CN110156941A - A kind of preparation method of patulin magnetic molecularly imprinted polymer - Google Patents
A kind of preparation method of patulin magnetic molecularly imprinted polymer Download PDFInfo
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Abstract
The invention discloses a kind of patulin magnetic molecularly imprinted polymers, the present invention can be realized in agricultural product by magnetic separation technique and molecular imprinting recognition technology to the specific recognition of patulin, the application for efficiently separating and being enriched with, with good absorption and separating property, the specific adsorption to patulin can be realized.
Description
Technical field
The present invention relates to patulin extraction and detection method field more particularly to a kind of patulin are magnetic molecularly imprinted
The preparation method of polymer.
Background technique
Molecularly imprinted polymer (Molecularly imprinted polymers, MIPs) is a kind of with stronger molecule
The novel high polymer biomimetic material of recognition capability has specificity, reservation property, preparation cost low and reusable etc. special
Point is highly suitable as solid phase extraction adsorbents for complex sample pre-treatment.Patulin be by Penicillium patulum, penicillium expansum,
The toxic metabolic products that the moulds such as Aspergillusclavatus generate.Patulin is widely present in the fruit of various mildews, and Penicillium patulum
Element belongs to small molecule compound, soluble easily in water, and thermal stability is high, more stable in an acidic solution, the side such as general heating, sunning
Method is difficult to be removed.So if the patulin that there may be in fruit juice will affect with the fruit process fruit juice of mildew
Fruit juice quality.Research has shown that patulin has teratogenesis, carcinogenic and mutagenesis to experimental animal, and human body takes in patulin
After can cause vomiting stomach function regulating irritation, lead to the damage of respiratory system and urinary system etc., make one neural paralysis, renal function declines
It exhausts.Patulin has been cited as third class suspecious carcinogen matter.And mould contamination is prevented and treated at present, and it ensures food safety, Wei Yiyou
The method of effect is to establish quickly and effectively detection method, reinforces the detection to patulin in agricultural product and monitors.It reports at present
The sample-pretreating method of patulin mainly has matrix solid phase dispersion extraction, gel permeation chromatography, Solid Phase Extraction etc..But due to preceding
It is big to handle cumbersome and Matrix effects, seriously limits conventional rapid detection method and instrument analytical method to Zhan Qing in complex sample
The remaining effective detection of mycin.In addition, the selective power of the pre-treating methods such as traditional QuEChERS and Solid Phase Extraction is poor, only
It is undesirable to change effect, impurity coextraction matrix effect can often occur, to influence the instrument analysis results in later period, therefore explores one
The pretreatment technology good, that purification enrichment ability is strong of kind selectivity is very necessary.It polymerize at present about the molecular engram of patulin
The most of of object preparation method use traditional bulk polymerization and precipitation polymerization process, and sample separating and extracting still need from
The heart crosses column, nitrogen and the complicated processes such as blows.
Magnetic nano-particle (magnetic manoparticles, MNPs)) it is a kind of functional nanomaterials and one
The Magnetic Isolation carrier of kind superior performance, is widely used in foranalysis of nucleic acids, clinical diagnosis, targeted drug, enzyme and cell fixation
It is played an important role in the quick detection of Hazard factor in equal numerous areas and agricultural product.Magnetic Nano material not only has
There is powerful specific surface area, and there is magnetic conductance tropism, the characteristic of superparamagnetism and ability, it may be connected to which functional material obtains
Biochemical activity.In magnetic nanometer surface Synthesis of Molecular Imprinting Polymers, polymer not only has big specific surface area and surpasses
Paramagnetism, binding site are also exposed to magnetic nanometer surface, are conducive to the elution of template, reduce elution time, can also have
Effect avoids template leakage from leading to problems such as quantitatively to be not allowed.As the pre-treatment material of sample, trace in sample can be improved
Separation, enrichment and the extracting power of substance eliminate centrifugation, cross the complex steps such as column, shorten time for sample pretreatment, reduce
The use of organic reagent.Therefore, the present invention uses surface imprinted technology, by molecularly imprinted polymer (MIP) and magnetic Nano
Particle coupling, prepares magnetic nanomolecules imprinted polymer, specific recognition and magnetic Nano based on molecularly imprinted polymer
The orientation efficiently concentrating performance and magnetic separation technique of particle establish the magnetic dispersive solid-phase extraction (MI-MDSPE) of patulin
Pre-treating method realizes the residual to patulin in fruit juice matrix in conjunction with liquid chromatography tandem mass spectrometry (LC-MS/MS)
Detection, has saved the time of sample pre-treatments, and reduces organic reagent use, effectively raises the speed of pre-treatment.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of patulin magnetic molecularly imprinted polymer.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention includes the following steps
1) CH=CH2 modification is carried out to Fe3O4 nanoparticle and be dissolved in methanol solution, the vinylated Fe3O4 receives
The preparation method of rice corpuscles the following steps are included:
The preparation of A Fe3O4 nanoparticle: the Fe3O4 nanoparticle is prepared using coprecipitation, and magnet collects Fe3O4
Nanoparticle with ethanol washing until eluate pH is in neutrality, and gained Fe3O4 solid is dissolved in saving in ethyl alcohol and obtains Fe3O4
Magnetic nanometer.
