CN105107482A - Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method - Google Patents
Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method Download PDFInfo
- Publication number
- CN105107482A CN105107482A CN201510579311.2A CN201510579311A CN105107482A CN 105107482 A CN105107482 A CN 105107482A CN 201510579311 A CN201510579311 A CN 201510579311A CN 105107482 A CN105107482 A CN 105107482A
- Authority
- CN
- China
- Prior art keywords
- preparation
- organic solvent
- magnetic
- concentration
- ferroferric oxide
- 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.)
- Pending
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method for a molecular imprinting material and the molecular imprinting material prepared through the preparation method. The preparation method comprises the steps that silicon oxide is coated on the surfaces of magnetic ferroferric oxide nanometer particles, the magnetic ferroferric oxide nanometer particles are modified with gamma-(methacryloyl chloride) amino propyl trimethoxy silane to obtain magnetic ferroferric oxide nanometer particles with propenyl on the surfaces, the magnetic ferroferric oxide nanometer particles with the propenyl on the surfaces serve as carriers, estrogen receptors are simulated, functional monomers are optimized, a surface imprinting technology is adopted, and then the molecular imprinting material which can simultaneously identify seven kinds of environmental endocrine disrupting chemicals is prepared. According to the preparation method, the easy separation of a magnetic nanometer material, the good water solubility of a silicon oxide nanometer material, the specific recognition ability of molecular imprinting polymers and the surface imprinting technology are mutually combined, the preparation technology is simple, the conditions are mild, the prepared molecular imprinting material is large in adsorption capacity, fast to respond, high in magnetism, good in chemical stability and high in repeating utilization rate, and the problems that at present, multiple trace, steroid and phenol environmental endocrine disrupting chemicals are difficult to simultaneously identify, separate and enrich are solved.
Description
Technical field
The present invention relates to the fields such as Environmental Chemistry, analytical chemistry, Food Chemistry, nanometer technology, in particular to a kind of preparation method and molecular engram material prepared therefrom of molecular engram material.
Background technology
Along with the fast development of modern industry, agricultural, pollution and the harm of environment incretion interferent (EnvironmentalEndocrineDisruptors, EDCs) have become the focus paid close attention to countries in the world.EPA definition EDCs be by disturb biology or the mankind those for keeping the synthesis of Equilibrium and the natural hormone that regulates growth course and produce in vivo, secretion, transport, combination, reaction and metabolism, thus to the xenobiotics that the reproduction of the biological or mankind, nerve and immune system etc. have an impact.Increasing research shows, even if most of EDCs content extremely low (ppt ~ ppb level or lower) also can produce harmful effect to the growth of animal and the mankind, reproductive function, even causes tumour (as breast cancer, oophoroma etc.).
Extensively be present in due to EDCs in the media such as food, water, air and soil, and enter in human body by various approach such as absorption, accumulation, cause extensive damage to human endocrine system, it can not be ignored to the threat that human survival causes.Given this, set up food and accurate, the sensitive detection technique of Environmental Trace EDCs, administrative department is carried out to assessment and the control of EDCs, and ensure that national health is all significant.
At present, the common method detecting EDCs in food, environmental sample mainly contains gas chromatography (GC), high performance liquid chromatography (HPLC)) and chromatograph-mass spectrometer coupling method (GC-MS, HPLC-MS) etc.These methods all need to carry out pretreatment technology in testing process.Conventional pretreatment technology comprises liquid-liquid extraction and SPE etc.
But these pretreatment technology complex operations, length consuming time, reagent requirement are large, and it is selective lower, when lower Food and environment sample usual in the face of complicated, the of a great variety and EDCs content of matrix, effectively can not avoid matrix interference, realize the efficient fast separating concentration of EDCs, significantly limit the quick and precisely highly sensitive detection of EDCs.Therefore, the identification material that development of new is efficient, specificity is good is the key of carrying out EDCs monitoring analysis in complex matrices.
Molecular imprinting (MolecularImprintingTechnology, MIT) be polymer chemistry, materials chemistry and biochemical cross discipline, so far the developing history of existing 70 years, in chromatographic isolation, SPE, biology sensor, mimetic enzyme catalysis, biomedicine etc., obtain increasingly extensive research and development, illustrate wide application prospect.Utilize MIT can leave the hole matched with template molecule size, shape and functional group space arrangement in the polymer, thus obtain the artificial antibody-molecularly imprinted polymer (MolecularlyImprintedPolymers, MIPs) target molecule to specific recognition capability and high-affinity.Compared with natural biological identification molecular antibody, acceptor, aptamer, MIPs not only has the recognition capability that can compare favourably with it, also has the advantage of the uniqueness such as structure effect precordainment, specific recognition, extensively practicality.Its anti-adverse environment ability is strong, stability is high, long service life, easily realize industrialization, and in separation and concentration food and environment, object presents the application prospect attracted people's attention.
At present, it is carrier that existing correlative study work reports with magnetic nano ferroferric oxide, and the EDCs such as bisphenol-A, diethylstilbestrol, estradiol are template molecule, prepares the material that can realize Separation of Solid and Liquid fast and effectively under outside magnetic field effect.But preparation technology is comparatively complicated, and with the magnetic nano-particle (Fe of coated with silica
3o
4siO
2) for the research work of carrier also relatively less; Simultaneously these research work often can only 2 ~ 3 kinds of EDCs compounds of enrichment similar, when structure inhomogeneity steroid EDCs and phenols EDCs exists jointly, can not carry out identifications also separation and concentration simultaneously.
In view of this, special proposition the present invention.
Summary of the invention
The first object of the present invention is the preparation method providing a kind of molecular engram material, is intended to solve the complicated process of preparation of existing molecular engram material and cannot be identified and the problem of the larger environment incretion interferent of separation and concentration various structures difference simultaneously.The method technique is simple; environmental friendliness is high; easier scale; the molecular engram material prepared identifies while achieving steroid and phenols EDCs, can be used for identification and the fast separating concentration of bisphenol-A (BPA) in environment and food samples, oestrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2), hexestrol (HES) and diethylstilbestrol (DES) these 7 kinds of EDCs.
