CN105085843B - A kind of preparation method of molecular engram material and molecular engram material prepared therefrom - Google Patents
A kind of preparation method of molecular engram material and molecular engram material prepared therefrom Download PDFInfo
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- CN105085843B CN105085843B CN201510579320.1A CN201510579320A CN105085843B CN 105085843 B CN105085843 B CN 105085843B CN 201510579320 A CN201510579320 A CN 201510579320A CN 105085843 B CN105085843 B CN 105085843B
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Abstract
The invention provides a kind of preparation method of molecular engram material and molecular engram material prepared therefrom.In preparation method, Fe is deposited on class graphite phase carbon nitride surface using coprecipitation first3O4Obtain Fe3O4‑g‑C3N4Nano material, and then obtain surface modification and have the magnetic silica class graphite phase carbon nitride nano material of acrylic, then using it as carrier, by optimizing function monomer, it is prepared using surface imprinted technology and while can quickly identifies the molecular engram material of seven kinds of environment incretion interferents.The molecular engram material adsorption capacity is big, selectivity is good, response is fast, chemical stability is good, easy to operation, repeatable utilization rate is high, identification and the separation and concentration of a variety of trace steroids and phenols environment incretion interferent can be realized simultaneously, extend existing magnetic Nano material, class graphite phase carbon nitride material, the application of molecular engram material.
Description
Technical field
The present invention relates to fields such as Environmental Chemistry, analytical chemistry, Food Chemistries, in particular to a kind of molecular engram
The preparation method of material and molecular engram material prepared therefrom.
Background technology
Environment incretion interferent (Environmental Endocrine Disruptors, EDCs) is that one kind can pass through
Disturb organism interior to keep Equilibrium and adjusting growth course and the synthesis of caused natural hormone, secretion, transport, knot
Conjunction, reaction and metabolic process, so as to be had an impact to reproduction, nerve and immune system of biology or the mankind etc. a kind of exogenous
Chemical substance.Correlative study shows that, even if content is horizontal in ppt~ppb, most of EDCs also can be to animal and the hair of the mankind
Educate, reproductive function generation harmful effect, or even trigger tumour (such as breast cancer, oophoroma).
But in recent years, with industry, the fast development of agricultural, EDCs has been widely present in food, water, air and soil
Enter Deng in medium, and by the various approach such as taking in, accumulating in human body, it threatens to human survival and can not be ignored.
The detection technique of trace EDCs in highly sensitive, high precision food, environmental sample is developed, to ensureing that it is great that national health also has
Meaning, it has also become the study hotspot of administrative department of various countries and research institution.
Because food, environmental sample matrix are complicated, various, EDCs contents are generally relatively low, conventional gas chromatography (GC),
High performance liquid chromatography (HPLC)) and chromatograph-mass spectrometer coupling method (GC-MS, HPLC-MS) be both needed to use certain pre-treatment skill
Art.But the pretreatment technology such as traditional liquid-liquid extraction and SPE, its is cumbersome, time-consuming, reagent requirement is big, choosing
Selecting property is relatively low, can not effectively avoid matrix interference, realizes EDCs efficient fast separating concentration, significantly limit dependent part
Monitoring and risk assessment of the door to EDCs.The pretreatment technology that exploitation is efficiently, economic, quick, specificity is good is in complex matrices
EDCs research and application is most important.
In recent years, molecularly imprinted polymer is known because it not only has with natural biologicals such as antibody, acceptor, aptamers
The specific recognition capability that other molecule compares favourably is also strong, steady with structure effect precordainment, extensive practicality, anti-adverse environment ability
It is qualitative it is high, service life is long, easily realizes unique advantage such as industrialization, chromatographic isolation, biology sensor, mimetic enzyme catalysis,
Biomedical, especially SPE etc. is obtained for extensive research and development.But conventional blocks molecular engram gathers
There is the shortcomings of slow mass transfer, leakage template in compound material, be not the ideal chose of sample pre-treatments.
Using surface imprinted technology, with reference to magnetic separation technique, using nano material as carrier, prepare that specific surface area is big, absorption
The magnetic Nano hydridization polyfunctional molecule imprinted polymer that performance is good, mass transfer velocity is fast is preferable solution method.With in environment points
Exemplified by secreting chaff interference, its molecular engram identification material focuses mostly in conventional blocks material, or with silica, titanium oxide, four
Fe 3 O, graphene etc. are hybrid material prepared by carrier, be yet there are no based on Fe3O4-g-C3N4Molecular engram material, and
These research work often can only the similar 2-3 kind EDCs compounds of Sync enrichment structure, when the different steroid of structure and
In the presence of phenols EDCs is common, tend not to realize fast and effectively Sync enrichment and detection.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of molecular engram material.This method preparation technology letter
Single, repeatable to utilize, cost is low, economical and practical, it is easy to operate it is quick, environmental friendliness is high, is more easy to scale, obtained molecule
Efficiently selective removal while imprinted material can be realized to a variety of steroids in environment and food samples and phenols EDCs
And enrichment, important technology support will be provided to the supervision of estrogen and risk assessment.
The second object of the present invention is to provide a kind of molecular engram material.The molecular engram material recognition performance is good, choosing
Selecting property is high, adsorption capacity is big, and magnetic is strong, adsorption rate is fast, efficiency high, can quickly identify simultaneously isolating environment and food water simultaneously
Bisphenol-A (BPA), oestrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2), hexestrol (HES) in sample, oneself
This 7 kinds of environment incretion interferents of the female phenol of alkene (DES).
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of molecular engram material, comprises the following steps：
(1) by g-C3N4Nano-particle ultrasonic disperse adds FeCl into the first organic solvent3·6H2O、FeCl2·
4H2O, ammoniacal liquor is added under 60-90 DEG C of stirring, react 20-60min, obtain magnetic class graphite phase carbon nitride nano-particle；
(2) the magnetic class graphite phase carbon nitride nano-particle is dispersed in the second organic solvent, while stirring successively
Add ammoniacal liquor and tetraethyl orthosilicate；30-50 DEG C is warming up to after all adding, continues to stir 10-13h, obtains coated with silica
Magnetic class graphite phase carbon nitride nano-particle；
(3) the magnetic class graphite phase carbon nitride nano-particle of the coated with silica is scattered in the 3rd organic solvent
In, γ-(methacryloxypropyl) propyl trimethoxy silicane is added while stirring, is continued after adding after stirring 20-24h, is obtained
The silica magnetic class graphite phase carbon nitride nano-particle of acrylic modification；
(4) that the silica magnetic class graphite phase carbon nitride nano-particle that the acrylic is modified is scattered in into the 4th is organic
In solvent, 17 beta estradiols, function monomer and crosslinking agent are sequentially added, adds initiator after stirring, after letting nitrogen in and deoxidizing
Reaction system is sealed, 20-24h is reacted at 50-85 DEG C, obtains molecular engram material；The function monomer includes metering system
Acid, to one kind or more in vinyl benzoic acid, Methacrylamide, 2- vinylpyridines or 2- (trifluoromethyl) acrylic acid
Kind.
