CN103965419A - Preparation method of magnetic imprinted polymer for separating and purifying ractopamine - Google Patents

Preparation method of magnetic imprinted polymer for separating and purifying ractopamine Download PDF

Info

Publication number
CN103965419A
CN103965419A CN201410214026.6A CN201410214026A CN103965419A CN 103965419 A CN103965419 A CN 103965419A CN 201410214026 A CN201410214026 A CN 201410214026A CN 103965419 A CN103965419 A CN 103965419A
Authority
CN
China
Prior art keywords
magnetic
atps
product
ractopamine hydrochloride
ractopamine
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
Application number
CN201410214026.6A
Other languages
Chinese (zh)
Other versions
CN103965419B (en
Inventor
汤轶伟
兰建兴
励建荣
高雪
张德福
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bohai University
Original Assignee
Bohai University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bohai University filed Critical Bohai University
Priority to CN201410214026.6A priority Critical patent/CN103965419B/en
Publication of CN103965419A publication Critical patent/CN103965419A/en
Application granted granted Critical
Publication of CN103965419B publication Critical patent/CN103965419B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to a preparation method of a magnetic molecularly-imprinted polymer for separating and purifying ractopamine, aiming to solve the problem of leakage of magnetic ferroferric oxide in the processes of template elution and practical application of an existing magnetic ractopamine molecularly-imprinted polymer. The method comprises the steps of (1) preparing magnetic ferroferric oxide nano microspheres; (2) preparing an ATPS-modified ferroferric oxide material (ATPS-Fe3O4); (3) preparing a magnetic Fe3O4 functional monomer (MAC-ATPS-Fe3O4); (4) preparing a magnetic RAC molecularly-imprinted polymer (Fe3O4@MIPs). The prepared ractopamine magnetic molecularly-imprinted polymer disclosed by the invention is stable in performance, and can solve the problem of leakage of magnetic ferroferric oxide; the magnetic polymer has a relatively fast adsorption rate to ractopamine, meets the needs of rapid detection, has a rapid magnetic separation capacity, and is very suitable for field sample treatment.

