CN112807744A - Magnetic dispersion solid phase extraction material for enriching pesticide and veterinary drug residues and preparation method thereof - Google Patents
Magnetic dispersion solid phase extraction material for enriching pesticide and veterinary drug residues and preparation method thereof Download PDFInfo
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- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
本发明涉及一种富集农兽药残留的磁性分散固相萃取材料及其制备方法，结构式如图。载体可为磺化、氨基化、羧基化、巯基化的含有苯环结构的聚合物为反应物，选择功能化聚苯化合物微球，采用静电吸附法一步制备一系列具有磁性的分散固相萃取材料。该磁性分散固相萃取材料具有粒度分布均一、水溶液中悬浮性好、比表面积大、吸附性好、表面反应能力强、制备简单和使用方便等优势。本发明可快速富集农兽药，富集方法具有灵敏度高、选择性好、耗时短等特点。式1一种功能化聚苯化合物结构示意图其中：
The invention relates to a magnetic dispersion solid phase extraction material for enriching pesticide and veterinary drug residues and a preparation method thereof. The structural formula is as shown in the figure. The carrier can be a sulfonated, aminated, carboxylated, or thiolated polymer containing a benzene ring structure as a reactant, and functionalized polyphenylene compound microspheres are selected to prepare a series of magnetic dispersion solid phase extraction by one step by electrostatic adsorption. Material. The magnetic dispersion solid phase extraction material has the advantages of uniform particle size distribution, good suspension in aqueous solution, large specific surface area, good adsorption, strong surface reaction ability, simple preparation and convenient use. The invention can quickly enrich the agricultural and veterinary drugs, and the enrichment method has the characteristics of high sensitivity, good selectivity, short time-consuming and the like. 
A schematic structural diagram of a functionalized polyphenylene compound of formula 1 wherein:
Description
Technical Field
The invention belongs to the field of food safety, and relates to a magnetic dispersion solid-phase extraction material for enriching veterinary drug residues and a preparation method thereof.
Background
The veterinary drug plays an important role in preventing and treating animal diseases, improving production efficiency, improving quality of animal products and the like. However, the phenomenon of veterinary drug abuse is now widespread in animal husbandry due to the lack of scientific knowledge and the pursuit of economic interest for breeders. The abuse of veterinary drugs easily causes the residue of harmful substances in animal-derived foods, which not only causes direct harm to human health, but also causes great harm to the development of animal husbandry and ecological environment. Therefore, establishing a rapid and efficient veterinary drug residue detection method has important significance in the aspects of life science, environmental science, medical science, agricultural production and the like.
The instrumental technique is widely used in the analysis and treatment of samples as the method for detecting veterinary drug residues. At the same time, however, with the outbreak of various food safety incidents, the demand for sample analysis techniques has been increasing. And due to the complexity of the sample matrix, the detection of trace, trace and even ultra-trace pollutants in the sample is difficult to directly measure, the accuracy is difficult to meet the requirement, and the damage to the instrument is large. Therefore, the pretreatment processes of purification, decontamination, separation, enrichment and concentration before the sample is detected by the instrument are particularly important.
The sample pretreatment technology is a technology for extracting, purifying and concentrating a sample by using a proper method or converting a component to be detected in a sample matrix into a measurable form by using a physical or chemical method so as to separate the component to be detected from impurities and further perform qualitative and quantitative analysis in order to eliminate the influence of interference components existing in the sample matrix on a measurement process. The method is a core part of detection and analysis, is a bottleneck of the whole analysis process, and is an important step for measuring the feasibility of the detection method.
The solid phase extraction method in the sample pretreatment technology is still used as a main sample pretreatment means through continuous improvement and is developed into a universal sample pretreatment technology due to the advantages of simple operation, less use of organic solvents and the like from birth in eighties to the present. But at the same time, the method also has the defects of long time consumption and the like.
The magnetic dispersion solid phase extraction material has the characteristics of simple preparation method, low price, convenient use, rapid enrichment and detection of veterinary drug residues in a sample, great shortening of sample pretreatment time and the like.
Currently, the most widely used solid phase extraction materials are microspheres with different functions prepared by functionalizing different groups on the surface of a polyphenolic compound microsphere. The ferroferric oxide nano particles are high-quality magnetic substances, have excellent magnetism, and can quickly separate solid from liquid by using a magnetic separation technology.
