CN111289663B - Polyethyleneimine functionalized block polymer magnetic nanoparticle composite material and preparation method and application thereof - Google Patents
Polyethyleneimine functionalized block polymer magnetic nanoparticle composite material and preparation method and application thereof Download PDFInfo
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- RXJZDLSKSHGPLY-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CO1.CC(=C)C(=O)OC(C)(C)C RXJZDLSKSHGPLY-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- -1 1mmol) Chemical compound 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the field of solid-phase extraction materials, and particularly relates to a polyethyleneimine functionalized block polymer magnetic nanocomposite and a preparation method and application thereof. The material includes a magnetic nanoparticle matrix, and a polymer network layer of block copolymer crosslinked with polyethyleneimine. The multiple action sites in the material realize the synchronous extraction and enrichment of the mycotoxins of multiple classes, and compared with a solid phase extraction material suitable for the mycotoxins of a single class, the extraction efficiency can be improved.
Description
Technical Field
The invention belongs to the field of solid-phase extraction materials, and particularly relates to a polyethyleneimine functionalized block polymer magnetic nanocomposite and a preparation method and application thereof.
Background
Mycotoxins (aflatoxin, fumonisin, zearalenone and the like) are highly concerned pollutants in agricultural products such as food, feed and the like, and the content of the mycotoxins is a parameter for monitoring the quality safety risk of the agricultural products and the key monitoring of risk assessment plans in China. The detection method of the mycotoxin comprises high performance liquid chromatography, liquid chromatography tandem mass spectrometry, immunoassay and the like. However, no matter what detection method is adopted, the pretreatment of the sample is the important factor in the whole analysis process, and the aim is to remove interferents existing in the actual sample and enrich target analytes so as to ensure the accuracy of the analysis result. The solid phase extraction technology is one of the commonly used sample pretreatment technologies, and is favored due to the advantages of small organic solvent consumption, high extraction efficiency and the like. Currently, mycotoxin solid phase extraction materials mainly focus on the extraction and enrichment of individual mycotoxins. The mycotoxins are various in types, have different physicochemical properties and toxicity, and have the condition of interactive pollution of the mycotoxins in agricultural products, so that the development of a sample pretreatment material suitable for separation and enrichment of the mycotoxins in multiple types has very important significance for guaranteeing the quality safety of the agricultural products.
Disclosure of Invention
In order to improve the technical problem, the invention provides a polyethyleneimine functionalized block polymer magnetic nanocomposite material, which comprises a magnetic nanoparticle matrix and a polymer network layer formed by crosslinking a block copolymer and polyethyleneimine.
According to an embodiment of the present invention, the composite material consists essentially of a magnetic nanoparticle matrix, a block copolymer bonded to the surface of the magnetic nanoparticle matrix, and a polyethyleneimine-crosslinked polymer network layer attached to the block copolymer.
According to an embodiment of the invention, the magnetic nanoparticle matrix is selected from Fe3O4Magnetic nanoparticles.
According to an embodiment of the invention, the magnetic nanoparticle matrix is Fe3O4The magnetic nanoparticles can be synthesized by chemical coprecipitation or the like.
According to an embodiment of the invention, the magnetic nanoparticle matrix has a particle size in the range of 5nm to 200nm, for example 10nm to 150nm, such as 20nm to 100 nm.
According to an embodiment of the present invention, the block polymer contains at least a polyglycidyl methacrylate segment.
According to the embodiment of the invention, the block polymer can also comprise one, two or more polymer segments of polymethacrylate, polystyrene, polyacrylamide and the like, such as poly (tert-butyl methacrylate) and the like, besides the poly (glycidyl methacrylate) segment.
According to an embodiment of the invention, the polyethyleneimine is a branched polyethyleneimine having a number average molecular weight of 5000 to 500000g/mol, for example 8000 to 300000g/mol, such as 10000 to 200000g/mol, 20000 to 100000 g/mol.