B Fe3O4@SiO2 particle preparation: above-mentioned Fe3O4 magnetic nanometer ultrasonic disperse is molten in the ethyl alcohol of 80% concentration
In liquid, the ammonium hydroxide of tetraethoxysilane (TEOS) and 25% concentration is added dropwise, is stirred to react 10-48h at room temperature, after reaction,
It is washed to eluate pH after reaction to be in neutrality, is dried in vacuo, obtains Fe3O4@SiO2 magnetic nanometer
The above-mentioned Fe3O4@SiO2 magnetic nanometer of preparation is dissolved in the acetic acid solution added with 10% concentration by C, and 3- (first is added
Base acryloyl-oxy) propyl trimethoxy silicane (MPS), it is stirred to react 3-12h at 30-80 DEG C, is alternately washed with water and methanol
It is in neutrality to eluate pH, and is stored in that methanol solution is spare to obtain vinylated Fe3O4 nanoparticle.
2- indolone standard items, 6- hydroxy niacin standard items are dissolved in methyl alcohol according to molar ratio 1:1-4, are added after dissolution
Enter function monomer 4-vinylpridine carry out prepolymerization 20-60min after, be added vinylated Fe3O4 nanoparticle, crosslinking agent and
Initiator after ultrasonic 5-20min, inflated with nitrogen deoxygenation 10-15 minutes, seals concussion (150-200rpm/min) in water-bath and reacts 8-
48h, 30-80 DEG C of reaction temperature.After reaction, sediment is separated with magnet, and with methanol repeated flushing until supernatant
Clarification is dried at 55 DEG C, with acetate-methanol solution eluted template, until can't detect template molecule.The template molecule is 2-
Indolone and 6- hydroxy niacin.
Specifically, the crosslinking agent is trimethylol-propane trimethacrylate (TRIM) or dimethacrylate second
Diol ester (EGDMA), the trimethylol-propane trimethacrylate is as preferred.
Preferably, the initiator is azodiisobutyronitrile (AIBN)
Specifically, the function monomer is 4-vinylpridine or methacrylic acid (MAA), the 4-vinylpridine
As preferred.
Preferably, the molar ratio of the crosslinking agent and the template molecule is 2-15:1.
Specifically, the function monomer and the template molecule molar ratio are 2-10:1.
Preferably, the volume ratio of the methanol and acetic acid is 6-10:1.
Specifically, the method for the coprecipitation preparation includes the FeCl2 by the FeCl36H2O of 1-3g and 0.1-1g
4H2O distinguishes ultrasonic disperse in ultra-pure water solution, will two solution mix after stirring be added ammonium hydroxide, 70 DEG C of reaction temperature, 50~
The sodium citrate of 0.05-0.2g is stirred to react and is added under 80 DEG C of water-baths, to be cooled to room temperature after reaction.