The second object of the present invention is to provide a kind of molecular engram material.This material solves the problem that existing molecular engram material cannot identify the also environment incretion interferent that separation and concentration various structures difference is larger simultaneously, there is more recognition site and good recognition performance, magnetic is strong, adsorption rate is fast, efficiency is high, can realize efficient selective identification and separation and concentration while multiple types steroid in environment and food samples and phenols EDCs.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
A preparation method for molecular engram material, comprises the steps:
(1) magnetic ferroferric oxide nano-particles is scattered in the first organic solvent, adds ammoniacal liquor and ethyl orthosilicate successively while stirring; Be warming up to 20-40 DEG C after all adding, continue to stir 10-16h, obtain silica magnetic nano particle;
(2) by described silica magnetic nanoparticle dispersion in the second organic solvent, add γ-(methacryloxypropyl) propyl trimethoxy silicane while stirring, after adding rear continuation stirring 20-24h, obtain the silica magnetic nano particle that acrylic is modified;
(3) the silica magnetic nanoparticle dispersion modified by described acrylic is in the 3rd organic solvent, add 17 beta estradiols, function monomer and crosslinking agent successively, initator is added again after stirring, seal after letting nitrogen in and deoxidizing, at 50-85 DEG C, react 20-24h, obtain molecular engram material; Described function monomer comprises methacrylic acid, to one or more in vinyl benzoic acid, Methacrylamide, 2-vinylpyridine or 2-(trifluoromethyl) acrylic acid.
Nano particle diameter is little, specific area is large except having for magnetic Nano material, absorption property is good, mass transfer velocity is fast, outside unique optical property and catalytic activity, also have that cost is low, the characteristic such as safety non-toxic and superparamagnetism, illustrate application prospect widely in fields such as compartment analysis, material, medical diagnosis on disease, biologic medical, environmental monitorings.But magnetic nano-particle is easily reunited in Synthesis and applications, oxidized and unstable in aqueous.
By method provided by the present invention, in magnetic nano particle sub-surface parcel layer of silicon dioxide, not only can utilize inertia and the heat-resisting quantity of silica, avoid the Swelling of magnetic microsphere in polar solvent, improve the biocompatibility of magnetic particle, non-oxidizability and dispersion stabilization, also help the further chemical modification to magnetic particle, realize the multifunction of nano material.
Acrylic is modified at carrier surface by the present invention, adopt " graftto " and surface imprinted technology by polymer graft to carrier surface, obtain surface coverage and have the magnetic, multi-functional of nanoscale molecular trace thin layer at material, reaction condition is easy, technological process is simple, material morphology is controlled, saves plenty of time and reagent.
In the present invention, by analysis mode ERs, optimal screening function monomer kind, successfully prepare the artificial receptors of environment incretion interferent, identify while successfully achieving steroid and phenols EDCs, can be used for identification and the fast separating concentration of bisphenol-A (BPA) in environment and food samples, oestrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2), hexestrol (HES) and diethylstilbestrol (DES) these 7 kinds of EDCs.
In step (1), by the hydrolysis of ammonia-catalyzed ethyl orthosilicate (TEOS) by coated with silica at Fe
3o
4nanoparticle surface, obtained silicon dioxide modified magnetic silica nano particle Fe
3o
4siO
2.In this step, preferably, to be describedly scattered in by magnetic ferroferric oxide nano-particles in the first organic solvent, the concentration of described magnetic ferroferric oxide nano-particles in described first organic solvent is 0.6-3mg/mL;
The concentration of described ammoniacal liquor is 25-28%, and the volume ratio of described ammoniacal liquor, described ethyl orthosilicate and described first kind solvent is 5:(0.35-1.05): (150-250).
In order to obtain the Fe that size is controlled, monodispersity is good
3o
4siO
2nano particle, further preferably, in step (1), described all add after be warming up to 20-40 DEG C, continue stir 10-16h, the step obtaining silica magnetic nano particle specifically comprises:
Be warming up to 20-40 DEG C after all adding, after continuing to stir 10-16h, reaction terminates, and rear use magnet collects product, and with ultra-pure water and ethanol washing, obtains silica magnetic nano particle after vacuum drying.
Based on same consideration, further preferably, in step (1), the temperature of described intensification controls at 25-35 DEG C.
In step (2), use γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) at Fe
3o
4siO
2nanoparticle surface modified acrylic.The Fe of appropriate acrylic and favorable dispersibility is had in order to obtain finishing
3o
4siO
2mPS nano particle, preferably, by described silica magnetic nanoparticle dispersion in the second organic solvent, the concentration of described silica magnetic nano particle in shown second organic solvent is 2-5mg/mL;
The ratio of the volume of described γ-(methacryloxypropyl) propyl trimethoxy silicane and described second organic solvent is (2-6): (40-80).
In order to make nearly all Fe
3o
4siO
2nanoparticle surface all modifies acrylic, further preferably, in step (2), described in add rear continuation and stir after 20-24h, the step obtaining the silica magnetic nano particle that acrylic is modified specifically comprises:
After adding rear continuation stirring 20-24h, reaction terminates; Use magnet to collect product, and with ultra-pure water and ethanol alternately washing, after vacuum drying, obtain the silica magnetic nano particle (Fe that acrylic is modified
3o
4siO
2mPS)
In order to obtain that uniform particle diameter, good dispersion, adsorbance are large, recognition site closer to surface, affinity is high, class specificity is good molecular engram material, preferably, in described step (3),
The silica magnetic nanoparticle dispersion modified by described acrylic is in the 3rd organic solvent, and the concentration of silica magnetic nano particle in described 3rd organic solvent that described acrylic is modified is 4-10mg/mL;
The concentration of described 17 beta estradiols in described 3rd organic solvent is 5-15 μm of ol/mL, the concentration of described function monomer in described 3rd organic solvent is 15-60 μm of ol/mL, the concentration of described crosslinking agent in described 3rd organic solvent is 80-300 μm of ol/mL, and the concentration of described initator in described 3rd organic solvent is 6.09-10.15 μm of ol/mL.
In order to obtain stable performance, molecular engram material that anti-adverse environment ability is strong, further preferably, in step (3), described crosslinking agent is ethylene glycol dimethacrylate or trimethylol-propane trimethacrylate, and described coupling agent is azodiisobutyronitrile.
Preferably, in order to obtain moderate in grain size, magnetic is good, monodispersity is good, stability is high magnetic nano-particle, in step (1), the preparation method of described magnetic ferroferric oxide nano-particles comprises the steps:
By FeCl
36H
2o, sodium acetate, PEG1000 and ethylene glycol ultrasonic disperse are placed in 170-200 DEG C of baking oven and react 8-15h, obtain magnetic ferroferric oxide nano-particles;
Wherein, described FeCl
36H
2o, sodium acetate, PEG1000 and ethylene glycol mole ratio be 1:(8-10): (0.1-0.3): (89-179).
Preferably, to stablize, molecular engram material that affinity is high in order to obtain recognition performance, in step (3), the temperature of described reaction is 60-65 DEG C, or, first at 50-60 DEG C of reaction 10-12h during described reaction, then be warming up to 70-80 DEG C, reaction 10-12h.
Preferably, in step (3), describedly at 50-85 DEG C, react 20-24h, the step obtaining molecular engram material specifically comprises:
After described reaction completes, collecting precipitation thing, and clarify to supernatant with acetonitrile wash, then wash with acetic acid methanol mixed solution, last vacuum drying, obtains molecular engram material.
