CN107266627B - A kind of the core-shell type molecularly imprinted polymer and preparation method of recognizable erythrosine - Google Patents

A kind of the core-shell type molecularly imprinted polymer and preparation method of recognizable erythrosine Download PDF

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CN107266627B
CN107266627B CN201710406530.XA CN201710406530A CN107266627B CN 107266627 B CN107266627 B CN 107266627B CN 201710406530 A CN201710406530 A CN 201710406530A CN 107266627 B CN107266627 B CN 107266627B
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erythrosine
polymer
preparation
silicon dioxide
methanol
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CN107266627A (en
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谢卫红
刘静静
张瑞
严恒
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Hubei University of Technology
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
    • B01D15/3852—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36 using imprinted phases or molecular recognition; using imprinted phases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08K9/00—Use of pretreated ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters

Abstract

The present invention is the core-shell type molecularly imprinted polymer and preparation method of a kind of recognizable erythrosine, belong to function of molecular engram field of material technology, specifically a kind of polymer material based on molecular imprinting technology preparation to synthetic food color erythrosine with special identification function, the silica that the present invention is modified using amination is core, using erythrosine pigment molecular as template, one layer of imprinted layer is wrapped up on its surface.Its advantage is that imprinted sites are in polymer surfaces, template is easy to elute from polymer, overcome adsorption/desorption process dynamics slowly and quality transfer the shortcomings that, specific recognition fast and accurately can be carried out to erythrosine, and simplified operation step of the present invention, the usage amount of solvent is reduced, the rate of recovery is improved.

Description

A kind of the core-shell type molecularly imprinted polymer and preparation method of recognizable erythrosine
Technical field
It is that a kind of prepared based on molecular imprinting technology is closed to artificial the invention belongs to function of molecular engram field of material technology There is the polymer material of special identification function at pigment erythrosine, can with the specific recognition of erythrosine with separate.
Background technique
Erythrosine is as a kind of synthetic food color, and due to its strong coloring force, stability is good, low in cost, is usually used in eating It is aesthetic to improve its in product.For most of artificial fabricated food colorants, it is not intended as a kind of nutriment, it cannot It is absorbed by the body, and it is prepared often using benzene, toluene as raw material, through a series of sulfonation, nitration reaction, and in the synthesis process The heavy metals such as arsenic and lead may be infiltrated, if abused it, huge threat is come to the health care belt of consumer.China is to food Colorant, which has, explicitly uses standard and limitation.Currently, according to GB 2760-2014 " national food safety standard food additives Use standard " regulation, allow using the food of erythrosine to be following several: fruit jelly class, cocoa products, chocolate and chocolate system Color make-up, composite flavouring, fruit juice on product (including substitute of cocoa fat chocolate and product) and candy, sauce and jam product, cake Beverage, soda, flavor beverage (only limiting fruit-flavored beverage), assembled alcoholic drinks are 0.05g/kg using limitation；Fried-in-oil nuts and seed Class, dilated food are 0.025g/kg using limitation；Meat enema class, canned meat class are 0.015g/kg using limitation；Decorative fruit Vegetable is 0.1 g/kg using limitation.
Currently, being mainly high performance liquid chromatography, ultraviolet spectrophotometer method, chromatography-matter for the detection method of pigment Spectrum combination, capillary electrophoresis and thin-layered chromatography etc..In order to reduce the influence of food substrate, the pre-treatment of sample is to subsequent Instrument precision detection plays a crucial role.Erythrosine belongs to more special one in several common food colors Kind, the Silon of the extraction for erythrosine, common national regulations is adsorbed to this and is not suitable for, and liquid-liquid extraction consumption Reagent is larger, and step is cumbersome, causes working efficiency low, and most of extractant has certain toxicity, long-time service pair Health and environment will cause certain injury.Furthermore Solid Phase Extraction is also a kind of more common pre-treating method, including magnetic solid phase Extraction, dispersive solid-phase extraction, micro- Solid Phase Extraction and the micro- Solid Phase Extraction of dispersion are widely used in multi-residue analysis, have simplified detection Step, has saved a large amount of solvent, but Solid Phase Extraction lacks selectivity for the extraction of pigment, the substance similar for structure without Method separation, and existing solid phase extraction method is not high to the rate of recovery of erythrosine at present.Therefore, the new method of one kind is explored for red The red detection of moss has great significance.