The beneficial effects of the present invention are:
The present invention can be realized in agricultural product by magnetic separation technique and molecular imprinting recognition technology to the special of patulin
The application that one property identifies, efficiently separates and be enriched with, there is good absorption and separating property, can be realized to patulin
Specific adsorption.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of patulin magnetic molecularly imprinted polymer of the present invention；
Fig. 2 is that (a) Fe3O4 nanoparticle, (b) Fe3O4@SiO2 particle, (c) of preparation of the embodiment of the present invention are vinylated
The XRD diagram of Fe3O4 nanoparticle；
Fig. 3 is that (a) Fe3O4 nanoparticle, (b) Fe3O4@SiO2 particle, (c) of preparation of the embodiment of the present invention are vinylated
The FT-IR spectrogram of Fe3O4 nanoparticle；
Specific embodiment
The present invention will be further explained below with reference to the attached drawings:
Embodiment 1
The preparation of Fe3O4 nanoparticle: Fe3O4 magnetic nanometer is prepared using coprecipitation.Weigh 2.12g FeCl3
6H2O, 0.5g FeCl24H2O distinguish ultrasonic disperse in 5mL ultrapure water.Above-mentioned two solution is transferred in there-necked flask,
And a certain amount of water is added into bottle again.It is put into electric-heated thermostatic water bath and is stirred to react, when temperature rises to 70 DEG C, be added
The ammonium hydroxide of 6mL 25% then raises temperature to 80 DEG C, is stirred to react 10min, and 0.05g sodium citrate is added, and stirs 10min.To anti-
It is cooled to room temperature after answering, is separated Fe3O4 with magnet, with ethanol washing until being in neutrality, and gained Fe3O4 solid is molten
It is saved in ethyl alcohol.
(2) prepared by Fe3O4@SiO2 particle
12mL pure water and 48mL second is added in 250mL three-neck flask in the Fe3O4 magnetic nanometer for taking above-mentioned steps to prepare
Alcohol, ultrasonic disperse 20min.The ammonium hydroxide of 1mL tetraethoxysilane (TEOS) and 2mL 25% is added, is stirred to react 12h at room temperature.
It is alternately rinsed several times with ethyl alcohol and ultrapure water after reaction.
The preparation of Fe3O4@SiO2-CH=CH2 particle
The Fe3O4@SiO2 magnetic nanometer of preparation is dissolved in added with 60mL acetic acid: tri- neck of 250mL of water (1:9, v/v) is burnt
In bottle, 100 μ L 3- (methacryloxypropyl) propyl trimethoxy silicanes (MPS) are added, is stirred to react 3h at 30 DEG C, uses water
It alternately washs several times, and saves spare in methyl alcohol with methanol.
The technology of preparing of Fe3O4@SiO2-CH=CH2@MIP
A certain amount of 2- indolone standard items and 6- hydroxy niacin standard items (the two molar ratio 1:3) are weighed in 150mL's
In round-bottomed flask, 30 methanol are added, 4-vinylpridine (being 2:1 with template molecule molar ratio) is added until completely dissolved, sets
In prepolymerization 20min on shaking table.It takes 100mg Fe3O4@SiO2-CH=CH2 particle to be added in the flask that prepolymerization finishes, adds
Enter trimethylol-propane trimethacrylate (molar ratio with template molecule is 7:1) and 10mg azodiisobutyronitrile, ultrasound
After 5min, inflated with nitrogen deoxygenation 12min is put into 40 DEG C of water-baths after sealing and shakes (150rpm/min) reaction 10h.Reaction terminates
Afterwards, sediment is separated with magnet, and is dried with methanol repeated flushing up at supernatant clarification, 55 DEG C.Acetic acid-first is used later
Alcohol (1:8, v/v) solution eluted template on Soxhlet extraction pipe, until can't detect template molecule.
Example 2
(1) Fe3O4 magnetic nanometer the preparation of Fe3O4 nanoparticle: is prepared using coprecipitation.Weigh 2.3g
FeCl36H2O, 0.9g FeCl24H2O distinguish ultrasonic disperse in 5mL ultrapure water.Above-mentioned two solution is transferred to three
In mouth bottle, and a certain amount of water is added into bottle again.It is put into electric-heated thermostatic water bath and is stirred to react, rise to 70 DEG C to temperature
When, the ammonium hydroxide of 10mL 25% is added, then raises temperature to 80 DEG C, is stirred to react 40min, 0.1g sodium citrate, stirring is added
20min.To be cooled to room temperature after reaction, Fe3O4 is separated with magnet, with ethanol washing until be in neutrality, and by gained
Fe3O4 solid, which is dissolved in ethyl alcohol, to be saved.
(2) prepared by Fe3O4@SiO2 particle
20mL pure water and 80mL second is added in 250mL three-neck flask in the Fe3O4 magnetic nanometer for taking above-mentioned steps to prepare
Alcohol, ultrasonic disperse 40min.The ammonium hydroxide of 2mL tetraethoxysilane (TEOS) and 1mL 25% is added, is stirred to react at room temperature for 24 hours.