Description

The magnetic blotting method for producing polymer of a kind of separation, purification Ractopamine hydrochloride
Technical field
The present invention relates to a kind of preparation method of core-shell type magnetic molecularly imprinted polymer, relate in particular to the preparation method of a kind of separation, purification, enrichment Ractopamine hydrochloride magnetic Nano molecularly imprinted polymer.
Background technology
Ractopamine hydrochloride (Ractopamine, RAC) belongs to β 2-stimulant, the β of alternative exciting cytolemma unstriated muscle 2-acceptor, clinically for preventing and treating congestive heart failure disease, bronchial asthma and muscular dystrophy etc.RAC is the one of " clenbuterol hydrochloride ", can show " nutrition redistribution effects ", by changing the pathways metabolism of nutritive ingredient, promote the deposition of animal body muscle growth and animal body protein, particularly protein synthetic in skeletal muscle, suppress the synthetic and accumulation of fat simultaneously, and reach effect of improving carcass quality, accelerating the speed of growth.But RAC residence time in blood is longer, and body is had to serious toxic side effect, can cause muscular tremor, vomiting, neuroticism, the illnesss such as palpitaition.China and European Union's majority state all forbid RAC to apply in livestock and poultry cultivation.
Molecular imprinting (MIT) is preparation has specific selectivity polymkeric substance technology to target molecule, in the molecularly imprinted polymer (MIPs) of preparing based on this technology, have and the space structure of target molecule complementation and the binding site of particular arrangement, this is that MIPs has the basis to target molecule specific selectivity.MIPs, with its exclusive specific recognition ability, physical and chemical stability, widespread popularity, obtains applications well in sample pre-treatments, biosensor, bionical immunoassay, chromatographic stationary phases.
At present, molecularly imprinted polymer preparation method taking RAC as target compound has gel-sol method (WangS, Liu L, Fang G, et al.J Sep Sci, 2009, 32 (9): 1333-1339.), bulk polymerization (ZhigangXu, Yufei Hu, Yuling Hu, et al.Journal of Chromatography A, 2010, 1217:3612-3618.), covalent linkage polymerization process (Yiwei Tang, Guozhen Fang, Shuo Wang, et al.Anal Bioanal Chem, 2011, 401 (7): 2275-2282.), MIPs prepared by these methods needs to grind to form the particulate with certain particle diameter and packs solid phase extraction column into as Solid-Phase Extraction material and apply on solid-phase extracting instrument, or with form extraction, the enrichment target molecule of dispersion extraction, not easily separated but dispersion extraction finishes rear MIPs, therefore limit the application of RAC-MIPs in sample pre-treatments.
Dependence to solid-phase extracting instrument while application as Solid-Phase Extraction material in order to reduce MIPs, facilitate dispersion extraction to finish the separation of rear MIPs, with magnetic Fe 3o 4for the magnetic MIPs of core successfully prepares (Yuling Hu, Yuanwen Li, Ruijin Liu, et al.Magnetic molecularly imprinted polymer beadsprepared by microwave heating for selective enrichment of β-agonists in pork and pigliver samples.Talanta, 2011,84:462-470.).The method is taking RAC as template molecule, and acrylamide (AM) is function monomer, and trimethylolpropane tris methyl acrylate (TRIM) is linking agent, and Diisopropyl azodicarboxylate is initiator, with the Fe of PEG-6000 modified 3o 4magnetic RAC molecularly imprinted polymer material has been prepared in nanoparticle copolymerization.But, PEG-6000 and Fe 3o 4combine by non covalent bond mode, a little less than interaction force, in polymerization process, be very easily subject to such environmental effects, destroy Fe 3o 4combination with PEG-6000, causes Fe 3o 4expose; Secondly the Fe that, PEG-6000 modifies 3o 4in MIPs preparation process, do not participate in polyreaction, in wash-out template molecule or actual application, may cause Fe 3o 4reveal, cause the paramagnetism of MIPs to weaken and affect the accuracy of laboratory test results.
Summary of the invention
Goal of the invention
For the above-mentioned deficiency of prior art, the preparation method who the present invention proposes a kind of separation, purification Ractopamine hydrochloride magnetic molecularly imprinted polymer, has mainly solved the existing magnetic Ractopamine hydrochloride molecularly imprinted polymer problem that magnetic ferroferric oxide is revealed in template removal and actual application.
Technical scheme
The present invention is achieved through the following technical solutions:
A magnetic blotting method for producing polymer for separation, purification Ractopamine hydrochloride, is characterized in that: step is as follows:
(1) prepare magnetic ferroferric oxide (Fe 3o 4) Nano microsphere:
By FeCl 24H 2o and FeCl 36H 2o is placed in there-necked flask, adds the deionized water after ultrasonic deoxygenation, mechanical stirring under nitrogen protection; Then by dropwise adding ammoniacal liquor after reaction system heating, dropwise rear thermostatic crystallization; After crystallization, make temperature naturally be down to room temperature, utilize black product Fe synthetic in magnet separation solution 3o 4, use deionized water rinsing Fe 3o 4, remove unreacted solvent until solution neutral is for subsequent use after product vacuum-drying;
(2) prepare the ferriferrous oxide material (ATPS-Fe that 3-aminopropyl trimethoxysilane (ATPS) is modified 3o 4):
Get Fe prepared by step (1) 3o 4the there-necked flask that Nano microsphere is placed in, then adds ethanol-water solution, with Glacial acetic acid adjusting pH to 4, under room temperature, after ultrasonic dispersion, adds ATPS, under nitrogen protection, heating in water bath, and mechanical stirring reaction 10～15h; Reaction finishes rear with magnet separation black product A TPS-Fe 3o 4, and wash product to without oily suspended substance with deionized water, dehydrated alcohol, anhydrous diethyl ether successively, for subsequent use after product vacuum-drying;
(3) prepare magnetic Fe 3o 4function monomer (MAC-ATPS-Fe 3o 4):
ATPS-Fe prepared by step (2) 3o 4material is placed in there-necked flask, adds toluene and K 2cO 3, sonic oscillation 20～30min under condition of ice bath, then stirring at room temperature also dropwise adds methacrylic chloride (MAC), uses the black product magnetic Fe in magnet separation solution after 10～12h 3o 4function monomer MAC-ATPS-Fe 3o 4, and rinsing successively with toluene, ethanol, acetonitrile, it is for subsequent use after dry that product is put into vacuum drying oven;
(4) preparation (Fe of magnetic RAC molecularly imprinted polymer 3o 4@MIPs):