The present invention by magnetic Nano material, class graphite phase carbon nitride material, earth silicon material preparation research, lead to
Cross optimization and modified technique flow is successfully prepared silicon dioxide modified magnetic class graphite phase carbon nitride material (g-C3N4-
Fe3O4@SiO2).With simple g-C3N4Nano material is compared, g-C3N4-Fe3O4@SiO2@MPS materials avoid g-C3N4Synthesizing
The shortcomings that with being not readily separated in application process；With Fe3O4Nano material is compared, g-C3N4-Fe3O4@SiO2With more preferable stable
Property, water solubility, absorption property, special optics, electrical properties；Meanwhile surface modification silica is advantageous to according to experiment mesh
Carrier is chemically modified, be easy to implement the function precordainment of nano-hybrid material.
The present invention has the g-C of double bond by that will study preparation surface modification3N4-Fe3O4@SiO2@MPS materials, mating surface
Engram technology, using " graft to " polymerization methodses are in g-C3N4-Fe3O4@SiO2Nano level molecular engram is successfully prepared
Thin layer, obtain magnetic, multi-functional material g-C3N4-Fe3O4@MIP。g-C3N4-Fe3O4@MIP materials have magnetic material concurrently and are easy to point
The absorption property and optics, electrical properties excellent from, molecular engram material efficient selective and class graphite phase carbon nitride, has
Good chemical stability, reusing, extend existing magnetic Nano material, class graphite phase carbon nitride material, molecule print
The application of mark material.
By simulating ERs, optimal screening function monomer species and ratio, it is successfully prepared environment incretion and does
Disturb the artificial receptor of thing, can be achieved bisphenol-A (BPA) in environment and food sample, oestrone (E1), estradiol (E2), estriol (E3),
This 7 kinds of trace steroids of ethinyloestradiol (EE2), hexestrol (HES), diethylstilbestrol (DES) and the interference of phenols environment incretion
The quick identification of thing and separation and concentration.
Preferably, in order to obtain the good g-C of uniform particle diameter, monodispersity3N4-Fe3O4Nano-particle, in step (1), institute
State g-C3N4Concentration of the nano-particle in first organic solvent is 0.2-0.5mg/mL, the FeCl3·6H2O, it is described
FeCl2·4H2Concentration of the O in first organic solvent is followed successively by 12-20 μm of ol/mL, 6-13.4 μm ol/mL, the ammoniacal liquor
Concentration be 25-28%, and the volume ratio of the ammoniacal liquor and first organic solvent is 1:(45-50).It is further preferred that
In step (1), mixing speed 500-900rpm.
Preferably, in step (2), complete g- is coated in order to obtain good magnetic, good dispersion and surface silica dioxide
C3N4-Fe3O4@SiO2Nano-particle, the magnetic class graphite phase carbon nitride nano-particle are dense in second organic solvent
Spend for 1.25-1.75mg/mL, the volume ratio of the tetraethyl orthosilicate, the ammoniacal liquor and second organic solvent is (0.5-
1.0)：5：200.It is further preferred that in step (2), mixing speed 600-1000.
Preferably, there is the g-C of appropriate acrylic to obtain homogeneous scattered and surface modification3N4-Fe3O4@SiO2@MPS receive
Rice corpuscles, in step (3), the silica magnetic class graphite phase carbon nitride nano-particle is in the 3rd organic solvent
Concentration is 3-6mg/mL, the volume of the γ-(methacryloxypropyl) propyl trimethoxy silicane and the 3rd organic solvent
Than for (3-6)：(40-70).It is further preferred that in step (3), mixing speed 600-1000rpm.
Preferably, in step (4), in order to obtain, good dispersion, magnetic are strong, adsorption capacity is good, recognition performance is excellent, identification
The g-C on site more convergence surface3N4-Fe3O4@MIP nano materials, the silica magnetic class graphite-phase of the acrylic modification
Concentration of the azotized carbon nano particle in the 4th organic solvent is 3-7mg/mL, and 17 beta estradiol has the described 4th
Concentration in solvent is 5-10 μm of ol/mL, and concentration of the function monomer in the 4th organic solvent is 15-50 μ
Mol/mL, concentration of the crosslinking agent in the 4th organic solvent are 60-400 μm of ol/mL, and the initiator is described
Concentration in four organic solvents is 0.8-3.0mg/mL.
Preferably, in order to obtain the molecular engram material that imprinting effect is good, recognition capability is strong, stability is good, step (4)
In, the crosslinking agent is ethylene glycol dimethacrylate or trimethylol-propane trimethacrylate, and the initiator is
Azodiisobutyronitrile.
Preferably, described to react 20-24h at 50-85 DEG C in step (4), the step of obtaining molecular engram material, is specific
Including：
20-24h is reacted at 60-65 DEG C, or, first at 50-60 DEG C after reaction 10-12h, then 70-80 DEG C is warming up to, and
10-12h is reacted at this temperature, obtains molecular engram material.
Preferably, in order to obtain the g-C that size is controllable, structure is homogeneous3N4Nano-particle, in step (1), the g-C3N4
The preparation method of nano-particle comprises the following steps：
Melamine is placed in crucible, is put into Muffle furnace with 3-5 DEG C/min programming rate heating muffle stove extremely
2-5h is calcined after 500-550 DEG C, is taken out after naturally cooling to room temperature, obtains g-C3N4Nano-particle.It is it is further preferred that described
The dosage of melamine is 5-10g.