Disclosure of Invention
The invention aims to provide a magnetic dispersion solid-phase extraction material for enriching pesticide and veterinary drug residues and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
placing a polymer containing a benzene ring structure and a functionalizing agent into a flask according to a certain molar ratio, heating, stirring, refluxing and reacting, washing reactants with methanol and water for several times after the reaction is finished, performing suction filtration, and drying in vacuum to constant weight to obtain the functionalized polyphenyl compound microsphere.
And then placing the functionalized polyphenyl compound microspheres and ferroferric oxide in a flask according to a certain molar ratio, adding ultrapure water to adjust the pH, washing the reactant with the ultrapure water after the reaction is finished, and drying in vacuum to constant weight to obtain the magnetic dispersed solid-phase extraction material.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
(1) The method for preparing the sulfonated polyphenyl compound microspheres comprises the following steps: mixing polymer microspheres containing benzene ring structures and concentrated sulfuric acid, placing the mixture in a flask, heating, stirring, refluxing and reacting, washing reactants with ethanol and ultrapure water for a plurality of times after the reaction is finished, soaking the reactants with ultrapure water overnight, filtering, and drying the reactants in vacuum to constant weight to obtain the sulfonated polyphenyl compound microspheres.
(2) The method for preparing the magnetic dispersion solid phase extraction material comprises the following steps: placing sulfonated polyphenyl compound microspheres and ferroferric oxide into a flask according to a certain molar ratio, adding ultrapure water, stirring and reacting at normal temperature, washing reactants with the ultrapure water after the reaction is finished, and drying the reactants in vacuum to constant weight to obtain the magnetic dispersion solid-phase extraction material.
Example 1
(1) Synthesis of sulfonated polystyrene microsphere SPS-1
Mixing polystyrene microspheres and concentrated sulfuric acid, placing the mixture in a flask, stirring and refluxing at 40-60 ℃ for reaction for 8-12h, pouring a reaction system into an ice-water mixture to finish the reaction, washing the reaction product with methanol and ultrapure water for a plurality of times after the reaction is finished, soaking the reaction product with ultrapure water overnight, performing suction filtration, and performing vacuum drying until the weight is constant to obtain the sulfonated polystyrene microspheres SPS-1.
(2) Magnetic dispersion solid phase extraction material Fe3O4Synthesis of/SPS-1
Placing the sulfonated polystyrene microsphere SPS-1 and ferroferric oxide into a flask according to a certain molar ratio, adding ultrapure water, after the reaction is finished, carrying out magnetic separation, and drying in vacuum to constant weight to obtain a magnetic dispersion solid phase extraction material Fe3O4/SPS-1。
(3) Applications of
Weighing a proper amount of magnetic dispersion solid phase extraction material Fe3O4/SPS-1, weighing 2g of pork sample, 20 mu L of clenbuterol internal standard, 20 mu L of clenbuterol external standard and 5ml of 0.2% mol/L ammonium acetate solution; placing the mixture into a water bath constant temperature oscillator for overnight enzymolysis at 37 ℃; then transferring the supernatant to another centrifuge tube by vortex centrifugation (10000r/min, 10min), adding 3ml of 4% trichloroacetic acid to remove substances such as protein, fat and the like in the supernatant; then vortex and centrifuge (10000r/min, 10min) to transfer the supernatant to another tube and stand for standby.
Then pouring the liquid for standby standing into a small test tube of the magnetic dispersion solid phase extraction material, placing the small test tube into a water bath constant temperature oscillator to shake for 30min, and removing the supernatant by magnetic separation; washing the magnetic ball with 3mL of deionized water, 0.2% formic acid water and methanol in sequence (adding liquid, mixing, shaking for 10min, and removing liquid by magnetic separation); then adding 5mL of 5% ammonia water methanol solution into the test tube, uniformly mixing, shaking for 15min by using a water bath constant temperature oscillator, and transferring the supernatant into a 10mL centrifuge tube by using magnetic separation; the liquid was blown dry (1 hour) using nitrogen in a water bath at 40 ℃; then adding 2mL of 0.1 percent formic acid water and acetonitrile with the volume ratio of 8: 2, and carrying out ultrasonic dispersion for 10 min; entering a sample injection vial through two layers of membranes; and performing on-machine analysis.
Example 2
(1) Synthesis of sulfonated polystyrene microsphere SPS-2
Mixing polystyrene microspheres and concentrated sulfuric acid, placing the mixture in a flask, stirring and refluxing at 40-60 ℃ for reaction for 20-30h, pouring a reaction system into an ice-water mixture to finish the reaction, washing the reaction product with methanol and ultrapure water for a plurality of times after the reaction is finished, soaking the reaction product with ultrapure water overnight, performing suction filtration, and drying in vacuum to constant weight to obtain the sulfonated polystyrene microspheres SPS-2.