Magnetic Fe prepared by step (3) 3o 4function monomer MAC-ATPS-Fe 3o 4be placed in round-bottomed flask with template molecule Ractopamine hydrochloride, solvent is acetonitrile, under room temperature, stirs after 3～5h, adds linking agent and initiator, and ice-bath ultrasonic is disperseed 5～10min, by mixed solution heating in water bath polymerization 24～30h at 60～65 DEG C, N when reaction 2protection, and mechanical stirring; Polymerization finishes rear solid phase and the liquid phase of utilizing in magnet separation solution, goes upper solution, obtains Fe 3o 4@MIPs product; Rinse Fe with methyl alcohol-methylene dichloride mixing solutions again 3o 4@MIPs product, then puts it in vacuum drying oven, and vacuum-drying is spent the night at 40～45 DEG C; By dried for product methyl alcohol-glacial acetic acid mixed solvent extract Ractopamine hydrochloride, until detect without Ractopamine hydrochloride, after extracting, put into again vacuum drying oven, vacuum-drying 24～30h at 40～45 DEG C.
FeCl in step (1) 24H 2o and FeCl 36H 2the mol ratio of O is 1:2; FeCl 24H 2o is 1mol:8～10L with the molecular volume ratio of deionized water; System Heating temperature is 60～65 DEG C; The ammoniacal liquor adding and FeCl 24H 2the volume mol ratio of O is 1.8～2L:1mol; Thermostatic crystallization temperature is 60～65 DEG C, and the time is 60～80min; Product vacuum-drying temperature is 40～45 DEG C, and the dry time is 24～30h.
Fe in step (2) 3o 4the mass volume ratio of Nano microsphere and ATPS is 1g:2～2.5mL; In the ethanol-water solution adding, the volume ratio of ethanol and water is 1:1; The time of ultrasonic dispersion is 10～20min; The temperature of heating in water bath is 60～65 DEG C; Vacuum drying temperature is 40～45 DEG C, and the dry time is 24～30h.
ATPS-Fe in step (3) 3o 4with the mass volume ratio of methacrylic chloride be 100mg:1mL; ATPS-Fe 3o 4with the mass volume ratio of toluene be 1mg:0.5～1.0mL; ATPS-Fe 3o 4with K 2cO 3mass ratio be 1:1～1.5; The vacuum drying temperature of product is 40～45 DEG C, 24～30h of vacuum drying time.
Linking agent described in step (4) is ethylene glycol dimethacrylate.
Initiator described in step (4) is Diisopropyl azodicarboxylate.
Magnetic Fe in step (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of template molecule Ractopamine hydrochloride be 1g:1mmol.
Magnetic Fe in step (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of linking agent be 1g:20mmol; Magnetic Fe in step (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of initiator be 1g:2～3mmol.
Magnetic Fe in step (4) 3o 4the mass volume ratio of function monomer and solvent acetonitrile is 1g:150～200mL.
In step (4), the volume ratio of methyl alcohol-methylene dichloride mixing solutions system for tax payment alcohol and methylene dichloride is 4:1; In the middle methyl alcohol-glacial acetic acid mixed solvent of step (4), the volume ratio of methyl alcohol and glacial acetic acid is 9:1.
Advantage and effect
Tool of the present invention has the following advantages and beneficial effect:
The RAC magnetic molecularly imprinted polymer that the ferriferrous oxide nano microballoon of modifying taking ATPS and MAC is successively prepared as function monomer, has avoided the leakage problem of polymkeric substance ferriferrous oxide nano microballoon in template removal and actual application; The RAC molecularly imprinted polymer of preparation has adsorption rate faster to RAC, can within the short period (20min), reach adsorption equilibrium, can meet the needs of rapid detection, and the saturation magnetization of the RAC polymkeric substance prepared of the present invention reaches 16emug -1, there is good paramagnetism, be convenient to the separation of MIPs after dispersion extraction, be very suitable for on-the-spot sample preparation.
Brief description of the drawings
Fig. 1 is Fe 3o 4, ATPS-Fe 3o 4, MAC-ATPS-Fe 3o 4and Fe 3o 4the infrared spectrogram of@MIPs.Known Fe in figure 3o 4nanoparticle is successfully prepared, the modification success to Z 250 with ATPS and MAC successively, and molecular imprinting process has also successfully been carried out.
Fig. 2 is Fe 3o 4(a), ATPS-Fe 3o 4(b), MAC-ATPS-Fe 3o 4(c), Fe 3o 4the XRD figure of@MIP (d).Fe in figure 3o 4characteristic peak 2 θ=30.33 °, 35.73 °, 43.40 °, 53.96 °, 57.37 ° and 63.13 ° of corresponding Emission in Cubic Fe of difference 3o 4(220), (311), (400), (422), (511) and (440) crystal face, with the Fe of standard 3o 4characteristic peak diffraction peak matches; The Fe modifying with ATPS and MAC 3o 4and the characteristic peak of the XRD of molecularly imprinted polymer and Fe 3o 4similar, Fe is described 3o 4in molecularly imprinted polymer, keep feature crystal formation, kept good superparamagnetism.
Fig. 3 is Fe 3o 4@MIPs magnetic hysteresis loop, as seen from the figure, the saturation magnetization of magnetic molecularly imprinted polymer is 16.64emu/g, magnetic molecularly imprinted polymer has good separating effect under externally-applied magnetic field.
Fig. 4 is Fe 3o 4@MIPs transmission electron microscope picture, as seen from the figure, molecularly imprinted polymer is successful at Fe 3o 4nanoparticle surface preparation.
Fig. 5 is Fe 3o 4@MIPs kinetics of adsorption, as seen from the figure, magnetic molecularly imprinted polymer can reach adsorption equilibrium in 20min.
Fig. 6 is Fe 3o 4the accurate second-order kinetic equation matching of@MIPs kinetics of adsorption data.
Fig. 7 is Fe 3o 4@MIPs and Fe 3o 4@NIPs isothermal adsorption curve.
Fig. 8 is Fe 3o 4@MIPs and Fe 3o 4the Choice tests of@NIPs absorption Ractopamine hydrochloride and other three kinds of analog Racemic isoproterenols, cardilan and terbutalines.Result shows: synthetic Fe 3o 4@MIPs has good selective recognition ability to target molecule RAC.
Embodiment
The present invention will be described in detail with reference to the accompanying drawings:
The present invention is the preparation method of a kind of separation, purification, enrichment Ractopamine hydrochloride magnetic molecularly imprinted polymer, modifies Fe successively with 3-aminopropyl trimethoxysilane (ATPS) and methacrylic chloride (MAC) by covalent method 3o 4as function monomer, taking RAC as template molecule, Diisopropyl azodicarboxylate (AIBN) is initiator afterwards, and ethylene glycol dimethacrylate (EDMA) is prepared RAC magnetic Nano molecularly imprinted polymer for linking agent.In the present invention, Fe 3o 4in@MIPs preparation process due to nanometer Fe 3o 4microballoon has participated in polyreaction, so overcome MIPs Fe in wash-out template molecule and actual application 3o 4the leakage problem of molecule, has increased the access times of magnetic MIPs.
The magnetic blotting method for producing polymer of this separation of the present invention, purification Ractopamine hydrochloride, its step is as follows:
(1) prepare magnetic ferroferric oxide (Fe 3o 4) Nano microsphere:
By FeCl 24H 2o and FeCl 36H 2o is placed in there-necked flask, adds the deionized water after ultrasonic degas, mechanical stirring under nitrogen protection; Then by dropwise adding ammoniacal liquor after reaction system heating, dropwise rear thermostatic crystallization; After crystallization, make temperature naturally be down to room temperature, utilize black product Fe synthetic in magnet separation solution 3o 4, use deionized water rinsing Fe 3o 4, remove unreacted solvent until solution neutral is for subsequent use after product vacuum-drying;
(2) prepare the ferriferrous oxide material (ATPS-Fe that 3-aminopropyl trimethoxysilane (ATPS) is modified 3o 4):
Get Fe prepared by step (1) 3o 4the there-necked flask that Nano microsphere is placed in, then adds ethanol-water solution (1:1, V:V), with Glacial acetic acid adjusting pH to 4, under room temperature, after ultrasonic dispersion, adds ATPS, under nitrogen protection, heating in water bath, and mechanical stirring reaction 10～15h; Reaction finishes rear with magnet separation black product A TPS-Fe 3o 4, and wash product to without oily suspended substance with deionized water, dehydrated alcohol, anhydrous diethyl ether successively, for subsequent use after product vacuum-drying;
(3) prepare magnetic Fe 3o 4function monomer (MAC-ATPS-Fe 3o 4):
ATPS-Fe prepared by step (2) 3o 4material is placed in there-necked flask, adds toluene and K 2cO 3, sonic oscillation 20～30min under condition of ice bath, then stirring at room temperature also dropwise adds methacrylic chloride (MAC), uses the black product magnetic Fe in magnet separation solution after 10～12h 3o 4function monomer MAC-ATPS-Fe 3o 4, and rinsing successively with toluene, ethanol, acetonitrile, it is for subsequent use after dry that product is put into vacuum drying oven;
(4) preparation (Fe of magnetic RAC molecularly imprinted polymer 3o 4@MIPs):
Magnetic Fe prepared by step (3) 3o 4function monomer MAC-ATPS-Fe 3o 4be placed in round-bottomed flask with template molecule Ractopamine hydrochloride, solvent is acetonitrile, under room temperature, stirs after 3～5h, adds linking agent and initiator, and ice-bath ultrasonic is disperseed 5～10min, by mixed solution heating in water bath polymerization 24～30h at 60～65 DEG C, N when reaction 2protection, and mechanical stirring; Polymerization finishes rear solid phase and the liquid phase of utilizing in magnet separation solution, goes upper solution, obtains Fe 3o 4@MIPs product; Use again methyl alcohol-methylene dichloride (4:1, V:V) mixing solutions to rinse Fe 3o 4@MIPs product, then puts it in vacuum drying oven, and vacuum-drying is spent the night at 40～45 DEG C; By dried for product methyl alcohol-glacial acetic acid (9:1, V:V) mixed solvent extract Ractopamine hydrochloride, until detect without Ractopamine hydrochloride, after extracting, put into again vacuum drying oven, vacuum-drying 24～30h at 40～45 DEG C.
FeCl in above-mentioned steps (1) 24H 2o and FeCl 36H 2the mol ratio of O is 1:2; FeCl 24H 2o is 1mol:8～10L with the molecular volume ratio of deionized water; System Heating temperature is 60～65 DEG C; The ammoniacal liquor adding and FeCl 24H 2the volume mol ratio of O is 1.8～2L:1mol; Thermostatic crystallization temperature is 60～65 DEG C, and the time is 60～80min; Product vacuum-drying temperature is 40～45 DEG C, and the dry time is 24～30h.
Fe in above-mentioned steps (2) 3o 4the mass volume ratio of Nano microsphere and ATPS is 1g:2～2.5mL; In the ethanol-water solution adding, the volume ratio of ethanol and water is 1:1; The time of ultrasonic dispersion is 10～20min; The temperature of heating in water bath is 60～65 DEG C; Vacuum drying temperature is 40～45 DEG C, and the dry time is 24～30h.
In above-mentioned steps (3), ATPS-Fe 3o 4with the mass volume ratio of methacrylic chloride be 100mg:1mL; ATPS-Fe 3o 4with the mass volume ratio of toluene be 1mg:0.5～1.0mL, ATPS-Fe 3o 4with K 2cO 3mass ratio be 1:1～1.5; The vacuum drying temperature of product is 40～45 DEG C, 24～30h of vacuum drying time.
Linking agent described in above-mentioned steps (4) is ethylene glycol dimethacrylate.
Initiator described in above-mentioned steps (4) is Diisopropyl azodicarboxylate.
Magnetic Fe in above-mentioned steps (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of template molecule Ractopamine hydrochloride be 1g:1mmol.
Magnetic Fe in above-mentioned steps (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of linking agent be 1g:20mmol.
Magnetic Fe in above-mentioned steps (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of initiator be 1g:2.0～3.0mmol.
Magnetic Fe in above-mentioned steps (4) 3o 4the mass volume ratio of function monomer and solvent acetonitrile is 1g:150～200mL.
In above-mentioned steps (4), the volume ratio of methyl alcohol-methylene dichloride mixing solutions system for tax payment alcohol and methylene dichloride is 4:1; In the middle methyl alcohol-glacial acetic acid mixed solvent of step (4), the volume ratio of methyl alcohol and glacial acetic acid is 9:1.
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:
A magnetic blotting method for producing polymer for separation, purification Ractopamine hydrochloride, its step is as follows:
(1) prepare magnetic ferroferric oxide nanometer microballoon:
Get 0.03mol FeCl 24H 2o and 0.06mol FeCl 36H 2o adds in there-necked flask, then adds the deionized water 300mL after ultrasonic degas, mechanical stirring under nitrogen protection.After reaction system is heated to 65 DEG C, dropwise add 60mL ammoniacal liquor, dropwise thermostatic crystallization 60min at latter 65 DEG C; After crystallization, make temperature naturally be down to room temperature, utilize black product Fe synthetic in magnet separation solution 3o 4, use deionized water rinsing Fe 3o 4, remove unreacted solvent until solution neutral, product is for subsequent use after vacuum-drying 24h at 45 DEG C.
(2) prepare the ferriferrous oxide material (ATPS-Fe that 3-aminopropyl trimethoxysilane (ATPS) is modified 3o 4):
Get Fe prepared by 1.5g step (1) 3o 4nano microsphere is placed in there-necked flask, then add the ethanol-water solution (1:1 of 200～250mL, V:V), with Glacial acetic acid adjusting pH to 4, ultrasonic dispersion 10min under room temperature, adds 3.268mL ATPS (3-aminopropyl trimethoxysilane), under nitrogen protection, heating in water bath at 60 DEG C, mechanical stirring 10h; Reaction finishes rear with magnet separation black product A TPS-Fe 3o 4, and be washed till without oily suspended substance with deionized water, dehydrated alcohol, anhydrous diethyl ether successively, for subsequent use after 45 DEG C of vacuum-drying 24h.
(3) prepare magnetic Fe 3o 4function monomer (MAC-ATPS-Fe 3o 4):
Get ATPS-Fe prepared by 400mg step (2) 3o 4material is placed in there-necked flask, adds 200mL toluene, 0.4g K 2cO 3, sonic oscillation 30min under condition of ice bath, stirring at room temperature also dropwise adds 4mL methacrylic chloride (MAC), uses the black product magnetic Fe in magnet separation solution after 12h 3o 4function monomer MAC-ATPS-Fe 3o 4, and rinsing successively with toluene, ethanol, acetonitrile, product is put into after 45 DEG C of vacuum-drying 24h of vacuum drying oven for subsequent use.