The invention also provides a preparation method of the polyethyleneimine functionalized block polymer magnetic nanocomposite, which comprises the following steps: firstly, synthesizing a magnetic nanoparticle matrix; secondly, modifying the surface of the magnetic nanoparticle matrix with a block polymer; thirdly, polyethylene imine functionalization.
According to an embodiment of the invention, the preparation method comprises the steps of:
1) performing silanization reaction on a magnetic nanoparticle substrate and 3-bromopropyltrimethoxysilane to obtain a substance Fe with bromine modified on the surface of the magnetic nanoparticle substrate3O4@Br；
2) Mixing the Fe prepared in the step 1)3O4The polymerization reaction of @ Br and glycidyl methacrylate to obtain Fe3O4@PGMA-Br；
Or optionally, further adding Fe3O4The @ PGMA-Br and at least one of methacrylate, styrene and acrylamide monomers are subjected to polymerization reaction to obtain Fe3O4@ (PGMA-co-PD), wherein PD is Fe and at least one of methacrylate, styrene and acrylamide monomers3O4A polymer chain segment obtained by the reaction of @ PGMA-Br;
3) fe prepared in the step 2)3O4@ PGMA-Br or Fe3O4The epoxidation reaction of @ (PGMA-co-PD) and polyethyleneimine is carried out to obtain the polyethyleneimineFunctionalized block polymer magnetic nanoparticles.
According to the embodiment of the invention, the block polymer modified magnetic nanoparticles are prepared by a surface-initiated atom transfer radical polymerization (SI-ATRP) method.
According to an embodiment of the present invention, in step 1), the 3-bromopropyltrimethoxysilane is used in an amount of 1mg of the magnetic nanoparticle substrate, and (1.2-5) μ L of 3-bromopropyltrimethoxysilane, for example (1.3-3.5) μ L of 3-bromopropyltrimethoxysilane, such as 1.5 μ L of 3-bromopropyltrimethoxysilane, is used.
According to an embodiment of the invention, in step 1), the silanization reaction is carried out under heated reflux.
According to an embodiment of the invention, in step 1), the solvent used for the silylation reaction is selected from ketone solvents, such as acetone.
According to an embodiment of the present invention, in step 2), the catalyst used in the polymerization reaction is pentamethyldiethylenetriamine and CuBr.
According to an embodiment of the invention, in the step 2), the polymerization reaction uses catalysts of diethylenetriamine and CuBr in a molar ratio to glycidyl methacrylate of (1-5): (1-3): 1, for example (1.5 to 3): (1-1.5): 1, as 2: 1: 1.
according to an embodiment of the invention, in step 2), the polymerization reaction is carried out under an atmosphere inert to the reaction, for example under a nitrogen atmosphere.
According to an embodiment of the present invention, in the step 2), the polymerization reaction is performed at 0 to 30 ℃.
According to an embodiment of the present invention, in step 2), the solvent used for the reaction is an alcoholic solvent, such as methanol.
According to an embodiment of the present invention, in step 2), the polymerization reaction is stopped by exposure to air.
According to an embodiment of the present invention, in step 3), the polyethyleneimine functionalizes the block polymer magnetic nanoparticles through chemical bonding, preferably by using the reaction of amine groups in the polyethyleneimine with epoxy groups in the polyglycidyl methacrylate.
According to an embodiment of the present invention, in the step 3), the reaction is performed at 0 to 30 ℃.
According to an embodiment of the present invention, in step 3), the solvent used for the reaction is an alcoholic solvent, such as methanol.
The invention also provides the polyethyleneimine functionalized block polymer magnetic nanoparticles prepared by the method.
The invention also provides application of the polyethyleneimine functionalized block polymer magnetic nanoparticles in mycotoxin extraction and enrichment.
According to an embodiment of the invention, the mycotoxin is selected from at least one of Deoxynivalenol (DON), acetyldeoxynivalenol (3-DON, 15-DON), Zearalenone (ZEN), aflatoxins (AFTB1, AFTB2), fumonisins (FB1, FB2, FB 3).