In order to obtain moderate in grain size, monodispersity is good, reunite few Fe
3o
4siO
2, preferably, in step (1), describedly to add successively while stirring in ammoniacal liquor and ethyl orthosilicate, the speed of described stirring is 500-1000rpm;
In step (2), in order to obtain homogeneous dispersion and the Fe that evenly modifies of MPS
3o
4siO
2mPS, describedly adds in γ-(methacryloxypropyl) propyl trimethoxy silicane while stirring, and the speed of described stirring is 600-1000rpm.
Preferably,
Described first organic solvent comprise in methanol aqueous solution, ethanol water or isopropanol water solution any one;
Described second organic solvent comprise in methyl alcohol, ethanol or toluene any one;
Described 3rd organic solvent comprise in acetonitrile, methyl alcohol, toluene or acetonitrile-DMSO mixed liquor any one.
The molecular engram material that a kind of preparation method provided by the invention is prepared from.
Molecular engram material provided by the present invention is the bionical identification hybrid material of core-shell type magnetic nano, this molecular engram material has more recognition site and good recognition performance, magnetic is strong, adsorption rate is fast, efficiency is high, can realize efficient selective identification and separation and concentration while multiple types steroid in environment and food samples and phenols EDCs.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention is that carrier prepares molecular engram material with magnetic silica, namely ensure that good magnetic property, dispersiveness and the stability of material, also be convenient to experimentally object and chemical modification is carried out to carrier, be conducive to the multifunction realizing nano-hybrid material.
(2) acrylic is modified at carrier surface by the present invention, adopt " graftto " and surface imprinted technology by polymer graft to carrier surface, obtain surface coverage and have the magnetic, multi-functional of nanoscale molecular trace thin layer at material, relative to prior art, reaction condition is easy, technological process is simple, and material morphology is controlled, saves plenty of time and reagent.
(3) the present invention is by analysis mode ERs, optimal screening function monomer kind and ratio, successfully prepare the artificial receptors of EDCs, identify while successfully achieving steroid and phenols EDCs, can be used for the fast separating concentration of bisphenol-A (BPA) in environment and food samples, oestrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2), hexestrol (HES) and diethylstilbestrol (DES) these 7 kinds of EDCs.
(4) molecular engram material that the present invention obtains has more recognition site and good recognition performance, magnetic is strong, adsorption rate is fast, efficiency is high, can realize removing and enrichment efficient selective while multiple types steroid in environment and food samples and phenols EDCs.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below.
Fig. 1 is the preparation flow schematic diagram of molecular engram material of the present invention;
Fig. 2 is magnetic nano ferroferric oxide (a), silica magnetic nano particle (b) of acrylic modification, the transmission electron microscope picture of molecular engram material (c) prepared by embodiment 1;
Fig. 3 be embodiment 1 prepare magnetic nano ferroferric oxide (a), silica magnetic nano particle (b), acrylic modify the transmission electron microscope picture (c) of silica magnetic nano particle, the XRD spectra of molecular engram material (d);
Fig. 4 is magnetic ferroferric oxide nanoparticle (a), silica magnetic nano particle (b) of acrylic modification, the hysteresis curve of molecular engram material (c) prepared by embodiment 1;
Fig. 5 is the molecular engram material (MIP) of embodiment 1 preparation and the adsorption isothermal curve to estradiol of non-molecular engram material (NIP);
Fig. 6 is the molecular engram material (MIP) of embodiment 1 preparation and the Dynamic Adsorption curve to estradiol of non-molecular engram material (NIP).
Fig. 7 is the molecular engram material (MIP) of embodiment 1 preparation and the suction-operated to E1, E2, E3, EE2, DES, BPA, HES seven kinds of environment incretion interferents of non-molecular engram material (NIP).
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturer suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
Embodiment 1
As shown in Figure 1, specifically comprise the steps:
S11: adopt water heat transfer magnetic ferroferric oxide (Fe
3o
4) nano particle
By 0.665gFeCl
36H
2o, 1.80g sodium acetate, 0.5gPEG1000 and 20mL ethylene glycol are placed in the Teflon internal lining pipe of 25mL reactor, tighten reactor, be placed in 180 DEG C of baking ovens and react 8h after ultrasonic disperse is even.Use externally-applied magnetic field to be separated by magnetic ferroferric oxide nano-particles after being cooled to room temperature after question response terminates, and wash to neutral with ultra-pure water and ethanol, vacuum drying, obtains magnetic ferroferric oxide nano-particles.
S12: the magnetic silica nano particle (Fe of Silica-coated
3o
4siO
2) preparation.
Get the 0.3g magnetic ferroferric oxide nano-particles ultrasonic disperse that obtains in S11 in 200mL80% methanol aqueous solution, 5mL ammoniacal liquor and 0.7mLTEOS is added successively under mechanical agitation, after 25 DEG C of continuation mechanical agitation 16h, use magnet separated and collected product, with ultra-pure water and ethanol washing, under vacuum drying, obtain Fe
3o
4siO
2nano particle.
S13: the magnetic silica nano particle (Fe that acrylic is modified
3o
4siO
2) preparation
Get the 200mgFe of S12 gained
3o
4siO
2nano particle ultrasonic disperse, in 50mL methyl alcohol, dropwise adds 4mLMPS under mechanical agitation, stirred at ambient temperature 24h, uses magnet separated and collected product, with ultra-pure water and ethanol washing, obtains the Fe that acrylic is modified under vacuum drying
3o
4siO
2nano particle.
S14: the Fe that the acrylic of 100mg is modified
3o
4siO
2nano particle ultrasonic disperse is in 20mL acetonitrile, add template molecule 27.2mg (0.1mmol) 17 beta estradiol successively, function monomer methacrylic acid 25.8mg (0.3mmol) and to vinyl benzoic acid 44.4mg (0.3mmol), crosslinking agent ethylene glycol dimethacrylate 594.0mg (2.5mmol) ultrasonic disperse is even, add initator azodiisobutyronitrile 30mg, sealed reaction system after letting nitrogen in and deoxidizing, reacts 24h under 65 DEG C of water-baths.React rear magnet collecting precipitation thing, and clarified with the supernatant of acetonitrile cyclic washing several times to separation, then washed away template with the acetic acid methanol mixed solution that volume ratio is 9:1, after product vacuum drying, obtain molecular engram material MIP.
Embodiment 2
This enforcement comprises the following steps
S21: adopt water heat transfer magnetic ferroferric oxide (Fe
3o
4) nano particle
By 0.945gFeCl
36H
2o, 2.87g sodium acetate, 0.8gPEG1000 and 20mL ethylene glycol are placed in the Teflon internal lining pipe of 25mL reactor, tighten reactor, be placed in 180 DEG C of baking ovens and react 8h after ultrasonic disperse is even.Be cooled to room temperature after question response terminates, use externally-applied magnetic field collects magnetic ferroferric oxide nano-particles, and washs to neutral with ultra-pure water and ethanol, and vacuum drying, both obtains ferriferrous oxide nano-particle.
