CN103467654B - Magnetic heterocyclic amine molecularly imprinted polymer and preparation method thereof - Google Patents
Magnetic heterocyclic amine molecularly imprinted polymer and preparation method thereof Download PDFInfo
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- CN103467654B CN103467654B CN201310413898.0A CN201310413898A CN103467654B CN 103467654 B CN103467654 B CN 103467654B CN 201310413898 A CN201310413898 A CN 201310413898A CN 103467654 B CN103467654 B CN 103467654B
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- heterocyclic amine
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Abstract
The invention discloses a magnetic heterocyclic amine molecularly imprinted polymer and a preparation method thereof. The magnetic heterocyclic amine molecularly imprinted polymer which takes heterocyclic amine as a template molecule and methacrylic acid (MAA) as a functional monomer is prepared by the method; the characteristics of the molecularly imprinted polymer are fully combined with those of the magnetic material; the magnetic heterocyclic amine molecularly imprinted polymer has the advantages of high selectivity, large adsorption capacity, rapid separation speed, high anti-interference capability and the like, and is suitable for analyzing heterocyclic amine in food and environment.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic heterocyclic amine molecular engram material, belong to new material research field.
Background technology
Molecular imprinting adopts manual method to prepare technology specific molecular to specificity keying action polymkeric substance from bionical angle, have that selectivity is single-minded, the advantage such as strong interference immunity, preparation are simple, good stability, long service life, thus in chromatographic stationary phases, Solid-Phase Extraction, membrane sepn, immunoassay, antibodies mimic, chemical sensor, catalyzer and synthetic enzyme etc., have vast potential for future development.
Magneticsubstance is a kind of good sample pretreatment parting material, its superparamagnetism not only can be utilized to be separated from medium under additional the action of a magnetic field, and by the approach such as copolymerization, surface modification, its surperficial multiple reactive functionality can be given, effective enrich target compound.
Magnetic molecularly imprinted polymer, had both had the feature of selective adsorption, had again the feature of the easy dynamic separation of magneticsubstance, can the enrichment of high degree simplification to target compound in complex sample.
Heterocyclic amine compound is that a class is made up of carbon, nitrogen, hydrogen atom, has the aromatics of polynuclear plane, has Mutagenicity and potential carinogenicity, is present in barbecue or the fried fish that processed and meat product.The sample pretreatment process complex operation of traditional meat product, length consuming time, and the feature such as meat product substrate is complicated, heterocyclic amine samples contg is low, traditional technique in measuring heterocyclic amine has certain difficulty.
Summary of the invention
The object of the invention is to prepare a kind of highly selective, loading capacity is large, velocity of separation is fast, the magnetic heterocyclic amine molecularly imprinted polymer that immunity from interference is strong, go for the enrichment of heterocyclic amine in complex sample.
Technical scheme of the present invention is as follows:
A kind of magnetic heterocyclic amine molecularly imprinted polymer, is characterized in that: this polymkeric substance is with Fe
3o
4nanoparticle is as core, core external parcel molecular engram material, described molecular engram material uses heterocyclic amine as template molecule, methacrylic acid is as function monomer (MAA), trimethoxypropane gave trimethacrylate (TRIM) and Vinylstyrene (DVB) are as linking agent, and Diisopropyl azodicarboxylate (AIBN) is prepared as initiator.
Wherein, the diameter of whole polymkeric substance is 50-60nm; As the Fe of core
3o
4diameter of nano particles is 30-40nm.