The invention also provides a method for extracting and enriching mycotoxin by using the polyethyleneimine functionalized block polymer magnetic nanoparticles, which comprises the following steps: mixing and stirring the polyethyleneimine functionalized block polymer magnetic nanoparticles and an aqueous solution containing mycotoxin to enable the mycotoxin to be adsorbed on the surfaces of the polyethyleneimine functionalized block polymer magnetic nanoparticles, carrying out magnetic separation on the polyethyleneimine functionalized block polymer magnetic nanoparticles with the mycotoxin adsorbed on the surfaces, and then eluting and desorbing by using a methanol solution containing formic acid with the volume fraction of 0.05-0.5% to carry out subsequent separation.
According to an embodiment of the invention, the adsorption time is 10s to 48h and the desorption time is 10s to 48 h.
The adsorption mechanism of the composite material of the invention to mycotoxin is as follows: the polyethyleneimine contains a large amount of amino (primary amine, secondary amine and tertiary amine), and adsorbs mycotoxins such as fumonisins, zearalenone and the like in an anion exchange mode; adsorbing aflatoxin, vomitoxin and other mycotoxins by a polymer hydrophobic skeleton in a reverse phase mode. The extraction process comprises the following steps: stirring and dispersing the polyethyleneimine functionalized block polymer magnetic nanoparticles in a mycotoxin mixture solution, stirring to enable the magnetic nanoparticles to be fully contacted with mycotoxin and adsorb the mycotoxin, after the adsorption process is finished, separating the adsorbent from the solution by adopting an external magnetic field, and removing supernatant. Adding an eluent, stirring, desorbing, magnetically separating, collecting the elution solution, and then carrying out qualitative and quantitative analysis on the mycotoxin in the elution solution.
Advantageous effects
1. The multiple action sites on the surface of the polyethyleneimine functionalized block polymer magnetic nanoparticle are utilized to realize synchronous extraction and enrichment of multi-class mycotoxins, and compared with a solid phase extraction material suitable for single-class mycotoxin, the extraction efficiency can be improved.
2. The chain length and the composition of the block copolymer are changed to accurately regulate and control the density and the hydrophobicity of chemical functional groups of the block copolymer, so that the selectivity and the application range of the adsorbent to mycotoxin are regulated and controlled.
3. Compared with the traditional solid phase extraction column, the magnetic nano material can realize rapid magnetic separation and simplify the pretreatment steps of the sample.
Drawings
FIG. 1 shows Fe prepared in example 13O4SEM image of @ PEI nanoparticle.
FIG. 2 is an extracted ion current chromatogram of 9 mycotoxins in the maize additive sample of example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
(1) Preparation of poly (glycidyl methacrylate-tert-butyl methacrylate) block copolymer modified magnetic nanoparticles (Fe)3O4@(PGMA-co-PtBMA))
(1.1) Synthesis of Fe by surface-initiated atom transfer radical polymerization (SI-ATRP)3O4@(PGMA-co-PtBMA)
Modifying ATRP initiation groups on the surface of magnetic nanoparticles, and specifically operating as follows: 50mg of Fe3O4Dispersing magnetic nanoparticles in 20mL of acetone, dropwise adding excessive 3-bromopropyltrimethoxysilane (75 mu L) into the mixture while stirring, heating and refluxing for 12 hours, cleaning the product with acetone, and placing and drying in a vacuum drying oven to obtain Fe3O4@Br。