S22: silicon dioxide modified magnetic silica nano particle (Fe
3o
4siO
2) preparation
Get the 0.45g magnetic nano-particle ultrasonic disperse that obtains in S21 in 250mL80% ethanol water, add 5mL ammoniacal liquor and 1.0mLTEOS successively under mechanical agitation, after 40 DEG C of continuation mechanical agitation 12h, use magnet separated and collected product, with ultra-pure water and ethanol washing, under vacuum drying, obtain Fe
3o
4siO
2nano particle.
S23: the magnetic silica nano particle (Fe that acrylic is modified
3o
4siO
2) preparation
Get the 300mgFe of step 2 gained
3o
4siO
2nano particle ultrasonic disperse, in 70mL methyl alcohol, dropwise adds 5mLMPS under mechanical agitation, stirred at ambient temperature 24h, uses magnet separated and collected product, with ultra-pure water and ethanol washing, obtains the Fe that acrylic is modified under vacuum drying
3o
4siO
2nano particle.
S24: the Fe that the acrylic of 200mg is modified
3o
4siO
2nano particle ultrasonic disperse is in 50mL acetonitrile, add template molecule 17 beta estradiol 81.6mg (0.3mmol) successively, function monomer methacrylic acid 51.6mg (0.6mmol) and Methacrylamide 51.0mg (0.6mmol), crosslinking agent ethylene glycol dimethacrylate 1.185g (6.0mmol) ultrasonic disperse is even, add initator azodiisobutyronitrile 60mg, sealed reaction system after letting nitrogen in and deoxidizing, reacts 24h under 60 DEG C of water-baths.React rear magnet collecting precipitation thing, and clarified with the supernatant of acetonitrile cyclic washing several times to separation, then washed away template with the acetic acid methanol mixed solution that volume ratio is 9:1, after product vacuum drying, obtain molecular engram material.
Embodiment 3
The present embodiment comprises the following steps
S31: adopt water heat transfer magnetic ferroferric oxide (Fe
3o
4) nano particle
By 0.810gFeCl
36H
2o, 2.21g sodium acetate, 0.7gPEG1000 and 20mL ethylene glycol are placed in the Teflon internal lining pipe of 25mL reactor, tighten reactor, be placed in 180 DEG C of baking ovens and react 8h after ultrasonic disperse is even.Be cooled to room temperature after question response terminates, use externally-applied magnetic field to be separated by magnetic ferroferric oxide nano-particles, and wash to neutral with ultra-pure water and ethanol, vacuum drying, both obtains ferriferrous oxide nano-particle.
S32: silicon dioxide modified magnetic silica nano particle (Fe
3o
4siO
2) preparation
Get the 0.2g magnetic nano-particle ultrasonic disperse that obtains in S31 in 200mL80% methanol aqueous solution, add 5mL ammoniacal liquor and 0.4mLTEOS successively under mechanical agitation, after 35 DEG C of continuation mechanical agitation 12h, use magnet separated and collected product, with ultra-pure water and ethanol washing, under vacuum drying, obtain Fe
3o
4siO
2nano particle.
S33: the magnetic silica nano particle (Fe that acrylic is modified
3o
4siO
2mPS) preparation
Get the 200mgFe of S32 gained
3o
4siO
2nano particle ultrasonic disperse, in 50mL ethanol, dropwise adds 5mLMPS under mechanical agitation, stirred at ambient temperature 24h, uses magnet separated and collected product, with ultra-pure water and ethanol washing, obtains Fe under vacuum drying
3o
4siO
2mPS nano particle.
S34: the Fe that the acrylic of 150mg is modified
3o
4siO
2nano particle ultrasonic disperse is in 30mL methyl alcohol, add template molecule 54.4mg (0.2mmol) 17 beta estradiol successively, function monomer 2-vinylpyridine 63mg (0.6mmol), 2-(trifluoromethyl) acrylic acid 84mg (0.6mmol), crosslinking agent ethylene glycol dimethacrylate 0.950g (4.8mmol) ultrasonic disperse is even, add initator azodiisobutyronitrile 40mg, sealed reaction system after letting nitrogen in and deoxidizing, 80 DEG C water-baths under again reacts 10h after reacting 10h under 60 DEG C of water-baths.React rear magnet collecting precipitation thing, and clarified with the supernatant of acetonitrile cyclic washing several times to separation, then washed away template with the acetic acid methanol mixed solution that volume ratio is 9:1, after product vacuum drying, obtain molecular engram material.
Embodiment 4
The present embodiment comprises the following steps
S41: adopt water heat transfer magnetic ferroferric oxide (Fe
3o
4) nano particle
By 1.08gFeCl
36H
2o, 2.65g sodium acetate, 0.4gPEG1000 and 20mL ethylene glycol are placed in the Teflon internal lining pipe of 25mL reactor, tighten reactor, be placed in 170 DEG C of baking ovens and react 15h after ultrasonic disperse is even.Be cooled to room temperature after question response terminates, use externally-applied magnetic field to be separated by magnetic ferroferric oxide nano-particles, and wash to neutral with ultra-pure water and ethanol, vacuum drying, both obtains ferriferrous oxide nano-particle.
S42: silicon dioxide modified magnetic silica nano particle (Fe
3o
4siO
2) preparation
Get the 0.09g magnetic nano-particle ultrasonic disperse that obtains in S41 in 150mL80% isopropanol water solution, 5mL ammoniacal liquor and 0.35mLTEOS is added successively under the stir speed (S.S.) of 500rpm, maintain same stir speed (S.S.), after continuing to stir 10h at 20 DEG C, use magnet separated and collected product, with ultra-pure water and ethanol washing, under vacuum drying, obtain Fe
3o
4siO
2nano particle.
S43: the magnetic silica nano particle (Fe that acrylic is modified
3o
4siO
2mPS) preparation
Get the 80mgFe of S42 gained
3o
4siO
2nano particle ultrasonic disperse, in 40mL toluene, dropwise adds 2mLMPS under the stir speed (S.S.) of 1000rpm, stirs 20h at 90 DEG C, uses magnet separated and collected product, with ultra-pure water and ethanol washing, obtains Fe under vacuum drying
3o
4siO
2mPS nano particle.
S44: the Fe that the acrylic of 120mg is modified
3o
4siO
2nano particle ultrasonic disperse is in 30mL toluene, add template molecule 40.8mg (0.15mmol) 17 beta estradiol successively, function monomer 2-vinylpyridine 15.75mg (0.15mmol), methacrylic acid 25.8mg (0.3mmol), crosslinking agent ethylene glycol dimethacrylate 0.475g (2.4mmol) ultrasonic disperse is even, add initator azodiisobutyronitrile 30mg, sealed reaction system after letting nitrogen in and deoxidizing, reacts 24h under 50 DEG C of water-baths.React rear magnet collecting precipitation thing, and clarified with the supernatant of acetonitrile cyclic washing several times to separation, then washed away template with the acetic acid methanol mixed solution that volume ratio is 9:1, after product vacuum drying, obtain molecular engram material.