It is alternately rinsed several times with ethyl alcohol and ultrapure water after reaction.
(3) preparation of Fe3O4@SiO2-CH=CH2 particle
The Fe3O4@SiO2 magnetic nanometer of preparation is dissolved in added with 100mL acetic acid: tri- neck of 250mL of water (1:9, v/v)
In flask, 150 μ L 3- (methacryloxypropyl) propyl trimethoxy silicanes (MPS) are added, 5h is stirred to react at 60 DEG C, uses
Water and methanol alternately wash several times, and save spare in methyl alcohol.
(4) technology of preparing of Fe3O4@SiO2-CH=CH2@MIP
A certain amount of 2- indolone standard items and 6- hydroxy niacin standard items (the two molar ratio 1:1) are weighed in 150mL's
In round-bottomed flask, 40 methanol are added, 4-vinylpridine (being 4:1 with template molecule molar ratio) is added until completely dissolved, sets
In prepolymerization 40min on shaking table.It takes 50mg Fe3O4@SiO2-CH=CH2 particle to be added in the flask that prepolymerization finishes, adds
Enter trimethylol-propane trimethacrylate (molar ratio with template molecule is 8:1) and 25mg azodiisobutyronitrile, ultrasound
After 10min, inflated with nitrogen deoxygenation 10min is put into 60 DEG C of water-baths after sealing and shakes (160rpm/min) reaction for 24 hours.Reaction knot
Shu Hou is separated sediment with magnet, and is dried with methanol repeated flushing up at supernatant clarification, 55 DEG C.Acetic acid-is used later
Methanol (1:9, v/v) solution eluted template on Soxhlet extraction pipe, until can't detect template molecule.
Example 3
(1) Fe3O4 magnetic nanometer the preparation of Fe3O4 nanoparticle: is prepared using coprecipitation.Weigh 2.8g
FeCl36H2O, 1.0g FeCl24H2O distinguish ultrasonic disperse in 5mL ultrapure water.Above-mentioned two solution is transferred to three
In mouth bottle, and a certain amount of water is added into bottle again.It is put into electric-heated thermostatic water bath and is stirred to react, rise to 70 DEG C to temperature
When, the ammonium hydroxide of 15mL 25% is added, then raises temperature to 80 DEG C, is stirred to react 40min, 0.2g sodium citrate, stirring is added
20min.To be cooled to room temperature after reaction, Fe3O4 is separated with magnet, with ethanol washing until be in neutrality, and by gained
Fe3O4 solid, which is dissolved in ethyl alcohol, to be saved.
(2) prepared by Fe3O4@SiO2 particle
20mL pure water and 70mL second is added in 250mL three-neck flask in the Fe3O4 magnetic nanometer for taking above-mentioned steps to prepare
Alcohol, ultrasonic disperse 30min.The ammonium hydroxide of 3mL tetraethoxysilane (TEOS) and 5mL 25% is added, is stirred to react 36h at room temperature.
It is alternately rinsed several times with ethyl alcohol and ultrapure water after reaction.
(3) preparation of Fe3O4@SiO2-CH=CH2 particle
The Fe3O4@SiO2 magnetic nanometer of preparation is dissolved in added with 120mL acetic acid: tri- neck of 250mL of water (1:9, v/v)
In flask, 200 μ L 3- (methacryloxypropyl) propyl trimethoxy silicanes (MPS) are added, 8h is stirred to react at 40 DEG C, uses
Water and methanol alternately wash several times, and save spare in methyl alcohol.
(4) technology of preparing of Fe3O4@SiO2-CH=CH2@MIP
A certain amount of 2- indolone standard items and 6- hydroxy niacin standard items (the two molar ratio 1:2) are weighed in 150mL's
In round-bottomed flask, 50 methanol are added, 4-vinylpridine (being 8:1 with template molecule molar ratio) is added until completely dissolved, sets
In prepolymerization 40min on shaking table.It takes 30mg Fe3O4@SiO2-CH=CH2 particle to be added in the flask that prepolymerization finishes, adds
Enter trimethylol-propane trimethacrylate (molar ratio with template molecule is 10:1) and 30mg azodiisobutyronitrile, ultrasound
After 10min, inflated with nitrogen deoxygenation 15min is put into 60 DEG C of water-baths after sealing and shakes (170rpm/min) reaction 48h.Reaction knot
Shu Hou is separated sediment with magnet, and is dried with methanol repeated flushing up at supernatant clarification, 55 DEG C.Acetic acid-is used later
Methanol (1:10, v/v) solution eluted template on Soxhlet extraction pipe, until can't detect template molecule.