Wherein, described heterocyclic amine comprises:
Amino-3 Methylimidazoles of IQ:2-also [4,5-F] quinoline
Amino-1 Methylimidazole of iso-IQ:2-also [4,5-F] quinoline
Amino-3,8-dimethyl-imidazos [4, the 5-F] quinoline of MeIQ:2-
IQx:2-amino-3-Methylimidazole also [4,5-f] quinoxaline
Amino-3,8-dimethyl-imidazos [4, the 5-f] quinoxaline of 8-MeIQx:2-
Amino-3,4-dimethyl-imidazos [4, the 5-f] quinoxaline of 4-MeIQx:2-
Amino-3,4, the 8-tri-methylimidazolium of 4,8-DiMeIQx:2-also [4,5-f] quinoxaline
Amino-3,7, the 8-tri-methylimidazolium of 7,8-DiMeIQx:2-also [4,5-f] quinoxaline
Amino-1,7-dimethyl-imidazo [4, the 5-g] quinoxaline of 7-MeIgQx:2-
Amino-1,7, the 9-tri-methylimidazolium of 7,9-DiMeIgQx:2-also [4,5-g] quinoxaline
PhIP:2-amino-1-methyl-6-phenyl imidazole also [4,5-b] pyridine
Amino-1,6-dimethyl-imidazo [4, the 5-b] pyridine of DMIP:2-
Amino-1,5, the 6-tri-methylimidazolium of 1,5,6-TMIP:2-also [4,5-b] pyridine
Amino-3,5, the 6-tri-methylimidazolium of 3,5,6-TMIP:2-also [4,5-b] pyridine
Phe-P-1:2-amino-5-phenyl pyridine
Norharman:9H-pyrido [3,4-b] indoles
Harman:1-methyl-9H-pyrido [3,4-b] indoles
Trp-P-2:3-amino-1-methyl-5H-pyrido [4,3-b] indoles
Trp-P-1:3-amino-Isosorbide-5-Nitrae-dimethyl-5H-pyrido [4,3-b] indoles
A α C:2-amino-9H-pyrido [2,3-b] indoles
MeA α C:2-amino-3-methyl-9H-pyrido [2,3-b] indoles
Glu-p-1:2-amino-6-methyl two pyridine [1,2-α: 3', 2'-d] imidazoles
Amino two pyridines [1,2-α: 3', the 2'-d] imidazoles of Glu-p-2:2-
Prepare a method for magnetic heterocyclic amine molecularly imprinted polymer, comprise the steps:
(1) Fe of superparamagnetism is synthesized
3o
4particulate;
(2) polyreaction: pipette the Fe that 1.0mmoL – 1.2mmoL step (1) synthesizes
3o
4magnetic particle is in container, add template molecule heterocyclic amine 0.5mmol – 0.6mmol, function monomer MAA110 μ L-120 μ L, linking agent TRIM480 μ L-490 μ L and DVB185 μ L – 188 μ L, add solvent toluene 20mL-22mL, acetonitrile 20mL-22mL again, after sonic oscillation 8min-10min, add 25mg-30mg initiator A IBN, nitrogen blows down oxygen 10min-15min; Stirring velocity 550r/min-650r/min, 58 DEG C of-62 DEG C of water-baths 20 hours-24-hour;
(3) after polyreaction completes, template molecule eluting solvent carries out repeatedly wash-out, until not containing template molecule in eluting solvent.
Wherein, described template molecule heterocyclic amine comprises IQ, iso-IQ, MeIQx, IQx, 8-MeIQx, 4-MeIQx, 4,8-DiMeIQx, 7,8-DiMeIQx, 7-MeIgQx, 7,9-DiMeIgQx, PhIP, DMIP, 1,5,6-TMIP, 3,5,6-TMIP, Phe-P-1, Norharman, Harman, Trp-P-2, Trp-P-1, A α C, MeA α C, Glu-p-1 and Glu-p-2.
Wherein, step (1) operation is as follows: take 1.28g-1.31g FeSO
47H
2o, 1.0g-1.3g FeCl
3, be dissolved in 25mL-35mL ultrapure water, solution mixing inserted in three-necked bottle; High-speed stirring under 400r/min-500r/min condition, passes into nitrogen 0.5 hour-1 hour simultaneously; Then slowly drip the NaOH of 5mL-8mL8mol/L – 5mol/L, control NaOH total amount is at 0.04mol; Continue stirring and be warmed up to 80 DEG C-90 DEG C after 0.5 hour-1 hour, keep this temperature to stir 0.5 hour-1 hour; After having reacted, repeatedly cleaned up by the black particle ultrapure water obtained, be scattered in ultrapure water, sealing saves backup.
Wherein, step (3) operation is as follows: described eluting solvent is methyl alcohol/ammoniacal liquor=9:1, V/V.
Wherein, the HPLC that is detected as of eluting solvent analyzes.
Wherein, after step (3) wash-out, after magnetic molecularly imprinted polymer particulate acetone cleans repeatedly, be scattered in acetone and preserve.