Embodiment 5
The present embodiment comprises the following steps
S51: adopt water heat transfer magnetic ferroferric oxide (Fe
3o
4) nano particle
By 0.54gFeCl
36H
2o, 1.765g sodium acetate, 0.6gPEG1000 and 20mL ethylene glycol are placed in the Teflon internal lining pipe of 25mL reactor, tighten reactor, be placed in 200 DEG C of baking ovens and react 8h after ultrasonic disperse is even.Be cooled to room temperature after question response terminates, use externally-applied magnetic field to be separated by magnetic ferroferric oxide nano-particles, and wash to neutral with ultra-pure water and ethanol, vacuum drying, both obtains ferriferrous oxide nano-particle.
S52: silicon dioxide modified magnetic silica nano particle (Fe
3o
4siO
2) preparation
Get the 0.75g magnetic nano-particle ultrasonic disperse that obtains in S51 in 250mL90% ethanol water, 5mL ammoniacal liquor and 1.05mLTEOS is added successively under the stir speed (S.S.) of 1000rpm, maintain same stir speed (S.S.), after continuing to stir 16h at 50 DEG C, use magnet separated and collected product, with ultra-pure water and ethanol washing, under vacuum drying, obtain Fe
3o
4siO
2nano particle.
S53: the magnetic silica nano particle (Fe that acrylic is modified
3o
4siO
2mPS) preparation
Get the 400mgFe of S52 gained
3o
4siO
2nano particle ultrasonic disperse, in 80mL toluene, dropwise adds 6mLMPS under the stir speed (S.S.) of 600rpm, stirring reaction 24h at 80 DEG C, uses magnet separated and collected product, with ultra-pure water and ethanol washing, obtains Fe under vacuum drying
3o
4siO
2mPS nano particle.
S54: the Fe that the acrylic of 600mg is modified
3o
4siO
2nano particle ultrasonic disperse is (volume ratio is 14:1) in 60mL acetonitrile/DMSO mixed solution, add template molecule 244.8mg (0.9mmol) 17 beta estradiol successively, function monomer Methacrylamide 153mg (1.8mmol), 2-(trifluoromethyl) acrylic acid 252mg (1.8mmol), crosslinking agent trimethylol-propane trimethacrylate 5.335g (18mmol) ultrasonic disperse is even, add initator azodiisobutyronitrile 100mg, sealed reaction system after letting nitrogen in and deoxidizing, reacts 20h under 85 DEG C of water-baths.React rear magnet collecting precipitation thing, and clarified with the supernatant of acetonitrile cyclic washing several times to separation, then washed away template with the acetic acid methanol mixed solution that volume ratio is 9:1, after product vacuum drying, obtain molecular engram material.
Comparative example
Comparative example provides the preparation method of non-molecular engram material (NIP), and with reference to embodiment 1, preparation process concrete in comparative example is not added except function monomer except in step S14, and all the other steps are all identical with embodiment 1.
In order to verify beneficial effect of the present invention, adopt the molecular engram material prepared by the embodiment of the present invention 1 to carry out Performance Detection, step is as follows:
(1) bisphenol-A (BPA), oestrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2), hexestrol (HES), diethylstilbestrol (DES) 7 kinds of environment incretion interferent standard items 10.0mg are accurately taken respectively in 7 10mL volumetric flasks, after dissolving with a small amount of methyl alcohol, by methanol constant volume to scale, make the standard reserving solution of 1.0g/L, save backup in 4 DEG C of refrigerators.
(2) it is in the 1mL acetonitrile solution of 10 ~ 180 μ g/mL that non-molecular engram material prepared by molecular engram material 20mg embodiment 1 prepared and comparative example joins E2 concentration respectively, after shaking 10min under room temperature, by externally-applied magnetic field, supernatant is separated, after 0.45 μm of organic filter membrane, utilize HPLC separation determination.Testing result as shown in Figure 5.
As seen from Figure 5, along with the increase of template molecule E2 concentration, the adsorption capacity to E2 of molecular engram material and non-molecular engram material is all tending towards increasing, but the adsorption capacity of molecular engram material to E2 is significantly higher than non-molecular engram material, this illustrate prepared by the absorption of molecular engram material to E2 be specific.Calculated from Scatch equation, molecular engram material and the saturated adsorption capacity of non-molecular engram material to E2 are respectively 2.98mg/g, 0.88mg/g.
(3) 20mg molecular engram material and non-molecular engram material being joined respectively 1mLE2 concentration is in the acetonitrile mixture of 20 μ g/mL, after shaking 1 ~ 30min under room temperature, by externally-applied magnetic field, supernatant is separated, after 0.45 μm of organic filter membrane, use HPLC separation determination.Testing result as shown in Figure 6, can be found out, the bionical hybrid material of magnetic Nano obtained in 10min can reach balance to the absorption of E2.
(4) 20mg molecular engram material and non-molecular engram material being added respectively 1mLE1, E2, E3, EE2, DES, BPA, HES concentration is in the acetonitrile mixture of 20 μ g/mL, after shaking 10min under room temperature, by externally-applied magnetic field, supernatant is separated, after 0.45 μm of organic filter membrane, utilize HPLC separation determination.Testing result as shown in Figure 7.The bionical hybrid material of magnetic Nano trace as seen from Figure 7 obtained by the present invention all has good specific adsorption effect to environment incretion interferent in above-mentioned 7, to can be used in environment and food samples efficient identification and separation and concentration while multiple types steroid and phenols EDCs.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.
Claims (10)
1. a preparation method for molecular engram material, is characterized in that, comprises the steps:
(1) magnetic ferroferric oxide nano-particles is scattered in the first organic solvent, adds ammoniacal liquor and ethyl orthosilicate successively while stirring; Be warming up to 20-40 DEG C after all adding, continue to stir 10-16h, obtain silica magnetic nano particle;
(2) by described silica magnetic nanoparticle dispersion in the second organic solvent, add γ-(methacryloxypropyl) propyl trimethoxy silicane while stirring, after adding rear continuation stirring 20-24h, obtain the silica magnetic nano particle that acrylic is modified;
(3) the silica magnetic nanoparticle dispersion modified by described acrylic is in the 3rd organic solvent, add 17 beta estradiols, function monomer and crosslinking agent successively, initator is added again after stirring, sealed reaction system after letting nitrogen in and deoxidizing, at 50-85 DEG C, react 20-24h, obtain molecular engram material; Described function monomer comprises methacrylic acid, to one or more in vinyl benzoic acid, Methacrylamide, 2-vinylpyridine or 2-(trifluoromethyl) acrylic acid.