Mixing Fe3O4Further synthesizing Fe by using @ Br as ATRP initiator3O4@ PGMA-Br, the specific operation is: mixing glycidyl methacrylate (GMA, 1mmol), pentamethyldiethylenetriamine (PMDETA, 2mmol), CuBr (143mg,1mmol) and methanol (30mL) in a reaction bottle, introducing nitrogen to remove oxygen for 30 minutes, and rapidly adding Fe3O4@ Br (50mg), reacting for 2 hours at room temperature in nitrogen atmosphere, exposing the reaction solution to air to terminate the reaction, cleaning the product with acetone, placing the product in a vacuum drying oven to dry, and preparing the obtained Fe3O4@ PGMA-Br as macroinitiator for further synthesizing Fe3O4@ (PGMA-co-PtBMA), the specific operation is: tert-butyl methacrylate (tBMA, 1mmol), pentamethyldiethylenetriamine (PMDETA, 2mmol), CuBr (143mg,1mmol) and methanol (30mL) were mixed in a reaction flask, nitrogen gas was introduced to remove oxygen for 30 minutes, and Fe was rapidly added3O4@ PGMA-Br (500mg), reacting for 2 hours under the condition of room temperature in nitrogen atmosphere, exposing the reaction solution to the air to terminate the reaction, cleaning the product with acetone, placing the product in a vacuum drying oven to dry, and finally obtaining the product Fe3O4@(PGMA-co-PtBMA)。
(2) Preparation of polyethyleneimine functionalized block polymer magnetic nanoparticles
Utilizing amino and Fe in polyethyleneimine3O4The epoxy group in @ (PGMA-co-PtBMA) reacts: polyethyleneimine (Wt ═ 80000g/mol, 1mL) and Fe3O4Adding @ (PGMA-co-PtBMA) (0.5g) into 20mL of methanol, stirring at room temperature for 24 hours, washing the product with methanol and water in sequence after the reaction is finished, and drying at 60 ℃ in a vacuum drying oven to obtain the product Fe3O4@ (. about.a) (PGMA-co-PtBMA) @ PEI. The SEM characterization result is shown in FIG. 1, and the structure is confirmed to be the target product.
Example 2
Enrichment and extraction of mycotoxin in corn
The composite material prepared in example 1 was used to extract 9 mycotoxins from corn. These 9 mycotoxins include: deoxynivalenol (DON), acetyldeoxynivalenol (3-DON, 15-DON), Zearalenone (ZEN), aflatoxins (AFTB1, AFTB2), fumonisins (FB1, FB2, FB 3). Accurately weighing 2.0g of the crushed and homogenized corn sample, and adding 9 mycotoxin mixture standard solutions (10. mu.g/mL, 100. mu.L, concentration is the concentration of each mycotoxin). Adding 10mL of the extractive solution (60% acetonitrile-40% water), shaking vigorously, shaking for 30 min, centrifuging (8000r/min) for 12 min, collecting supernatant (1 mL), and diluting with pure water to 5 mL. Adding 50mg of Fe into the sample solution3O4And (2) adopting @ PEI as an adsorbent, stirring for 10 minutes to uniformly disperse the adsorbent in the sample loading solution, after adsorption is finished (analyzing the supernatant after adsorption by adopting liquid chromatography tandem mass spectrometry, and qualitatively and quantitatively determining unadsorbed toxin, and when the concentration of the residual toxin in the supernatant is very low and does not change along with the prolonging of adsorption time, indicating that the adsorption process is balanced, namely adsorption is finished), carrying out magnetic separation and discarding the supernatant, and then adding 1mL of eluent (methanol solution containing formic acid with volume fraction of 0.1%). After stirring for 5 minutes for desorption, the eluate was collected and analyzed by liquid chromatography tandem triple quadrupole mass spectrometry. The added samples were analyzed and the results are shown in fig. 2. The recovery of 9 mycotoxins was calculated from FIG. 2 according to the following formula, and the results are shown in Table 1,
wherein, CeThe concentration of the mycotoxin in the eluent is obtained by analyzing the result of liquid chromatography tandem mass spectrometry; ve is the volume of the eluent; c0 is the mycotoxin concentration in the adsorption solution, and V0 is the volume of the adsorption solution.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The application of the polyethyleneimine functionalized block polymer magnetic nanoparticles in the extraction and enrichment of mycotoxin is characterized in that the polyethyleneimine functionalized block polymer magnetic nanocomposite comprises a magnetic nanoparticle matrix, a block copolymer bonded with the surface of the magnetic nanoparticle matrix, and a polyethyleneimine crosslinked polymer network layer connected with the block copolymer;
the magnetic nanoparticle matrix is selected from Fe3O4Magnetic nanoparticles;
the block copolymer contains a poly glycidyl methacrylate chain segment and a poly tert-butyl methacrylate chain segment;
the mycotoxin is at least one selected from deoxynivalenol, acetyl deoxynivalenol, zearalenone, aflatoxin and fumonisin.