The present invention has been prepared with Fe
3o
4nanoparticle is core, heterocyclic amine molecular engram material is the Fe of shell
3o
4@MAA nucleocapsid structure material.Wherein heterocyclic amine molecular engram material take heterocyclic amine as template molecule, methacrylic acid (MAA) is function monomer, trimethoxypropane gave trimethacrylate (TRIM) and Vinylstyrene (DVB) are linking agent, and Diisopropyl azodicarboxylate (AIBN) is prepared by precipitation polymerization method for initiator.This magnetic heterocyclic amine molecular engram material has the features such as highly selective, extraction efficiency be good.
Accompanying drawing explanation
Fig. 1 is Fe
3o
4(a), the scanning electron microscope (SEM) photograph of (c) and MIP extraction rear (d) before NIP (b), MIP extraction;
Fig. 2 is magnetic molecularly imprinted polymer particulate (MIP) extraction selectivity (sample concentration is 100 μ g/L)
Fig. 3 is that the loading capacity of Fig. 3 MIP and NIP to Nor-Harmande compares.
Embodiment
Embodiment 1
Coprecipitation method prepares magnetic particle: take 1.2986g(and be about 8mmol) FeSO
47H
2o, 1.1121g(are about 4mmol) FeCl
3, be dissolved in 30mL ultrapure water, solution mixing inserted in three-necked bottle.High-speed stirring under 400r/min condition, passes into nitrogen one hour simultaneously.Then slowly drip the NaOH of 8mL5mol/L, can see and have black particle to produce.Continue stirring and be warmed up to 90 DEG C after 1 hour, keep this temperature to stir 1 hour.After having reacted, repeatedly cleaned up by the black particle ultrapure water obtained, be scattered in ultrapure water, sealing saves backup.Collect with magnet, can see that particulate has stronger magnetic.
Precipitation polymerization method prepares magnetic molecularly imprinted polymer: the Fe pipetting the above-mentioned synthesis of 3.0mL
3o
4magnetic particle (about 0.323g, 1 mmoL) in 150mL three-necked bottle, add template molecule heterocyclic amine 0.57mmol, function monomer MAA110 μ L, linking agent TRIM485 μ L and DVB186 μ L, then add solvent toluene 20mL, acetonitrile 20mL, after sonic oscillation 10min, add 26mg initiator A IBN, nitrogen blows down oxygen 10min.Stirring velocity 600r/min, 60 DEG C of water-baths 24 hours.
After polyreaction completes, collect the brown magnetic particle being positioned at aqueous phase with magnet, visible granular has stronger magnetic.Template molecule eluting solvent (methyl alcohol/ammoniacal liquor=9:1, V/V) carries out repeatedly wash-out, until the analysis of eluting solvent HPLC sample introduction is not detected template molecule.After last magnetic molecularly imprinted polymer particulate acetone cleans repeatedly, be scattered in acetone and preserve.
Embodiment 2
In order to observe magnetic molecularly imprinted polymer pattern, test the Fe to synthesis
3o
4, the non-molecularly imprinted polymer of magnetic (NIP, building-up process except not adding template molecule Nor-Harman, remaining step with to prepare magnetic molecularly imprinted polymer identical) and magnetic molecularly imprinted polymer (MIP) carried out scanning electron microscope sign.As can be seen from Fig. 1 a, Fe
3o
4for form of spherical particles, its particle diameter about 30 ~ 40nm, due to anisotropic dipole magnetism, the Fe obtained
3o
4nanoparticle is often assembled and forms tufted.In Fig. 1 b and 1c, NIP and MIP is also in spheroidal particle, and its particle diameter is about 50 ~ 60nm, and this shows that polymkeric substance is successfully wrapped in Fe
3o
4on core, form Fe
3o
4the nucleocapsid structure of@MAA.Fig. 1 d is through the MIP after 30min ultrasonic extraction, contrasts with Fig. 1 c, finds the still intact preservation of its polymer shell Rotating fields, not from Fe
3o
4core peels off, and this illustrates that MIP has satisfactory stability.