Preferably, site affinity is high, the molecular engram material that specificity is good, stability is good in order to be identified, step
(4) described to react 20-24h at 50-85 DEG C in, the step of obtaining molecular engram material, specifically includes：
20-24h is reacted at 50-85 DEG C, after the completion of the reaction, collects sediment, and washed to supernatant with acetonitrile
Clarification, then washed with acetic acid methanol mixed solution, finally it is dried in vacuo, is identified the material with isolating environment incretion interferent
Material.
Preferably, first organic solvent includes any one in methanol aqueous solution or ethanol water；
Preferably, second organic solvent includes appointing in methanol aqueous solution, ethanol water or isopropanol water solution
Meaning is a kind of；
3rd organic solvent includes any one in methanol, toluene；
4th organic solvent is included in acetonitrile, methanol, toluene, acetonitrile methanol mixed liquor or acetonitrile-DMSO mixed liquors
Any one.
The molecular engram material that a kind of preparation method provided by the present invention is prepared.
The molecular engram material recognition performance is good, selectivity is high, adsorption capacity is big, and magnetic is strong, adsorption rate is fast, efficiency
Height, it can quickly identify simultaneously isolating environment and bisphenol-A (BPA), oestrone (E1), estradiol (E2), estriol in food samples
(E3), this 7 kinds of environment incretion interferents of ethinyloestradiol (EE2), hexestrol (HES), diethylstilbestrol (DES).
Compared with prior art, beneficial effects of the present invention are：
(1) present invention is ground by the preparation to magnetic Nano material, class graphite phase carbon nitride material, earth silicon material
Study carefully, silicon dioxide modified magnetic class graphite phase carbon nitride material (g- is successfully prepared by optimization and modified technique flow
C3N4-Fe3O4@SiO2).With simple g-C3N4Nano material is compared, g-C3N4-Fe3O4@SiO2@MPS materials avoid g-C3N4
The shortcomings that being not readily separated in synthesis and application process；With Fe3O4Nano material is compared, g-C3N4-Fe3O4@SiO2With more preferable
Stability, water solubility, absorption property, special optics, electrical properties；Meanwhile surface modification silica is advantageous to according to reality
Test purpose to be chemically modified carrier, be easy to implement the function pre-setting of nano-hybrid material.
(2) present invention has the g-C of double bond by that will study preparation surface modification3N4-Fe3O4@SiO2@MPS materials, with reference to table
Face engram technology, using " graft to " polymerization methodses are in g-C3N4-Fe3O4@SiO2Nano level molecule print is successfully prepared
Mark thin layer, obtain magnetic, multi-functional material g-C3N4-Fe3O4@MIP。g-C3N4-Fe3O4@MIP materials have magnetic material concurrently and are easy to point
The absorption property and optics, electrical properties excellent from, molecular engram material efficient selective and class graphite phase carbon nitride, has
Good chemical stability, reusing, extend existing magnetic Nano material, class graphite phase carbon nitride material, molecule print
The application of mark material.
(3) present invention is successfully prepared environment by simulating ERs, optimal screening function monomer species and ratio
The artificial receptor of incretion interferent, bisphenol-A (BPA) in environment and food sample, oestrone (E1), estradiol (E2), female can be achieved
In this 7 kinds of trace steroids of triol (E3), ethinyloestradiol (EE2), hexestrol (HES), diethylstilbestrol (DES) and phenols environment
Secrete quick identification and the separation and concentration of chaff interference.
(4) molecular engram material preparation technology produced by the present invention is simple, repeats utilization, and cost is low, economical and practical, knows
Other performance is good, selectivity is high, adsorption capacity is big, and magnetic is strong, adsorption rate is fast, efficiency high, quick, ring easily separated, easy to operate
Border friendliness is high, is more easy to scale, can be achieved in environment and food samples while a variety of steroid and phenols EDCs it is high
Effect ground selective removal and enrichment, important technology support will be provided to the supervision of estrogen and risk assessment.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described.
Fig. 1 is the preparation flow schematic diagram of embodiment 1；
Fig. 2 is Fe prepared by embodiment 13O4(a)、g-C3N4(b)、g-C3N4-Fe3O4(c)、g-C3N4-Fe3O4@SiO2
(d)、g-C3N4-Fe3O4@SiO2@MPS(e)、g-C3N4-Fe3O4@SiO2@MIP (f) transmission electron microscope picture；
Fig. 3 is Fe prepared by embodiment 13O4(a)、g-C3N4-Fe3O4(b)、g-C3N4-Fe3O4@SiO2(c)、g-C3N4-
Fe3O4@SiO2@MPS(d)、g-C3N4-Fe3O4@SiO2@MIP (e) X-ray diffraction；
Fig. 4 is Fe prepared by embodiment 13O4(a)、g-C3N4-Fe3O4(b)、g-C3N4-Fe3O4@SiO2(c)、g-C3N4-
Fe3O4@SiO2@MPS(d)、g-C3N4-Fe3O4@SiO2@MIP (e) hysteresis curve；
Fig. 5 is g-C prepared by embodiment 13N4-Fe3O4G-C prepared by@MIP and comparative example3N4-Fe3O4@NIP absorption etc.
Warm curve；
Fig. 6 is g-C prepared by embodiment 13N4-Fe3O4G-C prepared by@MIP and comparative example3N4-Fe3O4@NIP dynamic is inhaled
Attached curve.
Fig. 7 is g-C prepared by embodiment 13N4-Fe3O4G-C prepared by@MIP and comparative example3N4-Fe3O4@NIP to E1,
The suction-operated of seven kinds of environment incretion interferents such as E2, E3, EE2, DES, BPA, HES.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The present embodiment comprises the following steps
S11：G-C is prepared using thermal polymerization melamine method3N4Nano-particle
The melamine for weighing 10g is placed in the semi-enclosed crucibles of 100mL, then by crucible be placed in Muffle furnace with 3 DEG C/
Min programming rate is incubated 5h after being heated to 550 DEG C.Taken out after naturally cooling to room temperature, with mortar grinder to powdered rear guarantor
Deposit standby.
S12：Magnetic class graphite phase carbon nitride nano-particle (g-C3N4-Fe3O4) preparation
Weigh 125mg g-C3N4With (volume ratio 1 in 500mL ethanol/water mixed solutions：2), ultrasonic disperse 5h, divided
Dissipate uniform g-C3N4Suspension.By 1.838g FeCl3·6H2O (M=270) and 0.703g FeCl2·4H2O (M=198) adds
To above-mentioned g-C3N4In suspension, 10mL 28% (V/W) ammoniacal liquor reaction 30min is added at 80 DEG C after stirring 30min.Question response
Room temperature is cooled to after end, g-C is collected using externally-applied magnetic field3N4-Fe3O4Nano-particle, and washed with ultra-pure water and ethanol, 60
It is dried for standby at DEG C.