Molecular imprinting technology (Molecular Imprinting Technique, MIT) is a kind of imitative antibody technique, is referred to The technology for preparing the imprinted polymer that can be mutually distinguishable on three-dimensional space on particular combination site with template molecule, is one Kind can be used to simulate the identification function of natural materials, prepare the manual method with specific selectivity imprinted polymer.Molecule The basic principle of engram technology is specific function monomer to be selected, under the action of initiator using target molecule as template molecule It is condensed together under specific initiation conditions by the effect of crosslinking agent, then washing away template molecule with eluant, eluent can obtain To the polymer on three-dimensional space with specific structure and recognition site.Compared with antibody, enzyme, biomolecule, molecular engram The intrinsic feature that polymer is shown has following: the preparation of imprinted polymer is comparatively simple and economical；Polymer is shown The stability of good physics and chemistry；The binding characteristic of its template will not be lost under extreme electrochemical conditions.In recent years, The preparation of MIPs makes great progress, and has developed the preparation method of multiple polymers, as bulk polymerization, precipitating are poly- Conjunction, suspension polymerisation, surface aggregate etc. prepare various polymer.The pattern of common polymer mainly have it is block-like, Rodlike, spherical, molecular engram film and molecularly imprinted polymer nano material be such as: nano particle, nanotube, nano wire. Molecular imprinting technology is applied in fields such as chromatographic isolation, enzyme simulation, drug chiral separation and biomimetic sensors, While in terms of the enrichment of analytes in low concentration, reaction process balance the control and combinatorial chemical library shifted Certain progress is obtained.Due to molecularly imprinted polymer advantage and characteristic, if be used as a kind of adsorbent apply to it is red In the detection of moss haematochrome, the rate of recovery of erythrosine can be greatly improved, and there is presently no polymerize about erythrosine molecular engram The related article of object has the meaning of research.
Summary of the invention
The purpose of the invention is to overcome the shortcomings of existing methods (complex for operation step, a large amount of reagents of consumption, the rate of recovery It is low), provide it is a kind of can the hud typed molecular blotting polymer microsphere of specific recognition erythrosine preparation method, it be using point Sub- engram technology prepares the functional material of imitative antibody molecule recognition performance, and simplified operation step reduces the use of solvent Amount improves the rate of recovery.
In order to achieve the object of the present invention, the present inventor by a large number of experiments study and persistent exploration, be finally obtained as Lower technical solution:
First using silicon dioxide microsphere as carrier, amination modification is carried out on its surface, by amination after the completion of amination Kernel of the silica as polymerization reaction.Template and function monomer are carried out to be incubated at room temperature and then formed and is intended to polymerize Object.Then polymer, crosslinking agent and initiator is intended to be added in the reaction dissolvent containing amination silicon dioxide microsphere kernel Second step polymerization reaction is carried out, so that silicon dioxide microsphere surface forms the molecular engram outer shell of layer.Finally After the template of polymer surfaces is removed using eluant, eluent, it will leave template molecule in the molecular engram thin layer of microsphere surface Imprinted cavity, for being identified mutually with template molecule, it is specific the preparation method is as follows:
(1) preparation of activated silica microballoon: silicon dioxide microsphere is weighed in flask, NaOH is added, is placed on magnetic force 30 min are corroded in stirring at room temperature on blender, and then with ultrapure water elution, the silica being base treated uses Hcl 90 again Flow back 8 h under the conditions of DEG C, is eluted to neutrality with ultrapure water after reflux, dry, the concentration difference of the sodium hydroxide, hydrochloric acid For 0.25moL/L, 2moL/L.
(2) preparation of amination silicon dioxide microsphere: the silicon dioxide microsphere of activation is placed in flask, and first is added Benzene adds silane coupling agent, and 15 min of ultrasound, in 90 DEG C of 12 h of reflux, methanol washes away unreacted silane after reflux Coupling agent filters resulting amination silicon dioxide granule, and dry, spare, wherein silane coupling agent accounts for the 5% of volume of toluene, The silane coupling agent is 3- aminopropyl triethoxysilane (APTES),.