Embodiment 3
In order to investigate the identity of magnetic molecularly imprinted polymer, experiment have chosen the heterocyclic amine Harman similar with Nor-Harman molecular structure as reference compound.Get 1.5mg Nor-Harman respectively and carry out dispersion extraction experiment as Nor-Harman and Harman of MIP to 100 μ g/L of template molecule, the amount of substance of the determinand of polymer extraction is accounted for the per-cent of parent material total amount as extraction efficiency, its comparative result as shown in Figure 2, magnetic molecularly imprinted polymer has better extraction selectivity for template molecule Nor-Harman, mainly come from molecularly imprinted polymer surface to have and have template molecule binding site identical, " hole " that shape size is the same, so magnetic molecularly imprinted polymer is more suitable for the extraction of heterocyclic amine in complex sample.
Embodiment 4
Test the investigation also carried out MIP loading capacity.The standard specimen of template heterocyclic amine Nor-Harman is dissolved in hexanaphthene the standard model being configured to 100-1200 μ g/L different concns, gets 1.0mg MIP respectively and be filled in pillar and be connected on HPLC injection port, form on-line extraction detection system.Analyzed by different concns heterocyclic amine standard model sample introduction, test in contrast with NIP, its loading capacity schematic diagram as shown in Figure 3 simultaneously.Within the scope of finite concentration, along with the increase of Nor-Harman concentration, the adsorptive capacity of MIP and NIP increases until saturated gradually, i.e. the maximum adsorption capacity of sorbing material.Fig. 3 illustrates, MIP is 130 μ g/g to the loading capacity of Nor-Harman, far above the loading capacity 34 μ g/g of NIP to Nor-Harman, therefore, and the loading capacity that magnetic molecularly imprinted polymer prepared by the present invention has had.
Claims (8)
1. a magnetic heterocyclic amine molecularly imprinted polymer, is characterized in that: this polymkeric substance is with Fe
3o
4nanoparticle is as core, core external parcel molecular engram material, described molecular engram material uses heterocyclic amine as template molecule, methacrylic acid is as function monomer, trimethoxypropane gave trimethacrylate and Vinylstyrene are as linking agent, and Diisopropyl azodicarboxylate is prepared as initiator; Preparation method comprises the steps:
(1) Fe of superparamagnetism is synthesized
3o
4particulate;
(2) polyreaction: pipette the Fe that 1.0mmoL – 1.2mmoL step (1) synthesizes
3o
4magnetic particle is in container, add template molecule heterocyclic amine 0.5mmol – 0.6mmol, function monomer MAA 110 μ L-120 μ L, linking agent TRIM 480 μ L-490 μ L and DVB 185 μ L – 188 μ L, add solvent toluene 20mL-22mL, acetonitrile 20mL-22mL again, after sonic oscillation 8min-10min, add 25mg-30mg initiator A IBN, nitrogen blows down oxygen 10min-15min; Stirring velocity 550r/min-650r/min, 58 DEG C of-62 DEG C of water-baths 20 hours-24 hours;
(3) after polyreaction completes, template molecule eluting solvent carries out repeatedly wash-out, until not containing template molecule in eluting solvent;
The diameter of whole polymkeric substance is 50-60nm; As the Fe of core
3o
4diameter of nano particles is 30-40nm.
2. a kind of magnetic heterocyclic amine molecularly imprinted polymer as claimed in claim 1, it is characterized in that: described heterocyclic amine comprises IQ, iso-IQ, MeIQx, IQx, 8-MeIQx, 4-MeIQx, 4,8-DiMeIQx, 7,8-DiMeIQx, 7-MeIgQx, 7,9-DiMeIgQx, PhIP, DMIP, 1,5,6-TMIP, 3, at least one in 5,6-TMIP, Phe-P-1, Norharman, Harman, Trp-P-2, Trp-P-1, A α C, MeA α C, Glu-p-1 and Glu-p-2.
3. prepare a method for magnetic heterocyclic amine molecularly imprinted polymer, comprise the steps:
(1) Fe of superparamagnetism is synthesized
3o
4particulate;
(2) polyreaction: pipette the Fe that 1.0mmoL – 1.2mmoL step (1) synthesizes
3o
4magnetic particle is in container, add template molecule heterocyclic amine 0.5mmol – 0.6mmol, function monomer MAA 110 μ L-120 μ L, linking agent TRIM 480 μ L-490 μ L and DVB 185 μ L – 188 μ L, add solvent toluene 20mL-22mL, acetonitrile 20mL-22mL again, after sonic oscillation 8min-10min, add 25mg-30mg initiator A IBN, nitrogen blows down oxygen 10min-15min; Stirring velocity 550r/min-650r/min, 58 DEG C of-62 DEG C of water-baths 20 hours-24 hours;
(3) after polyreaction completes, template molecule eluting solvent carries out repeatedly wash-out, until not containing template molecule in eluting solvent.