S13：Silicon dioxide modified g-C3N4-Fe3O4Nano material g-C3N4-Fe3O4@SiO2Preparation
By the hydrolysis of ammonia-catalyzed tetraethyl orthosilicate (TEOS) by coated with silica in g-C3N4-Fe3O4Nano material
Surface.
Take 300mg g-C3N4-Fe3O4Nano-particle ultrasonic disperse is into 200mL80% methanol-waters, under mechanical agitation successively
5mL ammoniacal liquor and 0.7mL TEOS are added, after all adding, 40 DEG C of continuation mechanical agitation 12h are warming up to, with ultrapure after magnet separation
Water and ethanol wash, and are dried at 60 DEG C, obtain g-C3N4-Fe3O4@SiO2Nano-particle.
S14：The nano-hybrid material g-C of acrylic modification3N4-Fe3O4@SiO2@MPS preparation
Further using γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) in g-C3N4-Fe3O4@SiO2Nanometer
Particle surface modifies acrylic.Concrete operations are：
Weigh 200mg g-C3N4-Fe3O4@SiO2Nano-particle ultrasonic disperse is in 50mL methanol, under mechanical agitation dropwise
4mL MPS are added, 24h is stirred at room temperature, is washed after magnet separation with ultra-pure water and ethanol, dried at 60 DEG C and obtain g-C3N4-
Fe3O4@SiO2@MPS。
S15：The g-C that 100mg acrylic is modified3N4-Fe3O4@SiO2@MPS nano-particles ultrasonic disperses are in 30mL second
In nitrile, template molecule is sequentially added：The beta estradiols (M=272) of 68mg (0.25mmol) 17, function monomer methacrylic acid (M=
86) 43mg (0.5mmol) and to vinyl benzoic acid (M=148) 74mg (0.5mmol), crosslinking agent ethylene glycol dimethyl propylene
Acid esters (M=198) 792.0mg (4mmol) ultrasonic disperse is uniform, addition initiator azodiisobutyronitrile 40mg, after letting nitrogen in and deoxidizing
Reaction system is sealed, reacts 24h under 60 DEG C of water-baths.Sediment is collected with magnet after the completion of reaction, and is washed repeatedly with acetonitrile several
The secondary supernatant clarification to after separating, then template is washed away with 10% acetic acid methanol mixed solution, after reaction product vacuum drying, obtain
To molecular engram material g-C3N4-Fe3O4@MIP。
Embodiment 2
The present embodiment comprises the following steps
S21：G-C is prepared using thermal polymerization melamine method3N4Nano-particle
The melamine for weighing 5g is placed in the semi-enclosed crucibles of 100mL, and then crucible is placed in Muffle furnace.By Muffle
Stove is incubated 3h after being heated to 500 DEG C with 3 DEG C/min programming rate.Taken out after naturally cooling to room temperature, with mortar grinder to powder
Saved backup after last shape.
S22：Magnetic class graphite phase carbon nitride nano-particle (g-C3N4-Fe3O4) preparation
Weigh 100mg g-C3N4With (volume ratio 1 in 500mL ethanol/water mixed solutions：2) ultrasonic disperse 5h, disperseed
Uniform g-C3N4Suspension.By 1.62g FeCl3·6H2O (M=270) and 0.79g FeCl2·4H2O (M=198) is added to
State g-C3N4In suspension, 10mL 25% (V/W) ammoniacal liquor reaction 30min is added at 80 DEG C after stirring 30min.Question response terminates
After be cooled to room temperature, use externally-applied magnetic field collect g-C3N4-Fe3O4Nano-particle, and washed with ultra-pure water and ethanol, at 60 DEG C
It is dried for standby.
S23：Silicon dioxide modified g-C3N4-Fe3O4Nano material g-C3N4-Fe3O4@SiO2Preparation
By the hydrolysis of ammonia-catalyzed tetraethyl orthosilicate (TEOS) by coated with silica in g-C3N4-Fe3O4Nanometer
Particle surface.
Take 250mg g-C3N4-Fe3O4Nano-particle ultrasonic disperse is into 200mL80% methanol-waters, under mechanical agitation successively
5mL ammoniacal liquor and 0.5mL TEOS are added, 40 DEG C of continuation mechanical agitation 12h, is washed after magnet separation with ultra-pure water and ethanol, 60 DEG C
Lower drying, obtains g-C3N4-Fe3O4@SiO2Nano-particle.
S24：The nano-hybrid material g-C of acrylic modification3N4-Fe3O4@SiO2@MPS preparation
Further using γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) in g-C3N4-Fe3O4@SiO2Nanometer
Particle surface modifies acrylic.Concrete operations are：
Weigh 150mg g-C3N4-Fe3O4@SiO2Nano-particle ultrasonic disperse is in 40mL methanol, under mechanical agitation dropwise
3mL MPS are added, 24h is stirred at room temperature, is washed after magnet separation with ultra-pure water and ethanol, dried at 60 DEG C and obtain g-C3N4-
Fe3O4@SiO2@MPS。
S25：The g-C that 200mg acrylic is modified3N4-Fe3O4@SiO2@MPS nano-particles ultrasonic disperses are in 60mL second
In nitrile, the beta estradiols (M=272) of template molecule 108.8mg (0.4mmol) 17, function monomer 2- (trifluoromethyl) are sequentially added
Acrylic acid (M=140.06) 112mg (0.8mmol) and Methacrylamide (M=85.1) 68.1mg (0.8mmol), crosslinking agent
Ethylene glycol dimethacrylate (M=198) 1.584g (8mmol) ultrasonic disperse is uniform, adds initiator azodiisobutyronitrile
50mg, reaction system is sealed after letting nitrogen in and deoxidizing, after reacting 12h under 60 DEG C of water-baths, react 10h under 70 DEG C of water-baths.After the completion of reaction
Sediment is collected with magnet, and washs the supernatant clarification to after separating, then mixed with 10% acetic acid methanol several times repeatedly with acetonitrile
Close solution and wash away template, after reaction product vacuum drying, obtain the bionical identification hydridization of magnetic Nano of environment incretion interferent
Material g-C3N4-Fe3O4@MIP。
Embodiment 3
This implementation comprises the following steps
S31：G-C is prepared using thermal polymerization melamine method3N4Nano-particle
The melamine for weighing 8g is placed in the semi-enclosed crucibles of 100mL, and then crucible is placed in Muffle furnace.By Muffle
Stove is incubated 4h after being heated to 550 DEG C with 3 DEG C/min programming rate.Taken out after naturally cooling to room temperature, with mortar grinder to powder
Saved backup after last shape.
