CN111289663A - 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
- Publication number
- CN111289663A CN111289663A CN201911383003.7A CN201911383003A CN111289663A CN 111289663 A CN111289663 A CN 111289663A CN 201911383003 A CN201911383003 A CN 201911383003A CN 111289663 A CN111289663 A CN 111289663A
- Authority
- CN
- China
- Prior art keywords
- polyethyleneimine
- block polymer
- magnetic
- magnetic nanoparticle
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 48
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 41
- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 231100000678 Mycotoxin Toxicity 0.000 claims abstract description 41
- 239000002636 mycotoxin Substances 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 229920001400 block copolymer Polymers 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000002114 nanocomposite Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- MBMQEIFVQACCCH-UHFFFAOYSA-N trans-Zearalenon Natural products O=C1OC(C)CCCC(=O)CCCC=CC2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-UHFFFAOYSA-N 0.000 claims description 8
- MBMQEIFVQACCCH-QBODLPLBSA-N zearalenone Chemical compound O=C1O[C@@H](C)CCCC(=O)CCC\C=C\C2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-QBODLPLBSA-N 0.000 claims description 8
- LINOMUASTDIRTM-QGRHZQQGSA-N deoxynivalenol Chemical compound C([C@@]12[C@@]3(C[C@@H](O)[C@H]1O[C@@H]1C=C(C([C@@H](O)[C@@]13CO)=O)C)C)O2 LINOMUASTDIRTM-QGRHZQQGSA-N 0.000 claims description 7
- LINOMUASTDIRTM-UHFFFAOYSA-N vomitoxin hydrate Natural products OCC12C(O)C(=O)C(C)=CC1OC1C(O)CC2(C)C11CO1 LINOMUASTDIRTM-UHFFFAOYSA-N 0.000 claims description 7
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 6
- 229930002954 deoxynivalenol Natural products 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 6
- 229930195730 Aflatoxin Natural products 0.000 claims description 5
- 239000005409 aflatoxin Substances 0.000 claims description 5
- 239000003008 fumonisin Substances 0.000 claims description 5
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ADFIQZBYNGPCGY-UHFFFAOYSA-N Acetyldeoxynivalenol Natural products C1=C(C)C(=O)C(O)C2(CO)C1OC1C(OC(=O)C)CC2(C)C21CO2 ADFIQZBYNGPCGY-UHFFFAOYSA-N 0.000 claims description 3
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 claims description 3
- ADFIQZBYNGPCGY-KLOHDQKESA-N acetyldeoxynivalenol Chemical compound C12([C@]3(C)C[C@H]([C@H]1O[C@H]1[C@@]3([C@H](O)C(=O)C(C)=C1)CO)OC(=O)C)CO2 ADFIQZBYNGPCGY-KLOHDQKESA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000002444 silanisation Methods 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000006884 silylation reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000000523 sample Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- 239000003053 toxin Substances 0.000 description 2
- 231100000765 toxin Toxicity 0.000 description 2
- -1 1mmol) Chemical compound 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000005173 quadrupole mass spectroscopy Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- 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 is carried out between the @ (PGMA-co-PD) and the polyethyleneimine to obtain the polyethyleneimine functionalized block polymerAnd (3) 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 (10)
1. A polyethyleneimine functionalized block polymer magnetic nanocomposite is characterized by comprising a magnetic nanoparticle matrix and a polymer network layer formed by crosslinking a block copolymer and polyethyleneimine.
2. The composite material of claim 1, wherein the composite material consists essentially of a magnetic nanoparticle matrix, a block copolymer bonded to a surface of the magnetic nanoparticle matrix, and a polyethyleneimine-crosslinked polymer network layer attached to the block copolymer.
3. Composite material according to claim 1 or 2, characterized in that the magnetic nanoparticle matrix is selected from Fe3O4Magnetic nanoparticles.
Preferably, the size of the magnetic nanoparticle matrix particle size is 5nm to 200 nm.
Preferably, the block polymer contains at least a polyglycidyl methacrylate segment.
Preferably, the block polymer may further include one, two or more polymer segments of polymethacrylates, polystyrenes, polyacrylamides and the like, in addition to the polyglycidyl methacrylate segment.
Preferably, the polyethyleneimine is branched polyethyleneimine, and the number average molecular weight of the polyethyleneimine is 5000-500000 g/mol.
4. A method for preparing a composite material according to any one of claims 1 to 3, characterized in that it 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.
5. The method of claim 4, comprising 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 Fe3O4And performing epoxidation reaction on @ (PGMA-co-PD) and polyethyleneimine to obtain the polyethyleneimine functionalized block polymer magnetic nanoparticles.
6. The method according to claim 4 or 5, wherein in step 1), the 3-bromopropyltrimethoxysilane is used in an amount of 1mg of the magnetic nanoparticle matrix to 1 μ L of the 3-bromopropyltrimethoxysilane.
Preferably, in step 1), the silylation reaction is carried out under heated reflux.