(3) it is intended to the preparation of polymer: accurately weighing erythrosine and be dissolved in the mixture of methanol, water, and function list is added Body, at room temperature stirring be incubated for 2 h, the function monomer be 4-vinylpyridine (4-VP), methanol, water mixture in methanol, The volume ratio of water is 4:1.
(4) preparation method of erythrosine molecularly imprinted polymer: amination is sequentially added in the reactant of step (3) Silicon dioxide microsphere, crosslinking agent, initiator, ultrasound mix, and upper end installs threeway glass tube additional after magnetic agitation 10min at room temperature, It is passed through nitrogen 30-60min, to remove oxygen；And the closed container equipped with reaction solution is placed on magnetic stirring apparatus, persistently stir It mixes, oil bath heating at 60-70 DEG C, reaction is drawn off afterwards for 24 hours, and the polymer generated after reaction is taken out with G1 sand core funnel Filter, to filter off little particle.Then eluted template is carried out with the mode of the methanol Soxhlet extraction containing 10% ammonium hydroxide, used for the last time Methanol elution, washes away the ammonium hydroxide in polymer, and polymer is dry, can be collected into molecularly imprinted polymer, the crosslinking Agent is ethylene glycol dimethacrylate (EGDMA), and the initiator is azo such as azodiisobutyronitrile (AIBN), function Monomer, crosslinking agent molar ratio are 1:5, the percentage by volume 2% of function monomer, crosslinking agent in the reaction system.
It can obtain having the core-shell type molecularly imprinted polymer of specific recognition function micro- erythrosine using this method Ball can be used as a kind of adsorbent material, and erythrosine in food is identified and adsorbed.
Compared with prior art, advantages of the present invention are as follows: the present invention uses surface molecule print technology, is modified with amination Silica be core, using erythrosine pigment molecular as template, its surface wrap up one layer of imprinted layer.Its advantage are as follows: trace In polymer surfaces, template is easy to elute from polymer in site；Overcome adsorption/desorption process dynamics slowly and The shortcomings that quality is transferred the possession of.The basic principle of its adsorpting pigment is by the electrostatic interaction phase between erythrosine and 4-vinylpridine The hud typed imprinted polymer of mutually identification, preparation fast and accurately can carry out specific recognition to erythrosine.
Attached drawing and its explanation:
The synthetic route of the hud typed erythrosine molecular blotting polymer microsphere of Fig. 1 and its schematic diagram that erythrosine is identified.
Fig. 2 tests the infrared figure of silica obtained, amination silica, non-imprinted polymer microballoon (NIP) Spectrogram.
Adsorption dynamics adsorption kinetics figure of Fig. 3 .MIP/NIP microballoon to template molecule erythrosine.
Isothermal adsorption performance map of Fig. 4 .MIP/NIP microballoon to template molecule erythrosine.
Fig. 5 .MIP/ Silon marked graph.A indicates absorption stoste, and b indicates color of the stoste through Silon adsorption recovery Element, c indicate that stoste adsorbs recycled pigment through MIP, the concentration for scheming erythrosine in centrifuge tube in a is from left to right respectively as follows: 0, 1,5,10 μ g/mL, schemes b and figure c is corresponding with figure a.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention is further described, but of the invention Protection scope be not limited to these examples.It is all to be included in this hair without departing substantially from the change of present inventive concept or equivalent substitute Within bright protection scope.
(1) instrument and reagent
(1) apparatus
C-MAG HS7 magnetic stirring apparatus (German IKA company)；(city of Kunshan's ultrasonic instrument has KQ5200 ultrasonic cleaner Limit company)；AL104 precise electronic assay balance (Mei Tele-support benefit Instrument Ltd.)；7230 full-automatic novel of ZRD- Drying box (Shanghai ZHICHENG Anaiytical Instrument Manufacturing Co., Ltd.)；UV-Lambda 35 is ultraviolet-visible spectrophotometer (platinum Chinese mugwort Er Mo company)；VP30 vacuum filtration pump (Beijing LabTech instrument company)；2000 Fourier's infrared scanner of FT-IR；Electricity Hot thermostatic water bath (the upper macro experimental facilities Co., Ltd of Nereid)；TGL-16G desk centrifuge (Anting Scientific Instrument Factory, Shanghai's system It makes)；3000 high performance liquid chromatograph of Ultimate.