S32：Magnetic class graphite phase carbon nitride nano-particle (g-C3N4-Fe3O4) preparation
Weigh 150mg g-C3N4With (volume ratio 1 in 500mL ethanol/water mixed solutions：2) ultrasonic disperse 5h, disperseed
Uniform g-C3N4Suspension.By 2.430g FeCl3·6H2O (M=270) and 0.99g FeCl2·4H2O (M=198) is added to
Above-mentioned g-C3N4In suspension, 10mL 28% (V/W) ammoniacal liquor reaction 60min is added at 80 DEG C after stirring 30min.Question response knot
Room temperature is cooled to after beam, g-C is collected using externally-applied magnetic field3N4-Fe3O4Nano-particle, and washed with ultra-pure water and ethanol, 60 DEG C
Under be dried for standby.
S33：Silicon dioxide modified g-C3N4-Fe3O4Nano material g-C3N4-Fe3O4@SiO2Preparation
Silicon is coated on by g-C by the hydrolysis of ammonia-catalyzed tetraethyl orthosilicate (TEOS)3N4-Fe3O4Nanoparticle sublist
Face.
Take 350mg g-C3N4-Fe3O4Nano-particle ultrasonic disperse is into 200mL80% methanol-waters, under mechanical agitation successively
5mL ammoniacal liquor and 1.0mL TEOS are added, 40 DEG C of continuation mechanical agitation 12h, is washed after magnet separation with ultra-pure water and ethanol, 60 DEG C
Lower drying, obtains g-C3N4-Fe3O4@SiO2Nano-particle.
S34：The nano-hybrid material g-C of acrylic modification3N4-Fe3O4@SiO2@MPS preparation
Further using γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) in g-C3N4-Fe3O4@SiO2Nanometer
Particle surface modifies acrylic.Concrete operations are：
Weigh 300mg g-C3N4-Fe3O4@SiO2Nano-particle ultrasonic disperse is in 70mL methanol, under mechanical agitation dropwise
6mL MPS are added, 24h is stirred at room temperature, is washed several times with ultra-pure water and ethanol after magnet separation, dried at 60 DEG C and obtain g-
C3N4-Fe3O4@SiO2@MPS。
S35：The g-C that 150mg acrylic is modified3N4-Fe3O4@SiO2@MPS nano-particles ultrasonic disperses are in 45mL first
In alcohol, the beta estradiols (M=272) of template molecule 81.6mg (0.3mmol) 17, function monomer methacrylic acid (M=are sequentially added
86) 77.4mg (0.9mmol) and 2- vinylpyridines (M=105.14) 94.6mg (0.9mmol), crosslinking agent ethylene glycol dimethyl
Acrylate (M=198) 1.78g (10mmol) ultrasonic disperse is uniform, adds initiator azodiisobutyronitrile 60mg, letting nitrogen in and deoxidizing
After seal reaction system, react 24h under 65 DEG C of water-baths.Sediment is collected with magnet after the completion of reaction, and is washed repeatedly with acetonitrile
Supernatant clarification to after separating several times, then template is washed away with 10% acetic acid methanol mixed solution, after reaction product vacuum drying,
Obtain the bionical identification hybrid material g-C of magnetic Nano of environment incretion interferent3N4-Fe3O4@MIP。
Embodiment 4
This implementation comprises the following steps
S41：G-C is prepared using thermal polymerization melamine method3N4Nano-particle
The melamine for weighing 5g is placed in the semi-enclosed crucibles of 100mL, and then crucible is placed in Muffle furnace.By Muffle
Stove is incubated 2h after being heated to 500 DEG C with 5 DEG C/min programming rate.Taken out after naturally cooling to room temperature, with mortar grinder to powder
Saved backup after last shape.
S42：Magnetic class graphite phase carbon nitride nano-particle (g-C3N4-Fe3O4) preparation
Weigh 250mg g-C3N4With (volume ratio 1 in 500mL methanol/water mixed solutions：2) ultrasonic disperse 5h, disperseed
Uniform g-C3N4Suspension.By 2.7g FeCl3·6H2O (M=270) and 1.3266g FeCl2·4H2O (M=198) is added to
Above-mentioned g-C3N4In suspension, 10mL 26% (V/W) ammoniacal liquor reaction 40min is added at 90 DEG C after stirring 30min.Question response knot
Room temperature is cooled to after beam, g-C is collected using externally-applied magnetic field3N4-Fe3O4Nano-particle, and washed for several times with ultra-pure water and ethanol,
It is dried for standby at 60 DEG C.
S43：Silicon dioxide modified g-C3N4-Fe3O4Nano material g-C3N4-Fe3O4@SiO2 preparation
Silicon is coated on by g-C by the hydrolysis of ammonia-catalyzed tetraethyl orthosilicate (TEOS)3N4-Fe3O4Nanoparticle sublist
Face.
Take 350mg g-C3N4-Fe3O4Nano-particle ultrasonic disperse is into 200mL90% ethanol waters, under mechanical agitation successively
5mL ammoniacal liquor and 0.9mL TEOS are added, 50 DEG C of continuation mechanical agitation 13h, is washed after magnet separation with ultra-pure water and ethanol, 60 DEG C
Lower drying, obtains g-C3N4-Fe3O4@SiO2Nano-particle.