2. preparation method according to claim 1, is characterized in that, in step (1),
Describedly be scattered in by magnetic ferroferric oxide nano-particles in the first organic solvent, the concentration of described magnetic ferroferric oxide nano-particles in described first organic solvent is 0.6-3mg/mL;
The concentration of described ammoniacal liquor is 25-28%, and the volume ratio of described ammoniacal liquor, described ethyl orthosilicate and described first organic solvent is 5:(0.35-1.05): (150-250).
3. preparation method according to claim 1, is characterized in that, in step (2),
Described by described silica magnetic nanoparticle dispersion in the second organic solvent, the concentration of described silica magnetic nano particle in shown second organic solvent is 2-5mg/mL;
The ratio of the volume of described γ-(methacryloxypropyl) propyl trimethoxy silicane and described second organic solvent is (2-6): (40-80).
4. preparation method according to claim 1, is characterized in that, in described step (3),
The silica magnetic nanoparticle dispersion modified by described acrylic is in the 3rd organic solvent, and the concentration of silica magnetic nano particle in described 3rd organic solvent that described acrylic is modified is 4-10mg/mL;
The concentration of described 17 beta estradiols in described 3rd organic solvent is 5-15 μm of ol/mL, the concentration of described various function monomer in described 3rd organic solvent is respectively 15-60 μm of ol/mL, the concentration of described crosslinking agent in described 3rd organic solvent is 80-300 μm of ol/mL, and the concentration of described initator in described 3rd organic solvent is 6.09-10.15 μm of ol/mL.
5. preparation method according to claim 4, is characterized in that, in step (3), described crosslinking agent is ethylene glycol dimethacrylate or trimethoxypropane gave trimethyl acrylic ester, and described coupling agent is azodiisobutyronitrile.
6. the preparation method according to any one of claim 1-5, is characterized in that, in step (1), the preparation method of described magnetic ferroferric oxide nano-particles comprises the steps:
By FeCl
36H
2the mixing of O, sodium acetate, PEG1000 and ethylene glycol is placed in 170-200 DEG C of baking oven reacts 8-15h, obtains magnetic ferroferric oxide nano-particles;
Wherein, described FeCl
36H
2o, described sodium acetate, described PEG1000 and described ethylene glycol mole ratio be 1:(8-10): (0.1-0.3): (89-179).
7. the preparation method according to any one of claim 1-5, is characterized in that, in step (3), describedly at 50-85 DEG C, react 20-24h, the step obtaining molecular engram material specifically comprises:
20-24h is reacted at 50-85 DEG C, after described reaction completes, collecting precipitation thing, and clarify to supernatant with acetonitrile wash, then wash with acetic acid methanol mixed solution, last vacuum drying, obtain the material of identification and isolating environment incretion interferent.
8. the preparation method according to any one of claim 1-5, is characterized in that,
In step (1), describedly to add successively while stirring in ammoniacal liquor and ethyl orthosilicate, the speed of described stirring is 500-1000rpm;
In step (2), describedly add in γ-(methacryloxypropyl) propyl trimethoxy silicane while stirring, the speed of described stirring is 600-1000rpm.
9. preparation method according to claim 8, is characterized in that,
Described first organic solvent comprise in methanol aqueous solution, ethanol water or isopropanol water solution any one;
Described second organic solvent comprise in methyl alcohol, ethanol or toluene any one;
Described 3rd organic solvent comprise in acetonitrile, methyl alcohol, toluene or acetonitrile-DMSO mixed liquor any one.
10. the molecular engram material that the preparation method described in an any one of claim 1-9 is prepared from.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510579311.2A CN105107482A (en) | 2015-09-11 | 2015-09-11 | Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510579311.2A CN105107482A (en) | 2015-09-11 | 2015-09-11 | Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105107482A true CN105107482A (en) | 2015-12-02 |
Family
ID=54655724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510579311.2A Pending CN105107482A (en) | 2015-09-11 | 2015-09-11 | Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105107482A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105699567A (en) * | 2016-01-05 | 2016-06-22 | 南京医科大学 | Method for detecting giant knot weed metabolic substance group in rat plasma through combination of molecular imprinting nanometer magnetic bead dispersive solid-phase extraction and mass spectrum |
| CN105921129A (en) * | 2016-05-16 | 2016-09-07 | 南昌大学 | Preparation method of magnetic molecularly imprinted microspheres and application in separation and enrichment of cucurbitane triterpenoid |
| CN106378097A (en) * | 2016-10-11 | 2017-02-08 | 常州大学 | Preparation method of molecularly imprinted silica magnetic attapulgite and application of molecularly imprinted silica magnetic attapulgite to identification of tyrosine enantiomer |
| CN106633070A (en) * | 2016-12-30 | 2017-05-10 | 中国农业科学院农业质量标准与检测技术研究所 | Metal-organic framework imprinted material and preparation method thereof |
| CN106674449A (en) * | 2016-12-30 | 2017-05-17 | 中国农业科学院农业质量标准与检测技术研究所 | Core-shell recognition material and preparation method thereof |
| CN106947038A (en) * | 2017-04-07 | 2017-07-14 | 中国农业科学院农业质量标准与检测技术研究所 | Molecular imprinting stirring rod and preparation method thereof |
| CN107200812A (en) * | 2017-06-07 | 2017-09-26 | 中国农业大学 | A kind of preparation method of magnetic molecularly imprinted material |
| CN107224969A (en) * | 2017-06-09 | 2017-10-03 | 江苏省原子医学研究所 | A kind of preparation method and applications of PQQ DA trace magnetic nano-particles |
| CN107930599A (en) * | 2017-08-23 | 2018-04-20 | 公安部物证鉴定中心 | Magnetic material for aqueous solution drugs sample pre-treatment and preparation method thereof |
| CN108084375A (en) * | 2017-12-25 | 2018-05-29 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of triazole pesticide molecular blotting magnetic microsphere and its application |
| CN108579685A (en) * | 2018-05-17 | 2018-09-28 | 重庆大学 | A kind of preparation method of modified mesoporous silicon material and the application in removing Estrogen |
| CN109187479A (en) * | 2018-11-09 | 2019-01-11 | 中国农业科学院农业质量标准与检测技术研究所 | Hostathion detection kit based on quantum dot probe |
| CN109283168A (en) * | 2018-08-13 | 2019-01-29 | 浙江大学 | A kind of highly sensitive SERS molecular detecting method based on both sexes nano particle |