(4) preparation (Fe of magnetic RAC molecularly imprinted polymer 3o 4@MIPs):
Get magnetic Fe prepared by 100mg step (3) 3o 4function monomer MAC-ATPS-Fe 3o 4and 0.1mmol (0.0337g) template molecule Ractopamine hydrochloride RAC is to round-bottomed flask, solvent is 20mL acetonitrile, under room temperature, stir after 3h, get 2mmol (0.380mL) linking agent EGDMA and 0.2mmol initiator A IBN is added in round-bottomed flask, ice-bath ultrasonic is disperseed 5min; By mixed solution heating in water bath polymerization 24h at 65 DEG C, N when reaction 2protection, and mechanical stirring; Polymerization finishes the rear solid phase liquid phase of utilizing in magnet separation solution, goes upper solution, obtains black product Fe 3o 4@MIPs; Use again methyl alcohol-CH 2cl 2(4:1, V:V) mixing solutions rinses Fe 3o 4@MIPs product, then puts it in vacuum drying oven, and vacuum-drying is spent the night at 45 DEG C; By dried product soxhlet extraction method, use methyl alcohol-glacial acetic acid (9:1, V:V) mixed solvent to extract Ractopamine hydrochloride, until detect without Ractopamine hydrochloride RAC, after extracting, put into again vacuum drying oven, vacuum-drying 24h at 45 DEG C.
Embodiment 2:
A magnetic blotting method for producing polymer for separation, purification Ractopamine hydrochloride, its step is as follows:
(1) prepare magnetic ferroferric oxide nanometer microballoon:
Get 0.03mol FeCl 24H 2o and 0.06mol FeCl 36H 2o adds in there-necked flask, then adds the deionized water 240mL after ultrasonic degas, and mechanical stirring under nitrogen protection dropwise adds 54mL ammoniacal liquor after reaction system is heated to 60 DEG C, dropwises thermostatic crystallization 80min at latter 60 DEG C; After crystallization, make temperature naturally be down to room temperature, utilize black product Fe synthetic in magnet separation solution 3o 4, use deionized water rinsing Fe 3o 4, remove unreacted solvent until solution neutral, product is for subsequent use after vacuum-drying 30h at 40 DEG C.
(2) prepare the ferriferrous oxide material (ATPS-Fe that 3-aminopropyl trimethoxysilane (ATPS) is modified 3o 4):
Get Fe prepared by 1g step (1) 3o 4nano microsphere is placed in there-necked flask, then add the ethanol-water solution (1:1 of 200～250mL, V:V), with Glacial acetic acid adjusting pH to 4, ultrasonic dispersion 20min under room temperature, adds 2mL ATPS (3-aminopropyl trimethoxysilane), under nitrogen protection, heating in water bath at 65 DEG C, mechanical stirring 15h; Reaction finishes rear with magnet separation black product A TPS-Fe 3o 4, and be washed till without oily suspended substance with deionized water, dehydrated alcohol, anhydrous diethyl ether successively, for subsequent use after 40 DEG C of vacuum-drying 30h.
(3) prepare magnetic Fe 3o 4function monomer (MAC-ATPS-Fe 3o 4):
Get ATPS-Fe prepared by 500mg step (2) 3o 4material is placed in there-necked flask, adds 300mL toluene, 600mgK 2cO 3, sonic oscillation 20min under condition of ice bath, stirring at room temperature also dropwise adds 5mL methacrylic chloride (MAC), uses the black product magnetic Fe in magnet separation solution after 10h 3o 4function monomer MAC-ATPS-Fe 3o 4, and rinsing successively with toluene, ethanol, acetonitrile, product is put into after 40 DEG C of vacuum-drying 30h of vacuum drying oven for subsequent use.
(4) preparation (Fe of magnetic RAC molecularly imprinted polymer 3o 4@MIPs):
Get magnetic Fe prepared by 100mg step (3) 3o 4function monomer MAC-ATPS-Fe 3o 4and 0.1mmol (0.0337g) template molecule Ractopamine hydrochloride RAC is to round-bottomed flask, solvent is 15mL acetonitrile, under room temperature, stir after 5h, get 2mmol (0.380mL) linking agent EGDMA and 0.25mmol initiator A IBN is added in round-bottomed flask, ice-bath ultrasonic is disperseed 10min; By mixed solution heating in water bath polyase 13 0h at 60 DEG C, N when reaction 2protection, and mechanical stirring; Polymerization finishes the rear solid phase liquid phase of utilizing in magnet separation solution, goes upper solution, obtains black product Fe 3o 4@MIPs; Use again methyl alcohol-CH 2cl 2(4:1, V:V) mixing solutions rinses Fe 3o 4@MIPs product, then puts it in vacuum drying oven, and vacuum-drying is spent the night at 40 DEG C; By dried product soxhlet extraction method, use methyl alcohol-glacial acetic acid (9:1, V:V) mixed solvent to extract Ractopamine hydrochloride, until detect without Ractopamine hydrochloride RAC, after extracting, put into again vacuum drying oven, vacuum-drying 30h at 40 DEG C.
Embodiment 3:
A magnetic blotting method for producing polymer for separation, purification Ractopamine hydrochloride, its step is as follows:
(1) prepare magnetic ferroferric oxide nanometer microballoon:
Get 0.03mol FeCl 24H 2o and 0.06mol FeCl 36H 2o adds in there-necked flask, then adds the deionized water 270mL after ultrasonic degas, and mechanical stirring under nitrogen protection dropwise adds 57mL ammoniacal liquor after reaction system is heated to 62 DEG C, dropwises thermostatic crystallization 70min at latter 63 DEG C; After crystallization, make temperature naturally be down to room temperature, utilize black product Fe synthetic in magnet separation solution 3o 4, use deionized water rinsing Fe 3o 4, remove unreacted solvent until solution neutral, product is for subsequent use after vacuum-drying 28h at 42 DEG C.
(2) prepare the ferriferrous oxide material (ATPS-Fe that 3-aminopropyl trimethoxysilane (ATPS) is modified 3o 4):
Get Fe prepared by 1g step (1) 3o 4nano microsphere is placed in there-necked flask, then add the ethanol-water solution (1:1 of 200～250mL, V:V), with Glacial acetic acid adjusting pH to 4, ultrasonic dispersion 15min under room temperature, adds 2.5mL ATPS (3-aminopropyl trimethoxysilane), under nitrogen protection, heating in water bath at 62 DEG C, mechanical stirring 13h; Reaction finishes rear with magnet separation black product A TPS-Fe 3o 4, and be washed till without oily suspended substance with deionized water, dehydrated alcohol, anhydrous diethyl ether successively, for subsequent use after 42 DEG C of vacuum-drying 28h.
(3) prepare magnetic Fe 3o 4function monomer (MAC-ATPS-Fe 3o 4):
Get ATPS-Fe prepared by 500mg step (2) 3o 4material is placed in there-necked flask, adds 500mL toluene, 750mg K 2cO 3, sonic oscillation 25min under condition of ice bath, stirring at room temperature also dropwise adds 5mL methacrylic chloride (MAC), uses the black product magnetic Fe in magnet separation solution after 11h 3o 4function monomer MAC-ATPS-Fe 3o 4, and rinsing successively with toluene, ethanol, acetonitrile, product is put into after 42 DEG C of vacuum-drying 28h of vacuum drying oven for subsequent use.