S44：The nano-hybrid material g-C of acrylic modification3N4-Fe3O4@SiO2@MPS preparation
Further using γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) in g-C3N4-Fe3O4@SiO2Nanometer
Particle surface modifies acrylic.Concrete operations are：
Weigh 360mg g-C3N4-Fe3O4@SiO2Nano-particle ultrasonic disperse is warming up to 90 DEG C, machinery in 60mL toluene
6mL MPS are added dropwise under stirring, reacts 10h, is washed several times with ultra-pure water and ethanol after magnet separation, dry and obtain at 60 DEG C
g-C3N4-Fe3O4@SiO2@MPS。
S45：The g-C that 135mg acrylic is modified3N4-Fe3O4@SiO2@MPS nano-particles ultrasonic disperses are in 45mL first
In benzene, the beta estradiols (M=272) of template molecule 61.2mg (0.225mmol) 17, function monomer methacrylic acid (M are sequentially added
=86) 32.25mg (0.375mmol) and Methacrylamide (M=85.1) 25.53mg (0.3mmol), crosslinking agent ethylene glycol two
Methacrylate (M=198) 534.6mg (2.7mmol) ultrasonic disperse is uniform, adds initiator azodiisobutyronitrile 36mg,
Reaction system is sealed after letting nitrogen in and deoxidizing, reacts 24h under 60 DEG C of water-baths.Sediment is collected with magnet after the completion of reaction, and uses acetonitrile
The supernatant clarification several times to after separating is washed repeatedly, then washes away template with 10% acetic acid methanol mixed solution, and reaction product is true
After sky is dried, the bionical identification hybrid material g-C of magnetic Nano of environment incretion interferent is obtained3N4-Fe3O4@MIP。
Embodiment 5
This implementation comprises the following steps
S51：G-C is prepared using thermal polymerization melamine method3N4Nano-particle
The melamine for weighing 10g is placed in the semi-enclosed crucibles of 100mL, and then crucible is placed in Muffle furnace.By horse
Not stove is incubated 5h after being heated to 550 DEG C with 5 DEG C/min programming rate.Taken out after naturally cooling to room temperature, with mortar grinder extremely
Saved backup after powdered.
S52：Magnetic class graphite phase carbon nitride nano-particle (g-C3N4-Fe3O4) preparation
Weigh 100mg g-C3N4With (volume ratio 3 in 450mL ethanol/water mixed solutions：2) ultrasonic disperse 5h, disperseed
Uniform g-C3N4Suspension.By 1.70g FeCl3·6H2O (M=270) and 0.531g FeCl2·4H2O (M=198) is added to
Above-mentioned g-C3N4In suspension, 10mL 28% (V/W) ammonia is added at 60 DEG C after stirring 20min under 500rpm stir speed (S.S.)
Water reacts 30min.Question response is cooled to room temperature after terminating, and g-C is collected using externally-applied magnetic field3N4-Fe3O4Nano-particle, and with super
Pure water and ethanol wash, and are dried for standby at 60 DEG C.
S53：Silicon dioxide modified g-C3N4-Fe3O4Nano material g-C3N4-Fe3O4@SiO2Preparation
Silicon is coated on by g-C by the hydrolysis of ammonia-catalyzed tetraethyl orthosilicate (TEOS)3N4-Fe3O4Nanoparticle sublist
Face.Take 350mg g-C3N4-Fe3O4Nano-particle ultrasonic disperse is to 200mL methanol/waters (volume ratio 7:3) in, in 600rpm
Mechanical agitation speed under sequentially add 5mL ammoniacal liquor and 1.0mL TEOS, 50 DEG C of continuation mechanical agitation 13h, used after magnet separation
Ultra-pure water and ethanol wash, and are dried at 60 DEG C, obtain g-C3N4-Fe3O4@SiO2Nano-particle.
S54：The nano-hybrid material g-C of acrylic modification3N4-Fe3O4@SiO2@MPS preparation
Further using γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) in g-C3N4-Fe3O4@SiO2Nanometer
Particle surface modifies acrylic.Concrete operations are：
Weigh 180mg g-C3N4-Fe3O4@SiO2Nano-particle ultrasonic disperse is in 60mL toluene, in 600rpm machinery
It is added dropwise 6mL MPS under stir speed (S.S.), mechanic whirl-nett reaction 12h at 90 DEG C, is washed after magnet separation with ultra-pure water and ethanol
Several times, drying obtains g-C at 60 DEG C3N4-Fe3O4@SiO2@MPS。
S55：The g-C that 350mg acrylic is modified3N4-Fe3O4@SiO2@MPS nano-particles ultrasonic disperses are in 50mL second
Nitrile methyl alcohol mixed liquor (volume ratio 3:1) in, the beta estradiols (M=272) of template molecule 136mg (0.5mmol) 17 are sequentially added,
Function monomer 2- (trifluoromethyl) acrylic acid (M=140.06) 140.06mg (1mmol), to vinyl benzoic acid (M=148)
148mg (1mmol) and 2- vinylpyridines (M=105.14) 52.57mg (0.5mmol), crosslinking agent ethylene glycol dimethyl propylene
Acid esters (M=198) 3.98g (20mmol) ultrasonic disperse is uniform, addition initiator azodiisobutyronitrile 150mg, after letting nitrogen in and deoxidizing
Reaction system is sealed, reacts 20h under 85 DEG C of water-baths.Sediment is collected with magnet after the completion of reaction, and is washed repeatedly with acetonitrile several
The secondary supernatant clarification to after separating, then template is washed away with 10% acetic acid methanol mixed solution, after reaction product vacuum drying, obtain
To the bionical identification hybrid material g-C of magnetic Nano of environment incretion interferent3N4-Fe3O4@MIP。
Embodiment 6
This implementation comprises the following steps
S61：G-C is prepared using thermal polymerization melamine method3N4Nano-particle
The melamine for weighing 7g is placed in the semi-enclosed crucibles of 100mL, then by crucible be placed in Muffle furnace with 4 DEG C/
Min programming rate is incubated 2h after being heated to 530 DEG C.Taken out after naturally cooling to room temperature, with mortar grinder to powdered rear guarantor
Deposit standby.
S62：Magnetic class graphite phase carbon nitride nano-particle (g-C3N4-Fe3O4) preparation
Weigh 100mg g-C3N4With (volume ratio 1 in 500mL methanol/water mixed solutions：1), ultrasonic disperse 5h, divided
Dissipate uniform g-C3N4Suspension.By 1.62g FeCl3·6H2O (M=270) and 0.594gFeCl2·4H2O (M=198) is added to
Above-mentioned g-C3N4In suspension, 10mL28% (V/W) ammonia is added at 70 DEG C after stirring 30min under 900rpm stir speed (S.S.)