| 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 |
| CN109749117A (en) * | 2019-02-16 | 2019-05-14 | 江苏大学 | A kind of preparation method and its usage based on magnetic ferroferric oxide nano-particles-pH response type imprinted material |
| CN110066369A (en) * | 2019-04-02 | 2019-07-30 | 浙江工业大学 | Magnetic molecularly imprinted polymer and its preparation and application |
| CN110180509A (en) * | 2019-05-24 | 2019-08-30 | 吉林大学 | A kind of fluorescent molecule imprinted polymer tiny balloon and its preparation method and application |
| CN110577818A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | preparation method of graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material |
| CN110982022A (en) * | 2019-12-20 | 2020-04-10 | 中国药科大学 | Magnetic capsaicin molecularly imprinted polymer and preparation method thereof |
| CN113072710A (en) * | 2021-03-29 | 2021-07-06 | 佛山湘潭大学绿色智造研究院 | Gas response type resonance photon molecular imprinting sensor and preparation method thereof |
| CN113072711A (en) * | 2021-03-29 | 2021-07-06 | 佛山湘潭大学绿色智造研究院 | Magnetic and photon-based dual-response virus molecularly imprinted sensor and construction method thereof |
| CN114653347A (en) * | 2021-12-16 | 2022-06-24 | 四川省乾启生物科技有限公司 | Molecularly imprinted magnetic nanofiber membrane and preparation method and application thereof |
| CN114763414A (en) * | 2021-01-14 | 2022-07-19 | 南京理工大学 | 17 beta-estradiol magnetic molecularly imprinted polymer and preparation method thereof |
| CN114950394A (en) * | 2022-06-01 | 2022-08-30 | 江苏大学 | Preparation method of magnetic surface molecularly imprinted nano material for selective adsorption separation of diethylstilbestrol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382273A (en) * | 2011-07-12 | 2012-03-21 | 陕西师范大学 | Preparation method of 17 beta-estradiol molecular-imprinted composite microspheres |
| KR101131859B1 (en) * | 2009-11-30 | 2012-03-30 | 재단법인대구경북과학기술원 | Sensor chips for detecting estradiol and the methods thereof |
| CN102977288A (en) * | 2012-12-04 | 2013-03-20 | 温州医学院 | Molecularly imprinted magnetic microsphere, preparation method and application thereof |
| CN104193875A (en) * | 2014-06-25 | 2014-12-10 | 齐鲁工业大学 | Preparation method and application of magnetic diethylstilbestrol molecularly-imprinted polymer |
-
2015
- 2015-09-11 CN CN201510579311.2A patent/CN105107482A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101131859B1 (en) * | 2009-11-30 | 2012-03-30 | 재단법인대구경북과학기술원 | Sensor chips for detecting estradiol and the methods thereof |
| CN102382273A (en) * | 2011-07-12 | 2012-03-21 | 陕西师范大学 | Preparation method of 17 beta-estradiol molecular-imprinted composite microspheres |
| CN102977288A (en) * | 2012-12-04 | 2013-03-20 | 温州医学院 | Molecularly imprinted magnetic microsphere, preparation method and application thereof |
| CN104193875A (en) * | 2014-06-25 | 2014-12-10 | 齐鲁工业大学 | Preparation method and application of magnetic diethylstilbestrol molecularly-imprinted polymer |
Non-Patent Citations (4)
| Title |
|---|
| ERIC SCHILLINGER ET AL: ""An Artificial Estrogen Receptor through Combinatorial Imprinting"", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
| GUSTAF D. OLSSON ET AL: ""Theoretical Studies of 17-β-Estradiol-Imprinted Prepolymerization Mixtures: Insights Concerning the Roles of Cross-Linking and Functional Monomers in Template Complexation and Polymerization"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
| HANGZHEN LAN ET AL: ""An automated solid-phase microextraction method based onmagnetic molecularly imprinted polymer as fiber coating fordetection of trace estrogens in milk powder"", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| MEHDI ESFANDYARI-MANESH ET AL: ""Synthesis and Evaluation of Uniformly Sized Carbamazepine-Imprinted Microspheres and Nanospheres Prepared with Different Mole Ratios of Methacrylic Acid to Methyl Methacrylate for Analytical and Biomedical Applications"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105699567B (en) * | 2016-01-05 | 2017-03-15 | 南京医科大学 | Molecular imprinting nanometer magnetic bead dispersive solid-phase extraction is used for the detection method of giant knotweed metabolite group in rat plasma with mass spectrometry |
| CN105699567A (en) * | 2016-01-05 | 2016-06-22 | 南京医科大学 | Method for detecting giant knot weed metabolic substance group in rat plasma through combination of molecular imprinting nanometer magnetic bead dispersive solid-phase extraction and mass spectrum |
| CN105921129A (en) * | 2016-05-16 | 2016-09-07 | 南昌大学 | Preparation method of magnetic molecularly imprinted microspheres and application in separation and enrichment of cucurbitane triterpenoid |
| CN106378097B (en) * | 2016-10-11 | 2018-10-19 | 常州大学 | The preparation of molecular engram silica magnetic attapulgite is simultaneously applied to identification tyrosine enantiomer |
| CN106378097A (en) * | 2016-10-11 | 2017-02-08 | 常州大学 | Preparation method of molecularly imprinted silica magnetic attapulgite and application of molecularly imprinted silica magnetic attapulgite to identification of tyrosine enantiomer |
| CN106633070B (en) * | 2016-12-30 | 2018-03-23 | 中国农业科学院农业质量标准与检测技术研究所 | Metal framework imprinted material and preparation method thereof |
| CN106674449A (en) * | 2016-12-30 | 2017-05-17 | 中国农业科学院农业质量标准与检测技术研究所 | Core-shell recognition material and preparation method thereof |
| CN106633070A (en) * | 2016-12-30 | 2017-05-10 | 中国农业科学院农业质量标准与检测技术研究所 | Metal-organic framework imprinted material and preparation method thereof |
| CN106947038A (en) * | 2017-04-07 | 2017-07-14 | 中国农业科学院农业质量标准与检测技术研究所 | Molecular imprinting stirring rod and preparation method thereof |
| CN106947038B (en) * | 2017-04-07 | 2018-09-07 | 中国农业科学院农业质量标准与检测技术研究所 | Molecular imprinting stirring rod and preparation method thereof |
| CN107200812A (en) * | 2017-06-07 | 2017-09-26 | 中国农业大学 | A kind of preparation method of magnetic molecularly imprinted material |
| CN107224969A (en) * | 2017-06-09 | 2017-10-03 | 江苏省原子医学研究所 | A kind of preparation method and applications of PQQ DA trace magnetic nano-particles |
| CN107224969B (en) * | 2017-06-09 | 2019-09-27 | 江苏省原子医学研究所 | A kind of preparation method and applications of PQQ-DA trace magnetic nano-particle |
| CN107930599B (en) * | 2017-08-23 | 2021-03-16 | 公安部物证鉴定中心 | Magnetic material for pretreatment of aqueous solution drug test material and preparation method thereof |
| CN107930599A (en) * | 2017-08-23 | 2018-04-20 | 公安部物证鉴定中心 | Magnetic material for aqueous solution drugs sample pre-treatment and preparation method thereof |
