 was 5.9ng L -1 .4 samples at 50, 250 and 500ng L -1 The recovery rate of the concentration is 80.1-109.3%, and the relative standard deviation is less than 8.8%. Figure 2 shows a typical chromatogram for a tea beverage. The above results indicate that NH 2 -Fe 3 O 4 The @ COF is used as an adsorbent for magnetic solid phase extraction, has good adsorption effect on 6 benzoylurea insecticides in tea beverages, is not influenced by pigments and other interferents in the tea beverages in the adsorption process, and can be used for measuring trace benzoylurea insecticides in different tea beverages.
The invention successfully prepares the novel magnetic NH by utilizing a mild and simple room temperature method 2 -Fe 3 O 4 @ COFs materials. Amino-functionalised Fe 3 O 4 The magnetic microspheres are covalently connected with the COFs framework, so that the material has excellent magnetism and high specific surface area. Reacting NH 2 -Fe 3 O 4 The @ COFs is used as the adsorbent for magnetic solid phase extraction to extract the benzoylurea insecticides in the tea beverage, and compared with other food sample pretreatment methods based on the adsorption principle, the method is simpler and more convenient, wherein the obvious advantages are that the adsorbent dosage is less, the extraction time is obviously shortened, the magnetic separation speed is higher, and the separation can be completed within 10 seconds. On the basis, a novel method for analyzing 6 benzoylurea insecticides in tea beverages by magnetic solid phase extraction-liquid chromatography-tandem mass spectrometry is established, the method is good in reproducibility, wide in linear range, high in recovery rate and low in detection limit, can meet the detection requirement, and can realize rapid analysis and determination of trace benzoylurea insecticides in tea beverages.
It should be noted that the above examples are only used to illustrate the technical solution of the present invention and not to limit it. Although the present invention has been described in detail with reference to the examples given, it will be apparent to those skilled in the art that modifications and equivalents can be made thereto without departing from the spirit and scope of the invention as set forth in the appended claims.
Claims (18)
1.The magnetic adsorption material is characterized in that the magnetic adsorption material is NH 2 -Fe 3 O 4 @ COFs, the preparation method comprises: synthesis of NH 2 -Fe 3 O 4 (ii) a Based on NH by room temperature method 2 -Fe 3 O 4 Synthesis of NH 2 -Fe 3 O 4 @COFs；
Based on NH by room temperature 2 -Fe 3 O 4 Synthesis of NH 2 -Fe 3 O 4 Specific methods of @ COFs include: reacting NH 2 -Fe 3 O 4 Adding 2, 5-dimethoxybenzene-1, 4-dimethyl aldehyde DMTA into the mixed solution of 1, 4-dioxane and mesitylene for dispersion, adding an acetic acid solution for reaction, then adding the mixed solution of 1,3, 5-tri (4-aminophenyl) benzene dispersed in 1, 4-dioxane and mesitylene into the solution, and reacting at room temperature to obtain the product.
2. The magnetically adsorptive material of claim 1, wherein said NH 2 -Fe 3 O 4 The synthesis method comprises the following steps:
adding ferric trichloride, sodium acetate and hexamethylene diamine into ethylene glycol, and carrying out hydrothermal reaction to obtain NH 2 -Fe 3 O 4 。
3. The magnetic adsorption material according to claim 2, wherein the mass ratio of ferric trichloride to sodium acetate to hexamethylenediamine is 1-5;
the hydrothermal reaction conditions are as follows: reacting for 3-8 h at 180-220 ℃.
4. The magnetic adsorbent material according to claim 3, wherein the mass ratio of ferric trichloride, sodium acetate and hexamethylenediamine is 1; the hydrothermal reaction conditions are as follows: reacting for 6h at 200 ℃.
5. The magnetically attractable material of claim 2, wherein the method of synthesizing further comprises: after the reaction is finished, water and ethanol are used for alternately washing for 2-3 times, black precipitate is obtained through magnetic separation, and the black precipitate is obtained through drying.
6. The magnetically adsorptive material of claim 1, wherein said NH 2 -Fe 3 O 4 The mass ratio of the dimethyl acetal to 2, 5-dimethoxybenzene-1, 4-diformaldehyde DMTA is 1-5.
7. The magnetically attractable material of claim 6, wherein the mass ratio of NH2-Fe3O4 to 2, 5-dimethoxybenzene-1, 4-dimethaldehyde DMTA is 4.
8. The magnetically adsorptive material of claim 6, wherein the synthesis method further comprises: after the reaction is finished, obtaining brown precipitate, separating the precipitate by magnetic force, and washing with methanol to remove impurities; drying to obtain the product.
9. Use of the magnetically attractable material according to any one of claims 1-8 as a sorbent for magnetic solid phase extraction.
10. The use of the magnetic adsorbent material of claim 9 as an adsorbent for magnetic solid phase extraction, wherein the use comprises detection and analysis of benzoylurea insecticides in tea beverages.
11. A method for detecting benzoylurea insecticides in a tea beverage, the method comprising: performing magnetic solid phase extraction on a sample to be detected by using the magnetic adsorption material as claimed in any one of claims 1 to 8 as a magnetic solid phase extraction adsorbent; detection analysis was performed using liquid chromatography-tandem mass spectrometry.
12. The method according to claim 11, wherein in magnetic solid phase extraction, the extraction conditions are in particular: the pH is 2-10;
the mass-volume ratio of the magnetic solid phase extraction adsorbent to the sample solution to the analytic solution is 5-20 mg:10-50ml: 1-5 ml;
the analysis solution comprises methanol, acetonitrile, acetone and n-hexane.
13. The method of claim 11, wherein the extraction conditions are mildly acidic.
14. The method of claim 11, wherein the pH is 6.
15. The method of claim 11, wherein the mass to volume ratio of the magnetic solid phase extraction adsorbent, the sample solution, and the resolving fluid is 10mg:40ml:3ml.
16. The method of claim 11, wherein the resolving solution is methanol.
17. The method of claim 11, wherein the liquid chromatography conditions are C18 column: 2.1mm × 100mm,2.6 μm; mobile phase: phase A is 0.5mM ammonium acetate water, phase B is acetonitrile; gradient elution procedure: 0-7min, B phase is increased from 50% to 85%,7-10min, B phase is decreased from 85% to 50%; flow rate: 0.4mL min-1; column temperature: 25 ℃; sample injection amount: 10 mu L of the solution;
mass spectrum conditions ion spray voltage: -4500V; source temperature: 500 ℃; curtain gas: 40psi; inlet voltage: -10V; collision cell exit voltage: -13V; atomizer gas and turbine gas pressure: 50psi; the ion source gas 1 and the ion source gas 2 are both 50psi; the collision gas and the atomization gas are both nitrogen; the scanning mode adopts a multi-reaction monitoring mode.
18. The method of claim 11, wherein the benzoylurea insecticide comprises chlorfluazuron, triflumuron, hexaflumuron, teflubenzuron, novaluron and lufenuron.
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