(4) preparation (Fe of magnetic RAC molecularly imprinted polymer 3o 4@MIPs):
Get magnetic Fe prepared by 100mg step (3) 3o 4function monomer MAC-ATPS-Fe 3o 4and 0.1mmol (0.0337g) template molecule Ractopamine hydrochloride RAC is to round-bottomed flask, solvent is 18mL acetonitrile, under room temperature, stir after 4h, get 2mmol (0.380mL) linking agent EGDMA and 0.3mmol initiator A IBN is added in round-bottomed flask, ice-bath ultrasonic is disperseed 8min; By mixed solution heating in water bath polymerization 28h at 63 DEG C, N when reaction 2protection, and mechanical stirring; Polymerization finishes the rear solid phase liquid phase of utilizing in magnet separation solution, goes upper solution, obtains black product Fe 3o 4@MIPs; Use again methyl alcohol-CH 2cl 2(4:1, V:V) mixing solutions rinses Fe 3o 4@MIPs product, then puts it in vacuum drying oven, and vacuum-drying is spent the night at 42 DEG C; By dried product soxhlet extraction method, use methyl alcohol-glacial acetic acid (9:1, V:V) mixed solvent to extract Ractopamine hydrochloride, until detect without Ractopamine hydrochloride RAC, after extracting, put into again vacuum drying oven, vacuum-drying 28h at 42 DEG C.
Embodiment 4: the preparation (Fe of the non-imprinted polymer of magnetic 3o 4@MIPs): implementation condition is identical with embodiment 1, but does not add template molecule RAC.
Adopt Fourier infrared spectrograph to detect synthetic Fe 3o 4, ATPS-Fe 3o 4, MAC-ATPS-Fe 3o 4, Fe 3o 4@MIPs detects, and detected result as shown in Figure 1.Be respectively Fe by a, b, c, d infrared spectrogram in Fig. 1 3o 4, ATPS-Fe 3o 4, MAC-ATPS-Fe 3o 4, Fe 3o 4@MIPs.At Fe 3o 4in infrared spectrogram, 582cm -1peak Fe 3o 4the charateristic avsorption band of middle Fe-O key; At ATPS-Fe 3o 4in infrared spectrogram, 588cm -1for the charateristic avsorption band of Fe-O-Si key, 3442cm -1and 1635cm -1for N-H charateristic avsorption band; At MAC-ATPS-Fe 3o 4in infrared spectrogram, 1396cm -1for the absorption peak of secondary amide key, 1548cm -1it is the in-plane bending vibration absorption peak of N-H; Fe 3o 4@MIPs spectrogram explanation magnetic molecularly imprinted polymer is successfully prepared.
Experimental example 1:
By 7 parts of 20mg Fe 3o 4@MIPs adds respectively and contains in the Ractopamine hydrochloride acetonitrile solution that 10mL concentration is 100mg/L, then under room temperature these 7 parts of mixtures on horizontal oscillator tube to vibrate under 300rpm rotating speed 5,10,20,40,60,80,120 minutes.After duration of oscillation finishes, supernatant liquid magnet separated and collected, the not Ractopamine hydrochloride molecular conecentration high-performance liquid chromatogram determination of absorption, calculates loading capacity according to result.Result as shown in Figure 5, the magnetic Ractopamine hydrochloride Fe of known preparation 3o 4@MIPs has adsorption rate faster to target compound, under experimental concentration, can in 20 minutes, reach adsorption equilibrium.
According to accurate second-order kinetic equation curve of adsorption kinetics in Fig. 5 is carried out to matching, wherein q trepresent Ractopamine hydrochloride magnetic Fe 3o 4@MIPs is at the adsorptive capacity of different time, q efor the theoretical adsorptive capacity of second-order kinetic equation, k is first order kinetics reaction rate constant, and t is the time.As shown in Figure 6, Fig. 6 is Fe to fitting result 3o 4the accurate second-order kinetic equation fit equation of@MIPs kinetics of adsorption data, the Fe being prepared by example 4 by the matching of Origin8.0 analysis software 3o 4relation conefficient (the R of the accurate second-order kinetics matched curve equation of@MIPs 2) be 0.9974, when the balance calculated by formula, adsorptive capacity is 11.1mg/g, during with experiment gained balance, adsorptive capacity is close, and the Fe being prepared by example 4 is described 3o 4@MIPs meets accurate second-order kinetics model to the absorption of Ractopamine hydrochloride.
Experimental example 2:
Get that 10mL starting point concentration is respectively 20,40,60,80,100,120,140, the Ractopamine hydrochloride solution of 160mg/L in 50mL volumetric flask, the Fe that then adds respectively 20mg to be prepared by embodiment 4 3o 4@MIPs and Fe 3o 4@NIPs polymkeric substance, adsorbs 60 minutes under with 300rmp rotating speed at level oscillation instrument under room temperature.After time finishes, supernatant liquid magnet separated and collected, the not Ractopamine hydrochloride molecular conecentration high-performance liquid chromatogram determination of absorption, calculates loading capacity according to result.As shown in Figure 7, Fig. 7 is Fe to result 3o 4@MIPs and Fe 3o 4@NIPs isothermal adsorption curve, as shown in Figure 7, Fe 3o 4@MIPs and Fe 3o 4the loading capacity of@NIPs increases along with the increase of starting point concentration, when concentration is 120mg/L, and Fe 3o 4the maximum adsorption capacity of@MIPs is 11.38mg/g, Fe 3o 4@NIPs maximum adsorption capacity is 5.27mg/g.Fe 3o 4@MIPs is significantly higher than Fe to the loading capacity of Ractopamine hydrochloride 3o 4the loading capacity of@NIPs to Ractopamine hydrochloride, illustrates synthetic Fe 3o 4@MIPs has special adsorptivity to Ractopamine hydrochloride.
Experimental example 3:
In order to investigate the specific adsorption of molecularly imprinted polymer to template molecule RAC, select three analogs spies of RAC to walk his woods (TER), cardilan (ISOX), a competition thing that hydroxyl isoproterenol (ISOP) is RAC.Concrete operations are as follows:
Accurately take Fe 3o 4@MIPs and Fe 3o 4@NIPs20mg, in 50mL volumetric flask, adds 10mL100mg L -1rAC, TER, ISOX, the solution of ISOP, level oscillation instrument is to adsorb under 300rmp rotating speed 60 minutes.After duration of oscillation finishes, supernatant liquid magnet separated and collected, the not Ractopamine hydrochloride molecular conecentration high-performance liquid chromatogram determination of absorption, calculates loading capacity according to result.Calculate partition ratio (K according to following formula again d), select coefficient (k) and relative selection coefficient (k').
k d = { C i - C f C f } × { V ( ml ) } / { M ( g ) } , k d ( RAC ) k d ( X ) , k ′ = k ( Fe 3 O 4 @ MIPs ) k ( Fe 3 O 4 @ NIPs )
Wherein: C ifor the concentration of RAC in initial solution; C ffor the concentration of RAC in solution after absorption; V is the volume of RAC standardized solution, and M is amount of polymers; X is the analog of competitive adsorption, and RAC is Ractopamine hydrochloride.Experimental result is in table 1, as shown in Table 1, and magnetic Fe 3o 4@MIPs is 1.93 times of ISOP, is 0.517 times of TERB, is 31 times of ISOP the adsorption selectivity of Ractopamine hydrochloride, and recognition performance is remarkable.
Table 1 magnetic Fe 3o 4@MIPs and Fe 3o 4@NIPs selective adsorption result