(2) Magnetic dispersion solid phase extraction material Fe3O4Synthesis of/SPS-2
Placing the sulfonated polystyrene microsphere SPS-2 and ferroferric oxide into a flask according to a certain molar ratio, adding ultrapure water, after the reaction is finished, carrying out magnetic separation, and drying in vacuum to constant weight to obtain a magnetic dispersion solid phase extraction material Fe3O4/SPS-2。
(3) Applications of
Weighing a proper amount of magnetic dispersion solid phase extraction material Fe3O4/SPS-2, weighing 2g of pork sample, 20 mu L of clenbuterol internal standard, 20 mu L of clenbuterol external standard and 5ml of 0.2% mol/L ammonium acetate solution; placing the mixture into a water bath constant temperature oscillator for overnight enzymolysis at 37 ℃; then transferring the supernatant to another centrifuge tube by vortex centrifugation (10000r/min, 10min), adding 3ml of 4% trichloroacetic acid to remove substances such as protein, fat and the like in the supernatant; then vortex and centrifuge (10000r/min, 10min) to transfer the supernatant to another tube and stand for standby.
Then pouring the liquid for standby standing into a small test tube of the magnetic dispersion solid phase extraction material, placing the small test tube into a water bath constant temperature oscillator to shake for 30min, and removing the supernatant by magnetic separation; washing the magnetic ball with 3mL of deionized water, 0.2% formic acid water and methanol in sequence (adding liquid, mixing, shaking for 10min, and removing liquid by magnetic separation); then adding 5mL of 5% ammonia water methanol solution into the test tube, uniformly mixing, shaking for 15min by using a water bath constant temperature oscillator, and transferring the supernatant into a 10mL centrifuge tube by using magnetic separation; the liquid was blown dry (1 hour) using nitrogen in a water bath at 40 ℃; then adding 2mL of 0.1 percent formic acid water and acetonitrile with the volume ratio of 8: 2, and carrying out ultrasonic dispersion for 10 min; entering a sample injection vial through two layers of membranes; and performing on-machine analysis.
Example 3
(1) Synthesis of sulfonated polystyrene microsphere SPS-1
Mixing polystyrene microspheres and concentrated sulfuric acid, placing the mixture in a flask, stirring and refluxing at 40-60 ℃ for reaction for 8-12h, pouring a reaction system into an ice-water mixture to finish the reaction, washing the reaction product with methanol and ultrapure water for a plurality of times after the reaction is finished, soaking the reaction product with ultrapure water overnight, performing suction filtration, and performing vacuum drying until the weight is constant to obtain the sulfonated polystyrene microspheres SPS-1.
(2) Magnetic dispersion solid phase extraction material Fe3O4Synthesis of/SPS-3
Placing the sulfonated polystyrene microsphere SPS-1 and ferroferric oxide into a flask according to a certain molar ratio, adding ultrapure water, after the reaction is finished, carrying out magnetic separation, and drying in vacuum to constant weight to obtain a magnetic dispersion solid phase extraction material Fe3O4/SPS-3。
(3) Applications of
Weighing a proper amount of magnetic dispersion solid phase extraction material Fe3O4/SPS-3, weighing 2g of pork sample, 20 mu L of clenbuterol internal standard, 20 mu L of clenbuterol external standard and 5ml of 0.2% mol/L ammonium acetate solution; placing the mixture into a water bath constant temperature oscillator for overnight enzymolysis at 37 ℃; then transferring the supernatant to another centrifuge tube by vortex centrifugation (10000r/min, 10min), adding 3ml of 4% trichloroacetic acid to remove substances such as protein, fat and the like in the supernatant; then vortex and centrifuge (10000r/min, 10min) to transfer the supernatant to another tube and stand for standby.
Then pouring the liquid for standby standing into a small test tube of the magnetic dispersion solid phase extraction material, placing the small test tube into a water bath constant temperature oscillator to shake for 30min, and removing the supernatant by magnetic separation; washing the magnetic ball with 3mL of deionized water, 0.2% formic acid water and methanol in sequence (adding liquid, mixing, shaking for 10min, and removing liquid by magnetic separation); then adding 5mL of 5% ammonia water methanol solution into the test tube, uniformly mixing, shaking for 15min by using a water bath constant temperature oscillator, and transferring the supernatant into a 10mL centrifuge tube by using magnetic separation; the liquid was blown dry (1 hour) using nitrogen in a water bath at 40 ℃; then adding 2mL of 0.1 percent formic acid water and acetonitrile with the volume ratio of 8: 2, and carrying out ultrasonic dispersion for 10 min; entering a sample injection vial through two layers of membranes; and performing on-machine analysis.