(2) reagent
Ethylene glycol dimethacrylate (EGDMA), erythrosine (analyzing pure, Aladdin)；4-vinylpridine, methanol, Ammonium hydroxide, Silon (analyzing pure, Chinese medicines group chemical reagent)；Azodiisobutyronitrile (AIBN) (98%, source leaf biology)；0.45 μm water system filter membrane (acetate fiber；Upper Haixing County Asia scavenging material factory)；0.45 μm of organic phase filter membrane (nylon66 fiber；Saliva is grand)；0.22 μ M water system syringe needle filter (polyether sulfone, rub fast scientific equipment Co., Ltd in Shanghai)；0.22 μm of hydrophobic phase syringe needle filter (polytetrafluoroethyl-ne Alkene；Rub fast scientific equipment Co., Ltd in Shanghai)；Sodium hydroxide (analyzes pure, Sinopharm Chemical Reagent Co., Ltd.)；Hydrochloric acid (analysis is pure, and break a seal chemical reagent work, Dong great Chemical Co., Ltd.)；3- aminopropyl triethoxysilane (Aladdin)；Toluene (analysis is pure, Shanghai Ling Feng chemical reagent Co., Ltd).
(2) experimental procedure
Example 1: silica surface amination modification
1g solid sodium hydroxide is accurately weighed, 100mL ultrapure water is added to dissolve, is configured to the hydrogen-oxygen that concentration is 0.25 moL/L Change sodium water solution；It is accurate to measure 6.18mL hydrochloric acid, the dilution of 93.82mL ultrapure water is added, is configured to the hydrochloric acid that concentration is 2moL/L Aqueous solution.
(1) activation of silica: 10g silicon dioxide microsphere is accurately weighed in the round-bottomed flask of 250mL, is added 100 ML NaOH(0.25 moL/L), 30 min of stirring corrosion at room temperature are placed on magnetic stirring apparatus, then with ultrapure water elution；Quilt Alkali-treated silica is flowed back 8 h again with the Hcl of 100 mL, 2 moL/L under the conditions of 90 DEG C, with ultrapure after reflux Water elution is dry to neutrality.
(2) silica surface amination: silica that 10 g were activated is weighed in the round-bottomed flask of 250 mL, is added The toluene for entering 100 mL, adds the 3- aminopropyl triethoxysilane (APTES) of 5 mL, and 15 min of ultrasound flow back at 90 DEG C 12 h, methanol washes away unreacted APTES after reflux, and the amidized silicon dioxide granule of preparation is filtered, dry, standby With.
Example 2: the preparation of erythrosine molecularly imprinted polymer and non-molecularly imprinted polymer
Accurately weigh erythrosine 0.2375mmoL and be dissolved in 50 mL methanol: water=4:1(v/v) in, and by functive 4-VP (0.95mmoL) is added in solution, and stirring is incubated for 2 h at room temperature, then sequentially adds the silica (1 that surface modification is crossed G), crosslinking agent EGDMA(4.75mmoL), initiator A IBN(0.014 g), ultrasound mix, be then charged into round-bottomed flask, room temperature Upper end installs threeway glass tube additional after lower magnetic agitation 10min, nitrogen (60min) is passed through, to remove oxygen.
Closed container equipped with above-mentioned reaction solution is placed on magnetic stirring apparatus, appropriate revolving speed is adjusted and persistently stirs, 70 Oil bath heating at DEG C, reaction are drawn off afterwards for 24 hours, and polymerization occurs for reaction solution to prepare erythrosine molecularly imprinted polymer (MIP), the balloon apparatus in reaction process using tee tube remains the nitrogen environment of closed container, polymerize after reaction Object is filtered with G1 sand core funnel, to filter off little particle, is then eluted with the mode of the methanol Soxhlet extraction containing 10% ammonium hydroxide Template is eluted with methanol for the last time, washes away the ammonium hydroxide in polymer.Polymer is dry, collect MIP.Non- imprinted polymer (NIP) preparation is in addition to being not added template, and other steps are as MIP.