Claims (10)

1. a magnetic blotting method for producing polymer that separates, purifies Ractopamine hydrochloride, is characterized in that: step is as follows:
(1) prepare magnetic ferroferric oxide (Fe 3o 4) Nano microsphere:
By FeCl 24H 2o and FeCl 36H 2o is placed in there-necked flask, adds the deionized water after ultrasonic deoxygenation, mechanical stirring under nitrogen protection; Then by dropwise adding ammoniacal liquor after reaction system heating, dropwise rear thermostatic crystallization; After crystallization, make temperature naturally be down to room temperature, utilize black product Fe synthetic in magnet separation solution 3o 4, use deionized water rinsing Fe 3o 4, remove unreacted solvent until solution neutral is for subsequent use after product vacuum-drying;
(2) prepare the ferriferrous oxide material (ATPS-Fe that 3-aminopropyl trimethoxysilane (ATPS) is modified 3o 4):
Get Fe prepared by step (1) 3o 4nano microsphere is placed in there-necked flask, then adds ethanol-water solution, with Glacial acetic acid adjusting pH to 4, under room temperature, after ultrasonic dispersion, adds ATPS, under nitrogen protection, heating in water bath, and mechanical stirring reaction 10～15h; Reaction finishes rear with magnet separation black product A TPS-Fe 3o 4, and wash product to without oily suspended substance with deionized water, dehydrated alcohol, anhydrous diethyl ether successively, for subsequent use after product vacuum-drying;
(3) prepare magnetic Fe 3o 4function monomer (MAC-ATPS-Fe 3o 4):
ATPS-Fe prepared by step (2) 3o 4material is placed in there-necked flask, adds toluene and K 2cO 3, sonic oscillation 20～30min under condition of ice bath, then stirring at room temperature also dropwise adds methacrylic chloride (MAC), uses the black product magnetic Fe in magnet separation solution after 10～12h 3o 4function monomer MAC-ATPS-Fe 3o 4, and rinsing successively with toluene, ethanol, acetonitrile, it is for subsequent use after dry that product is put into vacuum drying oven;
(4) preparation (Fe of magnetic RAC molecularly imprinted polymer 3o 4@MIPs):
Magnetic Fe prepared by step (3) 3o 4function monomer MAC-ATPS-Fe 3o 4be placed in round-bottomed flask with template molecule Ractopamine hydrochloride, dispersion solvent is acetonitrile, under room temperature, stirs after 3～5h, adds linking agent and initiator, and ice-bath ultrasonic is disperseed 5～10min, by mixed solution heating in water bath polymerization 24～30h at 60～65 DEG C, N when reaction 2protection, and mechanical stirring; Polymerization finishes rear solid phase and the liquid phase of utilizing in magnet separation solution, goes upper solution, obtains Fe 3o 4@MIPs product; Rinse Fe with methyl alcohol-methylene dichloride mixing solutions again 3o 4@MIPs product, then puts it in vacuum drying oven, and vacuum-drying is spent the night at 40～45 DEG C; By dried for product methyl alcohol-glacial acetic acid mixed solvent extract Ractopamine hydrochloride, until detect without Ractopamine hydrochloride, after extracting, put into again vacuum drying oven, vacuum-drying 24～30h at 40～45 DEG C.
2. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: FeCl in step (1) 24H 2o and FeCl 36H 2the mol ratio of O is 1:2; FeCl 24H 2o is 1mol:8～10L with the molecular volume ratio of deionized water; System Heating temperature is 60～65 DEG C; The ammoniacal liquor adding and FeCl 24H 2the volume mol ratio of O is 1.8～2L:1mol; Thermostatic crystallization temperature is 60～65 DEG C, and the time is 60～80min; Product vacuum-drying temperature is 40～45 DEG C, and the dry time is 24～30h.
3. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: the Fe in step (2) 3o 4the mass volume ratio of Nano microsphere and ATPS is 1g:2～2.5mL; In the ethanol-water solution adding, the volume ratio of ethanol and water is 1:1; The time of ultrasonic dispersion is 10～20min; The temperature of heating in water bath is 60～65 DEG C; Vacuum drying temperature is 40～45 DEG C, and the dry time is 24～30h.
4. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: ATPS-Fe in step (3) 3o 4with the mass volume ratio of methacrylic chloride be 100mg:1mL; ATPS-Fe 3o 4with the mass volume ratio of toluene be 1mg:0.5～1.0mL; ATPS-Fe 3o 4with K 2cO 3mass ratio be 1:1～1.5; The vacuum drying temperature of product is 40～45 DEG C, 24～30h of vacuum drying time.
5. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: the linking agent described in step (4) is ethylene glycol dimethacrylate.
6. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: the initiator described in step (4) is Diisopropyl azodicarboxylate.
7. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: magnetic Fe in step (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of template molecule Ractopamine hydrochloride be 1g:1mmol.
8. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: magnetic Fe in step (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of linking agent be 1g:20mmol; Magnetic Fe in step (4) 3o 4function monomer MAC-ATPS-Fe 3o 4with the quality mol ratio of initiator be 1g:2～3mmol.
9. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: magnetic Fe in step (4) 3o 4the mass volume ratio of function monomer and solvent acetonitrile is 1g:150～200mL.
10. the magnetic blotting method for producing polymer of separation according to claim 1, purification Ractopamine hydrochloride, is characterized in that: in step (4), the volume ratio of methyl alcohol-methylene dichloride mixing solutions system for tax payment alcohol and methylene dichloride is 4:1; In the middle methyl alcohol-glacial acetic acid mixed solvent of step (4), the volume ratio of methyl alcohol and glacial acetic acid is 9:1.
CN201410214026.6A 2014-05-19 2014-05-19 A kind of separation, the magnetic blotting method for producing polymer of purification Ractopamine Expired - Fee Related CN103965419B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410214026.6A CN103965419B (en) 2014-05-19 2014-05-19 A kind of separation, the magnetic blotting method for producing polymer of purification Ractopamine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410214026.6A CN103965419B (en) 2014-05-19 2014-05-19 A kind of separation, the magnetic blotting method for producing polymer of purification Ractopamine