7. The process according to any one of claims 4 to 6, wherein in step 2), the catalyst used in the polymerization reaction is pentamethyldiethylenetriamine and CuBr.
Preferably, in the step 2), the molar ratio of the catalyst diethylenetriamine and CuBr to the glycidyl methacrylate used in the polymerization reaction is (1-5) to (1-3) to 1.
Preferably, in step 2), the polymerization reaction is carried out under an atmosphere inert to the reaction, for example under a nitrogen atmosphere.
Preferably, in the step 2), the polymerization reaction is carried out at 0-30 ℃.
8. The method according to any one of claims 4 to 7, wherein the reaction is carried out at 0 to 30 ℃ in step 3).
9. Use of the polyethyleneimine-functionalized block polymer magnetic nanoparticles as described in any one of claims 1 to 3 for extraction and enrichment of mycotoxins.
Preferably, the mycotoxin is selected from at least one of Deoxynivalenol (DON), acetyl deoxynivalenol (3-DON, 15-DON), Zearalenone (ZEN), aflatoxin (AFTB1, AFTB2) and fumonisins (FB1, FB2, FB 3).
10. The method for extracting and enriching mycotoxin by using the polyethyleneimine functionalized block polymer magnetic nanoparticles as described in any one of claims 1 to 3, wherein the method 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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911383003.7A CN111289663B (en) | 2019-12-27 | 2019-12-27 | Polyethyleneimine functionalized block polymer magnetic nanoparticle composite material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911383003.7A CN111289663B (en) | 2019-12-27 | 2019-12-27 | Polyethyleneimine functionalized block polymer magnetic nanoparticle composite material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111289663A true CN111289663A (en) | 2020-06-16 |
CN111289663B CN111289663B (en) | 2021-09-17 |
Family
ID=71024198
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911383003.7A Expired - Fee Related CN111289663B (en) | 2019-12-27 | 2019-12-27 | Polyethyleneimine functionalized block polymer magnetic nanoparticle composite material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111289663B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113274981A (en) * | 2021-05-24 | 2021-08-20 | 中国检验检疫科学研究院 | Magnetic nanoparticles and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003288108A1 (en) * | 2002-11-29 | 2004-06-23 | Henkel Kommanditgesellschaft Auf Aktien | Magnetic particles for separating microorganisms from technical media |
CN101341203A (en) * | 2005-12-09 | 2009-01-07 | 恰根有限公司 | Magnetic polymer particles |
CN102643374A (en) * | 2012-04-26 | 2012-08-22 | 北京化工大学 | High-performance cationic gene vectors with PGMA (polyglycidyl methacrylate) serving as framework constructed by ATRP (atom transfer radical polymerization) method |
CN102702407A (en) * | 2012-06-21 | 2012-10-03 | 萨恩化学技术(上海)有限公司 | ATRP method for constructing cationic gene vector with PGMA as skeleton |
CN103059312A (en) * | 2012-12-12 | 2013-04-24 | 中科院广州化学有限公司 | Amphipathic ternary molecular brush polymer constructed multichannel nanocapsule |
CN106540668A (en) * | 2015-09-18 | 2017-03-29 | 中华人民共和国淮安出入境检验检疫局 | Magnetic hydrophilic molecules trace composite and preparation method thereof |
CN107376870A (en) * | 2017-07-21 | 2017-11-24 | 成都理工大学 | A kind of preparation method of magnetic polymer dye sorbent |
CN108355625A (en) * | 2018-02-09 | 2018-08-03 | 江苏大学 | A kind of glycoprotein surface imprinted polymer and its preparation method and application affine based on team's boron |
-
2019
- 2019-12-27 CN CN201911383003.7A patent/CN111289663B/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003288108A1 (en) * | 2002-11-29 | 2004-06-23 | Henkel Kommanditgesellschaft Auf Aktien | Magnetic particles for separating microorganisms from technical media |
CN101341203A (en) * | 2005-12-09 | 2009-01-07 | 恰根有限公司 | Magnetic polymer particles |
CN102643374A (en) * | 2012-04-26 | 2012-08-22 | 北京化工大学 | High-performance cationic gene vectors with PGMA (polyglycidyl methacrylate) serving as framework constructed by ATRP (atom transfer radical polymerization) method |
CN102702407A (en) * | 2012-06-21 | 2012-10-03 | 萨恩化学技术(上海)有限公司 | ATRP method for constructing cationic gene vector with PGMA as skeleton |
CN103059312A (en) * | 2012-12-12 | 2013-04-24 | 中科院广州化学有限公司 | Amphipathic ternary molecular brush polymer constructed multichannel nanocapsule |
CN106540668A (en) * | 2015-09-18 | 2017-03-29 | 中华人民共和国淮安出入境检验检疫局 | Magnetic hydrophilic molecules trace composite and preparation method thereof |
CN107376870A (en) * | 2017-07-21 | 2017-11-24 | 成都理工大学 | A kind of preparation method of magnetic polymer dye sorbent |
CN108355625A (en) * | 2018-02-09 | 2018-08-03 | 江苏大学 | A kind of glycoprotein surface imprinted polymer and its preparation method and application affine based on team's boron |