Silica, amination silica and NIP are characterized by infrared spectrometer, it is as a result as shown in Fig. 2, right Than the silica of non-amination modification, it can be seen that amination silica is in 1500 cm in figure-1With 685 cm-1Place has Peak occurs, this is because amination silica is in 1500 cm-1Left and right at C-N key and in 685 cm-1The Si-C key at place Caused by stretching vibration, illustrate silica it is amido modified up.Compare the infrared figure of amination silica and NIP Spectrum finds NIP in 1700 cm-1There is peak at left and right, and amination silica does not have, this is because the flexible vibration of C=O in crosslinking agent Movable property life, illustrate successfully to have wrapped up one layer of shell outside amination silica.
Example 3: the adsorption kinetic data
7.2mg erythrosine solid sample is accurately weighed, is dissolved in 12mL ultrapure water, ultrasound mixes, and being configured to concentration is The erythrosine aqueous solution of 600 μ g/mL.10 4mL centrifuge tubes and marking serial numbers are taken, then weigh the MIP that 10mg is prepared respectively Microballoon and NIP microsphere solid are placed wherein, each 5 pipe of two kinds of microballoons.It is 600 μ g/mL that 1mL concentration is added into each centrifuge tube Erythrosine aqueous solution, ultrasound mix, then standing adsorption at room temperature.It is sampled when adsorption time is 5,15,30,45,60 min, Centrifuging and taking supernatant surveys its light absorption value at 533nm with spectrophotometry instrument (Uv-vis), passes through (1) formula meter Its adsorbance (Q) is calculated, observes its adsorbance with the changing rule of adsorption time.
Wherein, Q is adsorbance (μ g/mg)；C0For the concentration (μ g/mL) for adsorbing preceding erythrosine solution；C is red moss after absorption The concentration (μ g/mL) of red solution；V is adsorption liquid volume (mL)；M is the quality (mg) of polymer.With adsorption time (t) for horizontal seat Mark, adsorbance (Q) are ordinate mapping, study adsorbance (Q) with the variation relation of adsorption time.As a result as shown in figure 3, MIP Reach adsorption equilibrium in 15min with NIP.
Example 4: adsorption isotherm experiment
8mg erythrosine solid sample is accurately weighed, is dissolved in 8mL deionization pure water, ultrasound mixes, and is configured to 1mg/mL Erythrosine aqueous solution.8 4mL centrifuge tubes and marking serial numbers are taken, being configured to concentration is respectively 50 μ g/mL, 100 μ g/mL, 150 μ Each 3mL of erythrosine aqueous solution of g/mL, 200 μ g/mL, 250 μ g/mL, 350 μ g/mL, 600 μ g/mL, 800 μ g/mL.
Then it weighs respectively in the MIP microballoon and NIP microsphere solid placement 4mL centrifuge tube that 10mg is prepared, two kinds of microballoons Each 8 pipe, and the concentration for marking upper 50-800 μ g/mL different on each centrifuge tube, are successively added into each centrifuge tube according to label 1mL concentration is the erythrosine aqueous solution of 50-800 μ g/mL, and after ultrasound mixes, microballoon concentration is 10 mg/mL, stands inhale at room temperature Attached 20min.It after the completion of absorption, is centrifuged (15 min, 12000 r/min), takes supernatant, surveyed with spectrophotometry instrument Determine light absorption value of the erythrosine unadsorbed in solution at 533 nm.Erythrosine absorption front and back is calculated according to the variation of light absorption value Then the variation of concentration calculates the adsorbance for obtaining polymer by formula.As a result as shown in figure 4, the saturation of MIP is adsorbed Amount is about 29 μ g/mg.
Example 5: actual sample recovery testu
" NongFuGuoYuan fruit juice " beverage of the yellow without any synthetic food color is chosen as experimental subjects, in fruit juice sample Different amounts of erythrosine is added in product, spiked levels are prepared are as follows: 0,1,5,10 μ g/mL.
20 mg imprinted polymers (MIP) and each 4 parts of Silon are accurately weighed respectively in the centrifuge tube of 4 mL, then The erythrosine juice solution of 2 mL various concentrations is added, at room temperature 20 min of standing adsorption.After the completion of standing adsorption, centrifugation (12000 r/min, 15 min) remove supernatant, retain the substance in centrifuge tube.