Water reacts 30min.Question response is cooled to room temperature after terminating, and g-C is collected using externally-applied magnetic field3N4-Fe3O4Nano-particle, and with super
Pure water and ethanol wash, and are dried for standby at 60 DEG C.
S63：Silicon dioxide modified g-C3N4-Fe3O4Nano material g-C3N4-Fe3O4@SiO2Preparation
By the hydrolysis of ammonia-catalyzed tetraethyl orthosilicate (TEOS) by coated with silica in g-C3N4-Fe3O4Nano material
Surface.
Take 250mg g-C3N4-Fe3O4Nano-particle ultrasonic disperse is to 200mL ethanol/waters (volume ratio 7:3) in,
5mL ammoniacal liquor and 0.6mL TEOS are sequentially added under 1000rpm mechanical agitation speed, 30 DEG C are continued mechanical agitation 10h, magnet point
Washed from rear with ultra-pure water and ethanol, dried at 60 DEG C, obtain g-C3N4-Fe3O4@SiO2Nano-particle.
S64：The nano-hybrid material g-C of acrylic modification3N4-Fe3O4@SiO2@MPS preparation
Further using γ-(methacryloxypropyl) propyl trimethoxy silicane (MPS) in g-C3N4-Fe3O4@SiO2Nanometer
Particle surface modifies acrylic.Concrete operations are：
Weigh 120mg g-C3N4-Fe3O4@SiO2Nano-particle ultrasonic disperse is in 40mL isopropanols, in 1000rpm machine
3mL MPS are added dropwise under tool stir speed (S.S.), stirs 24h at room temperature, is washed after magnet separation with ultra-pure water and ethanol, at 60 DEG C
Drying obtains g-C3N4-Fe3O4@SiO2@MPS。
S65：The g-C that 100mg acrylic is modified3N4-Fe3O4@SiO2@MPS nano-particles ultrasonic disperses are in 30mL second
Nitrile-DMSO mixed liquor (volume ratios 9:1) in, the beta estradiols (M=272) of template molecule 68mg (mmol) 17, work(are sequentially added
Can monomer methacrylic acid (M=86) 43mg (0.5mmol) and to vinyl benzoic acid (M=148) 74mg (0.5mmol), hand over
It is uniform to join agent trimethylol-propane trimethacrylate (M=338.4) 4.06g (12mmol) ultrasonic disperse, adds initiator
Azodiisobutyronitrile 90mg, reaction system is sealed after letting nitrogen in and deoxidizing, first reacts 10h under 50 DEG C of water-baths, after be warming up to 80 DEG C it is anti-
Answer 12h.Sediment is collected with magnet after the completion of reaction, and washs the supernatant clarification to after separating several times repeatedly with acetonitrile, then
Template is washed away with 10% acetic acid methanol mixed solution, after reaction product vacuum drying, obtains molecular engram material g-C3N4-
Fe3O4@MIP。
Comparative example
Comparative example provides the preparation method of non-molecular engram material (NIP), with reference to embodiment 1, is specifically made in comparative example
For standby process in addition to function monomer is not added in step S14, remaining step is identical with embodiment 1.
In order to verify beneficial effects of the present invention, inventor uses the magnetic Nano prepared by the embodiment of the present invention 1 bionical
The carry out performance detection of identification hydridization material, step are as follows：
(1) accurately weigh respectively bisphenol-A (BPA), oestrone (E1), estradiol (E2), estriol (E3), ethinyloestradiol (EE2),
The environment incretion interferent standard items 10.0mg such as hexestrol (HES), diethylstilbestrol (DES) are used in 7 10mL volumetric flasks
After a small amount of methanol dissolving, with methanol constant volume to scale, 1.0g/L standard reserving solution is made, is saved backup in 4 DEG C of refrigerators.
(2) the bionical hybrid material of 20mg magnetic Nano traces and non-trace nano material are added separately into E2 concentration is
In 10-180 μ g/mL 1mL acetonitrile solutions, after shaking 10min at room temperature, supernatant is separated by externally-applied magnetic field, on
After clear liquid is using 0.45 μm of organic filter membrane, HPLC chromatogram separation determination is utilized.Testing result is as shown in Figure 5.As can be seen that with
The adsorption capacity to E2 of the increase of template molecule E2 concentration, the bionical trace hybrid material of magnetic Nano and non-trace nano material
All tend to increase, but nano print material is significantly higher than non-imprinted material to E2 adsorption capacity, the prepared magnetic of this explanation
Absorption of the nano bionic trace hybrid material to E2 is specific.Calculated from Scatch equations, the bionical print of magnetic Nano
Mark hybrid material and the saturated adsorption capacity to E2 of non-trace nano material are respectively 3.37mg/g, 0.95mg/g.
(3) the bionical hybrid material of 20mg magnetic Nano traces and non-trace nano material are added separately into E2 concentration is
In 20 μ g/mL 1mL acetonitrile mixtures, after shaking 2~30min at room temperature, supernatant is separated by externally-applied magnetic field,
After 0.45 μm of organic filter membrane, HPLC separation determinations are utilized.Testing result is as shown in Figure 6, it can be seen that obtained by 10min
Absorption of the bionical trace hybrid material of magnetic Nano to E2 reaches balance.