Publications (2)

Publication Number Publication Date
CN103965419A true CN103965419A (en) 2014-08-06
CN103965419B CN103965419B (en) 2016-08-17

Family

ID=51235458

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410214026.6A Expired - Fee Related CN103965419B (en) 2014-05-19 2014-05-19 A kind of separation, the magnetic blotting method for producing polymer of purification Ractopamine

Country Status (1)

Country Link
CN (1) CN103965419B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104356323A (en) * 2014-10-13 2015-02-18 北京大学 Magnetic molecularly imprinted nano-particle as well as preparation method and application thereof
CN104892868A (en) * 2015-05-14 2015-09-09 江苏科技大学 Silica gel surface molecularly imprinted polymer with specific adsorption of DEHP and preparation method and application thereof
CN104910339A (en) * 2015-06-23 2015-09-16 嘉兴学院 Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid
CN105363394A (en) * 2015-09-24 2016-03-02 济南大学 Preparation and application of magnetic fluorescent molecule imprinting nano-microspheres for detecting nitrobenzene
CN105754053A (en) * 2016-03-23 2016-07-13 广东省工程技术研究所 Preparation method of MIP (molecular imprinted polymer) magnetic mesoporous silica-based microspheres
CN106622179A (en) * 2016-09-27 2017-05-10 上海市农业科学院 Magnetic molecularly imprinted material for identifying chlorophyll, preparation method of material and application
CN109293855A (en) * 2018-09-05 2019-02-01 江西中医药大学 A kind of preparation method and applications of surface-functionalized magnetic nanomolecules imprinted polymer
CN109675531A (en) * 2018-12-21 2019-04-26 洛阳理工学院 A kind of preparation method of magnetic metal ion surface molecular engram material
CN111825814A (en) * 2020-07-29 2020-10-27 重庆医科大学 Catechol amine substance magnetic molecularly imprinted polymer, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
汤轶伟等: "《分子印迹技术在莱克多巴胺检测中的应用研究进展》", 《包装与食品机械》, vol. 32, no. 1, 28 February 2014 (2014-02-28), pages 55 - 59 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104356323A (en) * 2014-10-13 2015-02-18 北京大学 Magnetic molecularly imprinted nano-particle as well as preparation method and application thereof
CN104892868A (en) * 2015-05-14 2015-09-09 江苏科技大学 Silica gel surface molecularly imprinted polymer with specific adsorption of DEHP and preparation method and application thereof
CN104892868B (en) * 2015-05-14 2017-09-12 江苏科技大学 A kind of specific adsorption DEHP Silica Surface molecularly imprinted polymer and preparation method and application
CN104910339B (en) * 2015-06-23 2017-06-06 嘉兴学院 Magnetic molecularly imprinted poly ion liquid and its production and use for detecting Ractopamine
CN104910339A (en) * 2015-06-23 2015-09-16 嘉兴学院 Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid
CN105363394A (en) * 2015-09-24 2016-03-02 济南大学 Preparation and application of magnetic fluorescent molecule imprinting nano-microspheres for detecting nitrobenzene
CN105363394B (en) * 2015-09-24 2017-11-07 济南大学 A kind of preparation and application of the magnetic fluorescence molecular engram nanoparticle for detecting nitrobenzene
CN105754053A (en) * 2016-03-23 2016-07-13 广东省工程技术研究所 Preparation method of MIP (molecular imprinted polymer) magnetic mesoporous silica-based microspheres
CN106622179A (en) * 2016-09-27 2017-05-10 上海市农业科学院 Magnetic molecularly imprinted material for identifying chlorophyll, preparation method of material and application
CN106622179B (en) * 2016-09-27 2019-08-09 上海市农业科学院 A kind of magnetic molecularly imprinted material and its preparation method and application identifying chlorophyll
CN109293855A (en) * 2018-09-05 2019-02-01 江西中医药大学 A kind of preparation method and applications of surface-functionalized magnetic nanomolecules imprinted polymer
CN109293855B (en) * 2018-09-05 2020-12-01 江西中医药大学 Preparation method and application of surface functionalized magnetic nano molecularly imprinted polymer
CN109675531A (en) * 2018-12-21 2019-04-26 洛阳理工学院 A kind of preparation method of magnetic metal ion surface molecular engram material
CN111825814A (en) * 2020-07-29 2020-10-27 重庆医科大学 Catechol amine substance magnetic molecularly imprinted polymer, and preparation method and application thereof
CN111825814B (en) * 2020-07-29 2023-03-21 重庆医科大学 Catechol amine substance magnetic molecularly imprinted polymer, and preparation method and application thereof

Also Published As

Publication number Publication date
CN103965419B (en) 2016-08-17

Similar Documents

Publication Publication Date Title
CN103965419A (en) Preparation method of magnetic imprinted polymer for separating and purifying ractopamine
Andersson et al. A highly selective solid phase extraction sorbent for pre-concentration of sameridine made by molecular imprinting
Zhang et al. Preparation of core–shell magnetic ion-imprinted polymer for selective extraction of Pb (II) from environmental samples
Zhou et al. Restricted access magnetic imprinted microspheres for directly selective extraction of tetracycline veterinary drugs from complex samples
Zhang et al. Determination of β-lactam antibiotics in milk based on magnetic molecularly imprinted polymer extraction coupled with liquid chromatography–tandem mass spectrometry
Madrakian et al. Superparamagnetic surface molecularly imprinted nanoparticles for sensitive solid-phase extraction of tramadol from urine samples
Xi et al. Computational-aided design of magnetic ultra-thin dummy molecularly imprinted polymer for selective extraction and determination of morphine from urine by high-performance liquid chromatography
Wang et al. Magnetic molecularly imprinted nanoparticles based on dendritic-grafting modification for determination of estrogens in plasma samples
Wang et al. The preparation of high-capacity boronate affinity adsorbents by surface initiated reversible addition fragmentation chain transfer polymerization for the enrichment of ribonucleosides in serum
CN103497276B (en) A kind of preparation method and application of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer
CN108452784B (en) Catecholamine solid phase extraction functional composite material, preparation method and application thereof
Hu et al. Selective solid-phase extraction of tebuconazole in biological and environmental samples using molecularly imprinted polymers
Bie et al. Preparation of salbutamol imprinted magnetic nanoparticles via boronate affinity oriented surface imprinting for the selective analysis of trace salbutamol residues
CN103275273A (en) Preparation method of core-shell molecular imprinting nano-material, and application of nano-material
CN103289005B (en) The preparation method of sulphonamide molecular-imprintingsolid-phase solid-phase extraction columella and application
Dolak Selective separation and preconcentration of Thorium (IV) in bastnaesite ore using Thorium (IV)-Imprinted cryogel polymer
CN104193875B (en) The preparation method of stilboestrol magnetic molecularly imprinted polymer and application thereof
Chen et al. Magnetic molecularly imprinted polymers synthesized by surface‐initiated reversible addition‐fragmentation chain transfer polymerization for the enrichment and determination of synthetic estrogens in aqueous solution
Dolak Ion imprinted affinity Cryogels for the selective adsorption uranium in real samples
Peng et al. An investigation of template anchoring strategy for molecularly imprinting materials based on nanomagnetic polyhedral oligomeric silsesquioxanes composites
Mehdipour et al. Selective extraction of organophosphorous pesticides in plasma by magnetic molecularly imprinted polymers with the aid of computational design
CN104237184B (en) A kind of preparation method of ZnO nanorod molecular engram fluorescent optical sensor
Ganjavi et al. Computer‐aided design and synthesis of a highly selective molecularly imprinted polymer for the extraction and determination of buprenorphine in biological fluids
Gao et al. Selective recognition and preliminary separation of hepatoprotective component silybin from milk thistle seeds by the prepared core–shell magnetic molecularly imprinted polymer
CN103613722A (en) Method for preparing magnetic halloysite molecularly imprinted polymer with specific adsorption to 2,4-dichlorophenoxyacetic acid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160817

CF01 Termination of patent right due to non-payment of annual fee