Finally, it is noted that the disclosed embodiments are intended to facilitate a further understanding of the invention. But those skilled in the art will understand that: various substitutions and modifications are possible without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the present invention should not be limited to the disclosure of the embodiment. The scope of the invention is defined by the appended claims.
Claims (7)
1. A magnetic dispersion solid phase extraction material for enriching veterinary drug residues and a preparation method thereof are characterized in that: the carrier is functionalized polyphenyl compound microspheres, different functionalized polyphenyl compound microspheres are selected, and a series of magnetic dispersed solid phase extraction materials are prepared in one step by adopting an electrostatic adsorption method.
2. The carrier-functionalized polyphenylene compound microsphere of claim 1, having the following structure:
wherein,
is a styrene homopolymer or a copolymer of styrene and divinylbenzene or styrene and other mono-or diene-or triene monomers.
3. The polymer having a benzene ring structure according to claim 2 may be linear, crosslinked, macroporous or gelled.
4. The R group of claim 2 may have the structure shown in the following table
5. The preparation method of the magnetic dispersion solid phase extraction material for enriching the veterinary drug residue, which is disclosed by claim 2, has the following characteristics, taking sulfonic acid groups as an example, and comprises two preparation methods:
(1) uses polymer containing benzene ring structure as reactant and CCl4Or HCCl3Or CH2Cl2Swelling reactant with solvent for 1-3h, reacting at 40-60 deg.C for 0.5-1h with chlorosulfonic acid as sulfonating agent to obtain sulfonic acid type polystyrene with loading amount of 0.1-3.5mmol/g based on sulfur element content;
(2) taking a polymer containing a benzene ring structure as a reactant, taking concentrated sulfuric acid (98%) as a solvent and a sulfonating agent, and stirring for reaction at 40-60 ℃ for 8-12h to obtain the sulfonic acid type polystyrene with the loading capacity of 1.0-2.5mmol/g based on the sulfur content.
Taking nitro as an example, the method comprises the following preparation methods:
with CCl4Swelling a reactant by a solvent for 1-3h, preparing mixed acid by 65% nitric acid and 98% sulfuric acid according to a certain proportion at a low temperature, dropwise adding the mixed acid into a four-mouth bottle at room temperature, and violently stirring; after the mixed acid is dripped, heating to 45-55 ℃ and reacting for 10-12 h; washing the reaction solution to weak acidity with distilled water after the reaction is finished, dripping an organic phase into isopropanol, separating out a light yellow precipitate, performing suction filtration, washing with isopropanol, and drying a filter cake at 50-60 ℃ for 3 hours; the product is dissolved and precipitated for 2 times by DMF/isopropanol, and is dried for 24 hours in vacuum after being filtered.
Taking sulfydryl as an example, the preparation method comprises the following steps:
the thiourea and chloromethylated polystyrene resin are placed in absolute ethyl alcohol for reflux reaction for 3-5h to obtain thiourea-based polystyrene resin, 50% NaOH solution is used for hydrolysis for 10-12h at 70-80 ℃ under the protection of nitrogen to obtain crude product of the mercapto-based polystyrene resin, the crude product of the mercapto-based polystyrene resin is washed by water, washed by dilute hydrochloric acid and washed by water, the mercapto-based polystyrene resin is placed in absolute ethyl alcohol for reflux extraction for 6-8h, and vacuum drying is carried out to obtain the mercapto-based polystyrene resin.
Taking amino as an example, the method comprises the following preparation methods:
dissolving nitro polystyrene microspheres in NaOH solution, adding a reducing agent sodium dithionite, reacting for 3-5h, filtering the reaction mixture, washing with deionized water until the pH value is neutral, and drying to obtain yellow powder.
6. The magnetically dispersed solid phase extraction material of claim 1 having the following core-shell structure: the functionalized polyphenyl compound microsphere is used as a core, and the ferroferric oxide nano particle is used as a shell.
7. The method of preparing a magnetically dispersed solid phase extraction material of claim 6, having the following characteristics: mixing the functionalized polyphenyl compound microspheres, ferroferric oxide and ultrapure water according to a certain molar ratio, and reacting for 0.5-2 hours under the oscillation condition to obtain the magnetic dispersion solid-phase extraction material.
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