Example 4
(1) Fe3O4 magnetic nanometer the preparation of Fe3O4 nanoparticle: is prepared using coprecipitation.Weigh 2.3g
FeCl36H2O, 0.9g FeCl24H2O distinguish ultrasonic disperse in 5mL ultrapure water.Above-mentioned two solution is transferred to three
In mouth bottle, and a certain amount of water is added into bottle again.It is put into electric-heated thermostatic water bath and is stirred to react, rise to 70 DEG C to temperature
When, the ammonium hydroxide of 10mL 25% is added, then raises temperature to 80 DEG C, is stirred to react 40min, 0.1g sodium citrate, stirring is added
20min.To be cooled to room temperature after reaction, Fe3O4 is separated with magnet, with ethanol washing until be in neutrality, and by gained
Fe3O4 solid, which is dissolved in ethyl alcohol, to be saved.
(2) prepared by Fe3O4@SiO2 particle
20mL pure water and 80mL second is added in 250mL three-neck flask in the Fe3O4 magnetic nanometer for taking above-mentioned steps to prepare
Alcohol, ultrasonic disperse 40min.The ammonium hydroxide of 2mL tetraethoxysilane (TEOS) and 1mL 25% is added, is stirred to react at room temperature for 24 hours.
It is alternately rinsed several times with ethyl alcohol and ultrapure water after reaction.
(3) preparation of Fe3O4@SiO2-CH=CH2 particle
The Fe3O4@SiO2 magnetic nanometer of preparation is dissolved in added with 100mL acetic acid: tri- neck of 250mL of water (1:9, v/v)
In flask, 180 μ L 3- (methacryloxypropyl) propyl trimethoxy silicanes (MPS) are added, 5h is stirred to react at 60 DEG C, uses
Water and methanol alternately wash several times, and save spare in methyl alcohol.
(4) technology of preparing of Fe3O4@SiO2-CH=CH2@MIP
A certain amount of 2- indolone standard items and 6- hydroxy niacin standard items (the two molar ratio 1:1.5) are weighed in 150mL
Round-bottomed flask in, be added 40 methanol, until completely dissolved be added 4-vinylpridine (with template molecule molar ratio be 4:1),
It is placed in prepolymerization 40min on shaking table.50mg Fe3O4@SiO2-CH=CH2 particle is taken to be added in the flask that prepolymerization finishes,
Trimethylol-propane trimethacrylate (molar ratio with template molecule is 6:1) and 25mg azodiisobutyronitrile is added, surpasses
After sound 10min, inflated with nitrogen deoxygenation 10min is put into 60 DEG C of water-baths after sealing and shakes (160rpm/min) reaction for 24 hours.Reaction
After, sediment is separated with magnet, and is dried with methanol repeated flushing up at supernatant clarification, 55 DEG C.Second is used later
Acid-methanol (1:9, v/v) solution eluted template on Soxhlet extraction pipe, until can't detect template molecule.
Such as the spectral schematic that Fig. 1 is patulin magnetic molecularly imprinted polymer, patulin is magnetic molecularly imprinted to be gathered
Close object morphological rules, uniform particle diameter.
The preparation of non-molecularly imprinted polymer (Fe3O4@SiO2-CH=CH2@NIP) in addition to template is not added, remaining step with
Magnetic molecularly imprinted polymer (Fe3O4@SiO2-CH=CH2@MIP) is identical.
Samples of juice after accurate absorption 1mL is overanxious is added after patulin standard solution sufficiently in the centrifuge tube of 2mL
Vortex 30s, it is to be clean after standing 10-60min.5-40mg Fe3O4@SiO2-CH=CH2@MIP is accurately weighed, shaking table is placed in
It is eluted after upper room temperature concussion 3-20min, carries out Magneto separate using magnetic frame, taken after supernatant liquid filtering film in being examined on LC-MS/MS
It surveys.