2. Use according to claim 1, wherein the polyethyleneimine is a branched polyethyleneimine having a number average molecular weight of 5000 to 500000 g/mol.
3. The use according to claim 1, wherein the magnetic nanoparticle matrix has a particle size of 5nm to 200 nm.
4. Use according to claim 1, wherein the polyethyleneimine-functionalized block polymer magnetic nanocomposite is selected from Fe3O4The material is a @ PEI, and is a magnetic nanoparticle modified by a polyethyleneimine functionalized poly (glycidyl methacrylate-tert-butyl methacrylate) block copolymer.
5. The use according to any one of claims 1 to 4, wherein the method for preparing the magnetic nanocomposite of a polyethyleneimine-functionalized block polymer comprises the following steps:
firstly, synthesizing a magnetic nanoparticle matrix;
secondly, modifying the surface of the magnetic nanoparticle matrix with a block polymer;
and thirdly, functionalizing the polyethyleneimine.
6. Use according to claim 5, characterized in that it comprises the following steps:
1) performing silanization reaction on a magnetic nanoparticle substrate and 3-bromopropyltrimethoxysilane to obtain a substance Fe with bromine modified on the surface of the magnetic nanoparticle substrate3O4@Br；
2) Mixing the Fe prepared in the step 1)3O4The polymerization reaction of @ Br and glycidyl methacrylate to obtain Fe3O4@PGMA-Br；
Further adding Fe3O4The polymerization reaction of @ PGMA-Br and tert-butyl methacrylate monomer is carried out to obtain Fe3O4@ R (PGMA-co-PD) where PD is tert-butyl methacrylate monomer with Fe3O4Polymerization by reaction of @ PGMA-BrA chain segment;
3) fe prepared in the step 2)3O4And performing epoxidation reaction on @ (PGMA-co-PD) and polyethyleneimine to obtain the polyethyleneimine functionalized block polymer magnetic nanoparticles.
7. The use according to claim 6, characterized in that in step 1), the 3-bromopropyltrimethoxysilane and the magnetic nanoparticle matrix are used in a dosage ratio of (1.2-5) μ L3-bromopropyltrimethoxysilane to 1mg of the magnetic nanoparticle matrix.
8. The use according to claim 6, wherein in step 2), the catalyst used in the polymerization reaction is pentamethyldiethylenetriamine and CuBr.
9. The use according to claim 8, wherein in the step 2), the polymerization reaction uses pentamethyldiethylenetriamine and the molar ratio of CuBr to glycidyl methacrylate is (1-5): (1-3): 1.
10. use according to claim 9, wherein in step 2) the polymerization reaction is carried out under an atmosphere inert to the reaction.
11. The use according to claim 10, wherein in step 2), the polymerization reaction is in the range of 0 to 30%oAnd C, performing.
12. The use of claim 6, wherein in step 3), the reaction is in the range of 0 to 30%oAnd C, performing.
13. The method for extracting and enriching the mycotoxin is characterized by comprising the following steps:
mixing and stirring the magnetic nanocomposite material of the polyethyleneimine-functionalized block polymer according to any one of claims 1 to 4 with an aqueous solution containing mycotoxin to adsorb the mycotoxin on the surface of the magnetic nanoparticle of the polyethyleneimine-functionalized block polymer;
performing magnetic separation on the polyethyleneimine functionalized block polymer magnetic nanoparticles with mycotoxin adsorbed on the surfaces;
then, using methanol solution containing 0.05-0.5% by volume of formic acid to carry out elution and desorption for subsequent separation.
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