(4) the bionical hybrid material of 20mg magnetic Nano traces and non-trace nano material are separately added into 1mL and contain 20 μ g/
In mLE1, E2, E3, EE2, DES, BPA, HES acetonitrile mixture, after shaking 10min at room temperature, by externally-applied magnetic field by supernatant
Liquid is separated, and after supernatant is using 0.45 μm of organic filter membrane, utilizes HPLC separation determinations.Testing result is as shown in fig. 7, can be with
Find out that the bionical hybrid material of magnetic Nano trace obtained by the present invention is respectively provided with preferably to environment incretion interferent in above-mentioned 7
Specific adsorption effect, available for a variety of steroid and Polyphenols environment incretion interferents in environment and food samples
Efficiently remove and be enriched with simultaneously.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of molecular engram material, it is characterised in that comprise the following steps：
(1) by g-C3N4Nano-particle ultrasonic disperse adds FeCl into the first organic solvent3·6H2O、FeCl2·4H2O,
60-90 DEG C of stirring is lower to add ammoniacal liquor, reacts 20-60min, obtains magnetic class graphite phase carbon nitride nano-particle；
(2) the magnetic class graphite phase carbon nitride nano-particle is dispersed in the second organic solvent, sequentially added while stirring
Ammoniacal liquor and tetraethyl orthosilicate；30-50 DEG C is warming up to after all adding, continues to stir 10-13h, obtains the magnetic of coated with silica
Property class graphite phase carbon nitride nano-particle；
(3) the magnetic class graphite phase carbon nitride nano-particle of the coated with silica is scattered in the 3rd organic solvent, side
Stir side and add γ-(methacryloxypropyl) propyl trimethoxy silicane, continue after adding after stirring 20-24h, obtain acrylic
The silica magnetic class graphite phase carbon nitride nano-particle of modification；
(4) the silica magnetic class graphite phase carbon nitride nano-particle that the acrylic is modified is scattered in the 4th organic solvent
In, 17 beta estradiols, function monomer and crosslinking agent are sequentially added, initiator is added after stirring, is sealed after letting nitrogen in and deoxidizing
Reaction system, 20-24h is reacted at 50-85 DEG C, obtains molecular engram material；The function monomer includes methacrylic acid, right
One or more in vinyl benzoic acid, Methacrylamide, 2- vinylpyridines or 2- (trifluoromethyl) acrylic acid.
2. preparation method according to claim 1, it is characterised in that in step (1), the g-C3N4Nano-particle is in institute
It is 0.2-0.5mg/mL, the FeCl to state the concentration in the first organic solvent3·6H2O, the FeCl2·4H2O is described first
Concentration in organic solvent is followed successively by 12-20 μm of ol/mL, 6-13.4 μm ol/mL, and the concentration of the ammoniacal liquor is 25-28%, and institute
The volume ratio for stating ammoniacal liquor and first organic solvent is 1:(45-50).
3. preparation method according to claim 1, it is characterised in that in step (2), the magnetic class graphite phase carbon nitride
Concentration of the nano-particle in second organic solvent is 1.25-1.75mg/mL, the tetraethyl orthosilicate, the ammoniacal liquor and
The volume ratio of second organic solvent is (0.5-1.0)：5：200.
4. preparation method according to claim 1, it is characterised in that in step (3), the magnetic of the coated with silica
Concentration of the class graphite phase carbon nitride nano-particle in the 3rd organic solvent is 3-6mg/mL, the γ-(methacryl
Oxygen) volume ratio of propyl trimethoxy silicane and the 3rd organic solvent is (3-6)：(40-70).
5. preparation method according to claim 1, it is characterised in that in step (4), the titanium dioxide of the acrylic modification
Concentration of the silicon magnetic class graphite phase carbon nitride nano-particle in the 4th organic solvent is 3-7mg/mL, 17 β-female two
Concentration of the alcohol in the 4th organic solvent is 5-10 μm of ol/mL, and the function monomer is in the 4th organic solvent
Concentration is 15-50 μm of ol/mL, and concentration of the crosslinking agent in the 4th organic solvent is 60-400 μm of ol/mL, described to draw
It is 0.8-3.0mg/mL to send out concentration of the agent in the 4th organic solvent.
6. preparation method according to claim 5, it is characterised in that in step (4), the crosslinking agent is glycol dinitrate
Base acrylate or trimethylol-propane trimethacrylate, the initiator are azodiisobutyronitrile.
7. according to the preparation method described in claim any one of 1-6, it is characterised in that in step (1), the g-C3N4Nanometer
The preparation method of particle comprises the following steps：
5-10g melamines are placed in crucible, are put into Muffle furnace with 3-5 DEG C/min programming rate heating muffle stove extremely
2-5h is calcined after 500-550 DEG C, is taken out after naturally cooling to room temperature, obtains g-C3N4Nano-particle.
8. according to the preparation method described in claim any one of 1-6, it is characterised in that described at 50-85 DEG C in step (4)
Lower reaction 20-24h, the step of obtaining molecular engram material, specifically include：
20-24h is reacted at 50-85 DEG C, after the completion of the reaction, collects sediment, and is washed to supernatant and clarified with acetonitrile,
Washed with acetic acid methanol mixed solution, be finally dried in vacuo again, be identified the material with isolating environment incretion interferent.
9. according to the preparation method described in claim any one of 1-6, it is characterised in that
First organic solvent includes any one in methanol aqueous solution or ethanol water；
Second organic solvent includes any one in methanol aqueous solution, ethanol water or isopropanol water solution；
3rd organic solvent includes any one in methanol, toluene；
4th organic solvent includes appointing in acetonitrile, methanol, toluene, acetonitrile methanol mixed liquor or acetonitrile-DMSO mixed liquors
Meaning is a kind of.
10. the molecular engram material that the preparation method described in a kind of any one of claim 1-9 is prepared.
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| CN105924578A (en) * | 2016-05-10 | 2016-09-07 | 西北师范大学 | Preparation of difunctional monomer magnetic molecularly-imprinted polymer and application of polymer in adsorption on bisphenol A in wastewater |
| 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 |
| CN108409908B (en) * | 2018-03-26 | 2021-09-07 | 刘飞 | Preparation method of molecularly imprinted polymer, product and application thereof |
| CN108956736B (en) * | 2018-05-11 | 2020-08-07 | 河北科技大学 | Method for preparing diethylstilbestrol molecularly imprinted electrochemical sensor based on electropolymerized p-mercaptoaniline membrane and application of diethylstilbestrol molecularly imprinted electrochemical sensor |
| 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 |
| CN110180509B (en) * | 2019-05-24 | 2021-08-24 | 吉林大学 | Fluorescent molecularly imprinted polymer hollow microsphere and preparation method and application thereof |
| CN110339823A (en) * | 2019-07-01 | 2019-10-18 | 河南城建学院 | A kind of Eichhornia crassipes base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application |
| CN110632143B (en) * | 2019-09-10 | 2021-11-12 | 东南大学 | Electrochemical sensor based on magnetic molecularly imprinted nanocomposite and preparation method and application thereof |
| CN111085011B (en) * | 2019-12-30 | 2021-12-03 | 中南民族大学 | Preparation method of molecularly imprinted magnetic nano material and application of molecularly imprinted magnetic nano material in purification of gamma-aminobutyric acid |
| CN112763553B (en) * | 2020-12-25 | 2023-02-28 | 中北大学 | Electrochemical detection method for protein based on molecular imprinting technology |
| 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 |
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