| CN108084375A (en) * | 2017-12-25 | 2018-05-29 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of triazole pesticide molecular blotting magnetic microsphere and its application |
| CN108579685B (en) * | 2018-05-17 | 2020-12-15 | 重庆大学 | Preparation method of modified mesoporous silicon material and application of modified mesoporous silicon material in removal of steroid estrogen |
| CN108579685A (en) * | 2018-05-17 | 2018-09-28 | 重庆大学 | A kind of preparation method of modified mesoporous silicon material and the application in removing Estrogen |
| CN110577818A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | preparation method of graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material |
| CN110577818B (en) * | 2018-06-07 | 2022-07-05 | 山东欧铂新材料有限公司 | Preparation method of graphene oxide/ferroferric oxide/silicon dioxide wave-absorbing material |
| CN109283168A (en) * | 2018-08-13 | 2019-01-29 | 浙江大学 | A kind of highly sensitive SERS molecular detecting method based on both sexes nano particle |
| CN109283168B (en) * | 2018-08-13 | 2020-07-03 | 浙江大学 | High-sensitivity SERS molecule detection method based on amphoteric nanoparticles |
| 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 |
| CN109187479A (en) * | 2018-11-09 | 2019-01-11 | 中国农业科学院农业质量标准与检测技术研究所 | Hostathion detection kit based on quantum dot probe |
| CN109749117B (en) * | 2019-02-16 | 2021-10-08 | 江苏大学 | Preparation method and application of magnetic ferroferric oxide nanoparticle-pH response type imprinting material |
| CN109749117A (en) * | 2019-02-16 | 2019-05-14 | 江苏大学 | A kind of preparation method and its usage based on magnetic ferroferric oxide nano-particles-pH response type imprinted material |
| CN110066369A (en) * | 2019-04-02 | 2019-07-30 | 浙江工业大学 | Magnetic molecularly imprinted polymer and its preparation and application |
| CN110180509B (en) * | 2019-05-24 | 2021-08-24 | 吉林大学 | Fluorescent molecularly imprinted polymer hollow microsphere and preparation method and application thereof |
| CN110180509A (en) * | 2019-05-24 | 2019-08-30 | 吉林大学 | A kind of fluorescent molecule imprinted polymer tiny balloon and its preparation method and application |
| CN110982022B (en) * | 2019-12-20 | 2021-07-09 | 中国药科大学 | Magnetic capsaicin molecularly imprinted polymer and preparation method thereof |
| CN110982022A (en) * | 2019-12-20 | 2020-04-10 | 中国药科大学 | Magnetic capsaicin molecularly imprinted polymer and preparation method thereof |
| CN114763414A (en) * | 2021-01-14 | 2022-07-19 | 南京理工大学 | 17 beta-estradiol magnetic molecularly imprinted polymer and preparation method thereof |
| CN113072710A (en) * | 2021-03-29 | 2021-07-06 | 佛山湘潭大学绿色智造研究院 | Gas response type resonance photon molecular imprinting sensor and preparation method thereof |
| CN113072711A (en) * | 2021-03-29 | 2021-07-06 | 佛山湘潭大学绿色智造研究院 | Magnetic and photon-based dual-response virus molecularly imprinted sensor and construction method thereof |
| CN114653347A (en) * | 2021-12-16 | 2022-06-24 | 四川省乾启生物科技有限公司 | Molecularly imprinted magnetic nanofiber membrane and preparation method and application thereof |
| CN114950394A (en) * | 2022-06-01 | 2022-08-30 | 江苏大学 | Preparation method of magnetic surface molecularly imprinted nano material for selective adsorption separation of diethylstilbestrol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105107482A (en) | Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method | |
| CN105085843B (en) | A kind of preparation method of molecular engram material and molecular engram material prepared therefrom | |
| Lu et al. | Flow injection chemiluminescence sensor based on core–shell magnetic molecularly imprinted nanoparticles for determination of chrysoidine in food samples | |
| Ma et al. | Molecular imprinted polymers based on magnetic chitosan with different deep eutectic solvent monomers for the selective separation of catechins in black tea | |
| CN104479072B (en) | A kind of method preparing magnetic molecularly imprinted adsorbent | |
| Zhang et al. | Homochiral fluorescence responsive molecularly imprinted polymer: Highly chiral enantiomer resolution and quantitative detection of L-penicillamine | |
| CN107478823B (en) | A method of bisphenol-A is detected based on acetylcholine ester enzyme signal amplification principle | |
| CN107200812A (en) | A kind of preparation method of magnetic molecularly imprinted material | |
| CN107746841B (en) | Zwitterion magnetic composite hydrogel immobilized enzyme carrier and preparation method thereof | |
| CN103992450A (en) | Method for preparing Cyhalothrin magnetic fluorescent molecularly imprinted material | |
| CN101225306B (en) | Method for preparing fluorescent rare earth complex compound silicon nano particles | |
| CN103910836B (en) | Preparation method of magnetic carbon nano-tube surface molecular imprinting polymer for biological sample pretreatment | |
| CN108318421B (en) | Magnetic graphene molecular imprinting Raman enhancement substrate, and preparation method and application thereof | |
| CN105498694A (en) | Temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof | |
| CN102558463A (en) | One-pot synthesis phenylboronic acid polymer magnetic nano composite material and preparation method and application thereof | |
| CN109164076A (en) | Fluorescent nano probe, preparation method based on La-ZIF-8 and its application in bioluminescence sensing | |
| CN107129562B (en) | Magnetic nanocrystalline cellulose grafted graphene oxide surface molecularly imprinted polymer | |
| Tan et al. | Development of surface imprinted core–shell nanoparticles and their application in a solid-phase dispersion extraction matrix for methyl parathion | |
| CN105056915A (en) | Preparation and application for magnetic metal organic framework medium modified by nucleic acid aptamer | |
| CN110215737A (en) | A kind of affine integral post and preparation method thereof loading aptamer based on graphene-nanogold compound interface superelevation | |
| CN106883411A (en) | The preparation and the application as solid extracting agent of the structure mesoporous molecularly imprinted polymer of superparamagnetic core-shell | |
| CN106633070A (en) | Metal-organic framework imprinted material and preparation method thereof | |
| CN105153367A (en) | Preparation method of dicyandiamide mesoporous surface molecularly imprinted polymer microspheres | |
| CN106512958B (en) | A kind of preparation method and application of aptamer modified chitosan nano fiber | |
| Lan et al. | Study on the polypeptide-functionalized magnetic chitosan microspheres that specifically adsorb Hg (II) ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151202 |
|
| RJ01 | Rejection of invention patent application after publication |