As shown in Fig. 2, (a) manufactured in the present embodiment Fe3O4 nanoparticle, (b) Fe3O4@SiO2 particle, (c) vinyl
Change the XRD diagram of Fe3O4 nanoparticle.As seen from the figure in 2 θ within the scope of 10 °~80 °, there is typical diffractive peak in Fe3O4's,
And no change has taken place for the position of appearance.XRD spectrum shows that Fe3O4 particle is the material of highly crystalline and is spinelle knot
Structure, during modified and surface synthetic polymer, no change has taken place for the crystal form of Fe3O4 particle.MMIPs particle
Diffraction peak intensity is substantially reduced, the change of the peak width difference reaction of particle and average grain diameter, with the increase of partial size, XRD spectrum
There is relatively narrow peak width in figure.The process that surface prepares imprinted polymer as a result, does not change the crystal form of Fe3O4 nanoparticle, particle
Size certain change has occurred.
It is received by (a) Fe3O4 nanoparticle, (b) Fe3O4@SiO2 particle, (c) vinylated Fe3O4 that are prepared to example
The FT-IR spectrogram (Fig. 3) of rice corpuscles.As seen from the figure, 571.9cm-1 is the stretching vibration peak of Fe-O key；1087.9cm-1 being Si-
The eigen vibration peak of O-Si shows that Fe3O4 nanoparticle surface successfully connects SiO2；1632.4cm-1 being C=C stretching vibration table
Bright MPS is successfully connected in Fe3O4@SiO2 particle surface.
Result evaluation
(1) range of linearity of method, detection limit
This test selects fruit juice for sample substrate, sample after matrix dispersion-Magnetic solid phases extraction (DMSPE) method purification,
The patulin standard solution for being 0.5~100 μ g/L with its blank sample extracting solution compound concentration.Patulin peak area with it is dense
Degree is in good linear relationship, resulting related coefficient (r2) it is all larger than 0.998.It is to be measured corresponding to 3 for taking signal-to-noise ratio (S/N)
Detection limit of the material concentration as this method, quantitative limit of 10 times of signal-to-noise ratio as this method.As shown in Table 1, patulin
Detection is limited to 0.05 μ g/L.
Addition recycling and detection limit of 1 patulin of table in grape juice, cider juice and orange juice sample
(2) patulin recovery experiment
To select grape juice, cider juice and orange juice be sample substrate for test, is arranged three pitch-based spheres, respectively 1 μ g/L,
10 μ g/L, 50 μ g/L, dMSPE methods detect, matrix external standard sample purification, enrichment with Liquid Chromatography-Tandem Mass Spectrometry
Standard measure.The rate of recovery is the result shows that (see Table 1 for details), the rate of recovery of patulin are opposite to mark between 79.4%~97.9%
Quasi- deviation is not more than 4.7% (n=3).
Polymer adsorption performance study:
It weighs 10mg MMIPs to be placed in 2ml centrifuge tube, is separately added into 20,30,50,80,100,120,160mg/l exhibition
The aqueous solution 1ml of penicillin.The centrifugation seal of tube is placed in oscillator, vibrates 2h at room temperature.Supercentrifuge centrifuge separation is inhaled
Attached solution takes appropriate centrifugate to dilute, 0.22 μm of film filtering.Absorption is measured at 278nm using high performance liquid chromatograph
Patulin concentration in solution, each sample measurement are averaged three times.According to patulin content in the solution of absorption front and back
Variation,
Polymer is calculated to the balance binding capacity Q of patulin using following formula.
Wherein Q is the equilibrium adsorption capacity of trace and non-imprinted polymer to template molecule patulin to Q=(C0-C) × V/m
(mg/g)；C0 is the initial concentration (mg/l) for being adsorbed patulin in solution；Patulin when C is adsorption equilibrium in solution
Concentration (mg/l)；V is the volume (ml) of adsorbent solution；M is the quality (mg) for the polymer being added.
The result shows that the increase MMIPs with patulin initial concentration is in rising trend to the adsorbance of substrate, it is molten
The concentration of patulin is bigger in liquid, and the concentration difference of patulin is bigger in adsorbent surface and solution, and absorption power is bigger, table
The adsorbance revealed is bigger.Reach maximum equilibrium adsorption capacity 8.17mg/g in the solution of 160mg/l.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should be included within the scope of the present invention within principle.