Non-Patent Citations (6)
Title |
---|
GULAY BAYRAMOGLU ET AL: "Adsorption of Cr(VI) onto PEI immobilized acrylate-based magnetic beads: Isotherms, kinetics and thermodynamics study", 《CHEMICAL ENGINEERING JOURNAL》 * |
MINGLIANG MA ET AL: "Preparation of magnetic Fe3O4 /P(GMA‐DVB) ‐PEI/Pd highly efficient catalyst with core‐shell structure", 《APPL ORGANOMETAL CHEM》 * |
XITONG SUN ET AL: "Synthesis of polyethylenimine-functionalized poly(glycidyl methacrylate)magnetic microspheres and their excellent Cr(VI) ion removal properties", 《CHEMICAL ENGINEERING JOURNAL》 * |
孙西同: "磯性高分子复合材料的制备及对Cr(VI)的吸附性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
杨玉东: "《生物医学纳米磁性材料原理及应用》", 31 October 2005, 吉林人民出版社 * |
茅群龙 等: "红外光谱法实时跟踪支化聚乙烯亚胺/甲基丙烯酸缩水甘油酯的官能团反应", 《高分子材料科学与工程》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113274981A (en) * | 2021-05-24 | 2021-08-20 | 中国检验检疫科学研究院 | Magnetic nanoparticles and preparation method thereof |
CN113274981B (en) * | 2021-05-24 | 2023-07-07 | 中国检验检疫科学研究院 | Magnetic nanoparticle and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111289663B (en) | 2021-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109092254B (en) | Preparation and application method of double-virtual-template phthalate molecularly imprinted magnetic material | |
Lan et al. | Development of a novel magnetic molecularly imprinted polymer coating using porous zeolite imidazolate framework-8 coated magnetic iron oxide as carrier for automated solid phase microextraction of estrogens in fish and pork samples | |
Wu et al. | Hierarchically imprinted organic–inorganic hybrid sorbent for selective separation of mercury ion from aqueous solution | |
Xu et al. | Preparation and evaluation of superparamagnetic surface molecularly imprinted polymer nanoparticles for selective extraction of bisphenol A in packed food | |
CN114130374B (en) | Application of magnetic carboxylated covalent organic framework material as magnetic solid-phase extraction adsorbent | |
CN113295795B (en) | Method and kit for detecting zearalenone mycotoxins and application thereof | |
Zhao et al. | Magnetic surface molecularly imprinted poly (3-aminophenylboronic acid) for selective capture and determination of diethylstilbestrol | |
An et al. | Novel ionic surface imprinting technology: design and application for selectively recognizing heavy metal ions | |
CN109354657B (en) | Preparation and application methods of alkylphenol composite template molecularly imprinted polymer modified magnetic graphene oxide | |
CN111289663B (en) | Polyethyleneimine functionalized block polymer magnetic nanoparticle composite material and preparation method and application thereof | |
Wang et al. | Ion-imprinted thiol-functionalized silica gel sorbent for selective separation of mercury ions | |
CN105498728A (en) | Preparation and application of di(2-ethyl hexyl) phthalate surface molecular imprinting magnetic nanometer material | |
Wu et al. | Synthesis of ion-imprinted mesoporous silica gel sorbent for selective adsorption of copper ions in aqueous media | |
CN113617338B (en) | Salvianolic acid A surface molecularly imprinted magnetic nano material, and preparation method and application thereof | |
CN113670700B (en) | Enrichment and separation of aflatoxin B1Magnetic photonic crystal microsphere of (2), preparation method and application thereof | |
CN104874359A (en) | Preparing method of calixarene modified magnetic material | |
Madrakian et al. | Solid phase extraction and spectrofluorometric determination of leached bisphenol A from some polycarbonate products under simulated use conditions using surface molecularly imprinted magnetite nanospheres | |
CN112979893B (en) | Preparation of magnetic fluorescent material @ molecularly imprinted particle and method for preparing composite membrane by using same | |
CN106565915B (en) | A kind of preparation method of the mesoporous imprinted polymer of double temperature sensitive types | |
CN111269364B (en) | Temperature response type aminoglycoside antibiotic imprinted magnetic nanoparticle based on polysaccharose and preparation method and application thereof | |
Wang et al. | An imprinted organic–inorganic hybrid sorbent for selective separation of copper ion from aqueous solution | |
Zhang et al. | Surface molecularly imprinted polymers based on NH2-MIL-53 for selective extraction ochratoxin A in real sample | |
CN111437891A (en) | Anion exchange resin and preparation method and application thereof | |
Hashemi-Moghaddam et al. | Synthesis and comparison of new layer-coated silica nanoparticles and bulky molecularly imprinted polymers for the solid-phase extraction of glycine | |
CN112457456B (en) | Polystyrene-divinylbenzene modified magnetic carbon nanotube composite material and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210917 |