4. a kind of method preparing magnetic heterocyclic amine molecularly imprinted polymer as claimed in claim 3, it is characterized in that: the template molecule heterocyclic amine described in step (2) comprises IQ, iso-IQ, MeIQx, IQx, 8-MeIQx, 4-MeIQx, 4,8-DiMeIQx, 7,8-DiMeIQx, 7-MeIgQx, 7,9-DiMeIgQx, PhIP, DMIP, 1,5,6-TMIP, 3, at least one in 5,6-TMIP, Phe-P-1, Norharman, Harman, Trp-P-2, Trp-P-1, A α C, MeA α C, Glu-p-1 and Glu-p-2.
5. a kind of method preparing magnetic heterocyclic amine molecularly imprinted polymer as claimed in claim 3, is characterized in that:
Step (1) operation is as follows: take 1.28g-1.31g FeSO
47H
2o, 1.0g-1.3g FeCl
3, be dissolved in 25mL-35mL ultrapure water, solution mixing inserted in three-necked bottle; High-speed stirring under 400r/min-500r/min condition, passes into nitrogen 0.5 hour-1 hour simultaneously; Then slowly drip the NaOH of 5mL-8mL 8mol/L – 5mol/L, control NaOH total amount is at 0.04mol; Continue stirring and be warmed up to 80 DEG C-90 DEG C after 0.5 hour-1 hour, keep this temperature to stir 0.5 hour-1 hour; After having reacted, repeatedly cleaned up by the black particle ultrapure water obtained, be scattered in ultrapure water, sealing saves backup.
6. a kind of method preparing magnetic heterocyclic amine molecularly imprinted polymer as claimed in claim 3, is characterized in that:
Step (3) operation is as follows: described eluting solvent is methyl alcohol/ammoniacal liquor=9:1, V/V.
7. a kind of method preparing magnetic heterocyclic amine molecularly imprinted polymer as claimed in claim 3, is characterized in that:
The HPLC that is detected as of eluting solvent analyzes.
8. a kind of method preparing magnetic heterocyclic amine molecularly imprinted polymer as claimed in claim 3, is characterized in that: after step (3) wash-out, after magnetic molecularly imprinted polymer particulate acetone cleans repeatedly, is scattered in acetone and preserves.
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| CN104655695B (en) * | 2015-02-11 | 2017-10-31 | 江南大学 | A kind of magnetic molecularly imprinted sensor for detecting Gram-negative bacteria signaling molecule |
| CN105294935A (en) * | 2015-11-23 | 2016-02-03 | 天津科技大学 | Preparation method and application of polar heterocyclic amine specific separation material |
| PL238942B1 (en) * | 2017-11-24 | 2021-10-25 | Inst Chemii Fizycznej Polskiej Akademii Nauk | Synthetic nucleotide polymer with the recognizing layer, production of such a polymer and application for selective determination of carcinogenic heterocyclic aromatic amine by means of the chemical sensor |
| CN110302838B (en) * | 2019-06-20 | 2022-04-15 | 苏州大学 | Magnetic Fe with PNH surface modified2O3Nano-beads and their use in water treatment |
| CN110699082B (en) * | 2019-09-27 | 2022-10-14 | 天津科技大学 | Preparation method and application of 2-aminobenzimidazole false template molecularly imprinted fluorescent sensing material |
| CN111999401A (en) * | 2020-07-21 | 2020-11-27 | 广东石油化工学院 | Method for detecting amine hazardous substances in food |
| CN114920892A (en) * | 2022-05-19 | 2022-08-19 | 中国烟草总公司郑州烟草研究院 | Magnetic heterocyclic amine molecularly imprinted composite material and preparation method and application thereof |
| CN114917881A (en) * | 2022-05-19 | 2022-08-19 | 中国烟草总公司郑州烟草研究院 | Heterocyclic amine molecularly imprinted composite material and preparation method and application thereof |
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| Biomonitoring of urinary metabolites of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) following human consumption of cooked chicken;H.Frandsen et al.;《Food and Chemical Toxicology》;20080930;第46卷;2.5部分 * |
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