Claims (8)
1. a kind of preparation method of patulin magnetic molecularly imprinted polymer, it is characterised in that:
Include the following steps
1) preparation of vinylated Fe3O4 nanoparticle
CH=CH2 modification is carried out to Fe3O4 nanoparticle and is dissolved in methanol solution, the vinylated Fe3O4 nanoparticle
Preparation method the following steps are included:
The preparation of A Fe3O4 nanoparticle: the Fe3O4 nanoparticle is prepared using coprecipitation, and magnet collects Fe3O4 nanometers
Grain with ethanol washing until eluate pH is in neutrality, and gained Fe3O4 solid is dissolved in saving in ethyl alcohol and obtains Fe3O4 magnetic and receives
Rice corpuscles.
The preparation of B Fe3O4@SiO2 particle: by above-mentioned Fe3O4 magnetic nanometer ultrasonic disperse in the ethanol solution of 80% concentration,
The ammonium hydroxide of tetraethoxysilane (TEOS) and 25% concentration is added dropwise, is stirred to react 10-48h at room temperature, after reaction, reaction knot
It is washed to eluate pH after beam to be in neutrality, is dried in vacuo, obtains Fe3O4@SiO2 magnetic nanometer
The above-mentioned Fe3O4@SiO2 magnetic nanometer of preparation is dissolved in the acetic acid solution added with 10% concentration by C, and 3- (methyl-prop is added
Alkene acyl-oxygen) propyl trimethoxy silicane (MPS), be stirred to react 3-12h at 30-80 DEG C, with water and methanol alternately washing to washing
Liquid pH is in neutrality out, and is stored in that methanol solution is spare to obtain vinylated Fe3O4 nanoparticle.
2) preparation of Fe3O4@SiO2-CH=CH2@MIP
2- indolone standard items, 6- hydroxy niacin standard items are dissolved in methyl alcohol according to molar ratio 1:1-4, function is added after dissolution
After energy monomer 4-vinylpridine carries out prepolymerization 20-60min, vinylated Fe3O4 nanoparticle, crosslinking agent and initiation is added
Agent after ultrasonic 5-20min, inflated with nitrogen deoxygenation 10-15 minutes, seals concussion (150-200rpm/min) in water-bath and reacts 8-48h,
30-80 DEG C of reaction temperature.After reaction, sediment is separated with magnet, and with methanol repeated flushing until supernatant clarify,
It is dried at 55 DEG C, with acetate-methanol solution eluted template, until can't detect template molecule.The template molecule is 2- indoles
Ketone and 6- hydroxy niacin.
2. the preparation method of patulin magnetic molecularly imprinted polymer according to claim 1, it is characterised in that: described
Crosslinking agent be trimethylol-propane trimethacrylate (TRIM) or ethylene glycol dimethacrylate (EGDMA), it is described
Trimethylol-propane trimethacrylate is as preferred.
3. the preparation method of patulin magnetic molecularly imprinted polymer according to claim 1, it is characterised in that: described
Initiator is azodiisobutyronitrile (AIBN).
4. the preparation method of patulin magnetic molecularly imprinted polymer according to claim 1, it is characterised in that: described
Function monomer is 4-vinylpridine or methacrylic acid (MAA), and the 4-vinylpridine is as preferred.
5. the preparation method of patulin magnetic molecularly imprinted polymer according to claim 1 or 2, it is characterised in that:
The molar ratio of the crosslinking agent and the template molecule is 2-15:1.
6. the preparation method of patulin magnetic molecularly imprinted polymer according to claim 1 or 4, it is characterised in that:
The function monomer and the template molecule molar ratio are 2-10:1.
7. the preparation method of patulin magnetic molecularly imprinted polymer according to claim 1, it is characterised in that: described
Methanol and acetic acid volume ratio be 6-10:1.
8. the preparation method of patulin magnetic molecularly imprinted polymer according to claim 1, it is characterised in that: institute
The method for stating coprecipitation preparation includes that the FeCl24H2O difference ultrasonic disperse of the FeCl36H2O and 0.1-1g of 1-3g exists
In ultra-pure water solution, ammonium hydroxide is added in stirring after two solution are mixed, and 70 DEG C of reaction temperature, is stirred to react under 50~80 DEG C of water-baths
And the sodium citrate of 0.05-0.2g is added, to be cooled to room temperature after reaction.
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