Substance in centrifuge tube is done into two kinds of processing, one is the elution that 2 mL are added in first removal of impurities in each centrifuge tube Liquid (V Water:V Formic acid:V Methanol=4:2:4), ultrasound elution, be centrifuged (12000 r/min, 15 min), remove supernatant, then with eluant, eluent into Row template removal.Another method is direct progress template removal, the process that centre does not elute is added 2 in centrifuge tube The ammoniated methanol solution of mL 10% carries out template removal, and ultrasound is centrifuged (12000 r/min, 15 min), takes supernatant.
Obtained supernatant is crossed to 0.22 μm of organic system syringe needle filter, then will supernatant place water-bath in steam to 200 μ L or so add methanol to redissolve, and cross the hydrophobic system's syringe needle filter of 0.22 μm of polytetrafluoroethylene (PTFE), are then analyzed with HPLC, count Calculate its rate of recovery.As a result as shown in table 1 and table two and Fig. 5, it is higher than without the MIP rate of recovery of rinsing step and contains rinsing step The rate of recovery, and the rate of recovery of MIP is higher than Silon, 85% or more.The above is the result shows that erythrosine molecular engram Polymer can be used for being selectively adsorbing and separating for erythrosine in food samples, and does not need rinsing step in the process and saved greatly The organic solvent of amount, can be as a kind of potential Solid Phase Extraction adsorbent material.
HPLC analysis condition:
Ultraviolet device detection, Detection wavelength: 254nm.
Mobile phase: methanol: ammonium acetate solution (pH=4,0.02moL/L).
Gradient elution: methanol: 20%-35%, 3%/min；35%-98%, 9%/min；98% continues 6min.
Flow velocity: 1mL/min.
Ammonium acetate solution configuration: 1.54g ammonium acetate solid sample is accurately weighed, water is added to be dissolved to 1000mL, ultrasound makes it Sufficiently dissolution crosses 0.45 μm of organic filter membrane of water system with acetic acid tune pH to 4.
The rate of recovery and accuracy of 1 erythrosine of table in mark-on fruit juice
Note: including rinsing step during the experiment.
The rate of recovery and accuracy of 2 erythrosine of table in mark-on fruit juice

Claims (1)

1. a kind of preparation method of the core-shell type molecularly imprinted polymer of recognizable erythrosine, which is characterized in that this method includes Following steps:
(1) preparation of activated silica microballoon: silicon dioxide microsphere is weighed in flask, NaOH is added, is placed on magnetic agitation 30 min are corroded in stirring at room temperature on device, and then with ultrapure water elution, the silica being base treated uses HCL in 90 DEG C of items again Flow back 8 h under part, is eluted to neutrality with ultrapure water after reflux, dry；
(2) preparation of amination silicon dioxide microsphere: the silicon dioxide microsphere of activation is placed in flask, and toluene is added, then Silane coupling agent is added, 15 min of ultrasound, in 90 DEG C of 12 h of reflux, methanol washes away unreacted silane coupled after reflux Resulting amination silicon dioxide granule is filtered in agent, and dry, spare, wherein silane coupling agent accounts for the 5% of volume of toluene, described Silane coupling agent be 3- aminopropyl triethoxysilane；
(3) preparation method of erythrosine molecularly imprinted polymer: weighing erythrosine and be dissolved in the mixture of methanol, water, and adds Enter function monomer, stirring is incubated for 2 h at room temperature, then sequentially adds amination silicon dioxide microsphere, crosslinking agent, initiator, surpasses Sound mixes, and upper end installs threeway glass tube additional after magnetic agitation 10min at room temperature, is passed through nitrogen 30-60min, and will be equipped with anti- The closed container of liquid is answered to be placed on magnetic stirring apparatus, lasting to stir, oil bath heating at 60-70 DEG C, reaction is taken afterwards for 24 hours Out, the polymer generated after reaction filters, and to filter off little particle, last eluted template, ammonium hydroxide are dry by polymer, i.e., Collect molecularly imprinted polymer；
The function monomer is 4-vinylpyridine (4-VP)；
The crosslinking agent is ethylene glycol dimethacrylate (EGDMA)；
The initiator is azodiisobutyronitrile (AIBN)；
Wherein function monomer, crosslinking agent molar ratio are 1:5, the percentage by volume 2% of function monomer, crosslinking agent in the reaction system；
The methanol, water mixture in methanol, water volume ratio be 4:1.
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