CN107266627A - The hud typed molecularly imprinted polymer and preparation method of a kind of recognizable erythrosine - Google Patents

The hud typed molecularly imprinted polymer and preparation method of a kind of recognizable erythrosine Download PDF

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CN107266627A
CN107266627A CN201710406530.XA CN201710406530A CN107266627A CN 107266627 A CN107266627 A CN 107266627A CN 201710406530 A CN201710406530 A CN 201710406530A CN 107266627 A CN107266627 A CN 107266627A
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erythrosine
polymer
preparation
molecularly imprinted
imprinted polymer
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CN107266627B (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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    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • 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
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Abstract

The present invention is the hud typed molecularly imprinted polymer and preparation method of a kind of recognizable erythrosine, belong to function of molecular engram field of material technology, it is specifically a kind of that the polymeric material to synthetic food color erythrosine with special identification function is prepared based on molecular imprinting technology, the silica of the invention 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 imprinted sites in polymer surfaces, template is easily eluted from polymer, overcome slow and quality transfer the shortcoming of dynamics of adsorption/desorption process, 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

The core-shell type molecularly imprinted polymer and preparation method of a kind 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 polymeric material of special identification function into pigment erythrosine, can be with the specific recognition of erythrosine with separating.
Background technology
Erythrosine is as a kind of synthetic food color, due to its strong coloring force, and stability is good, with low cost, is usually used in food It is aesthetic to improve its in product.For most of artificial fabricated food colouring agents, it is not intended as a kind of nutriment, it is impossible to 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 building-up 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 Colouring agent, which has, clearly uses standard and limitation.At present, according to GB 2760-2014《National food safety standard food additives Use standard》Regulation, it is allowed to which the food for using erythrosine is 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 limit fruit-flavored beverage）, assembled alcoholic drinks, using limitation be 0.05g/kg；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；Ornamental fruit Vegetable, is 0.1 g/kg using limitation.
At present, the detection method for pigment is mainly high performance liquid chromatography, ultraviolet spectrophotometer method, chromatogram-matter 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 follow-up Instrument precision detection plays vital effect.Erythrosine belongs to more special one in several conventional food colors Kind, for the extraction of erythrosine, the Silon of conventional national regulations is adsorbed to this and not applied to, and liquid-liquid extraction consumption Reagent is larger, and step is cumbersome, causes inefficiency, and most of extractant has certain toxicity, long-term use pair Health and environment can cause certain injury.In addition SPE is also a kind of more common pre-treating method, including magnetic solid phase Extraction, dispersive solid-phase extraction, micro- SPE and scattered micro- SPE are widely used in multi-residue analysis, and it has simplified detection Step, has saved substantial amounts of solvent, but SPE lacks selectivity for the extraction of pigment, for the similar material of structure without Method is separated, and it is not high to the rate of recovery of erythrosine to have solid phase extraction method at present.Therefore, a kind of new method 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 the imprinted polymer that can be mutually distinguishable on particular combination site with template molecule on three dimensions is prepared, is one Kind can for simulate natural materials identification function, prepare with specific selectivity imprinted polymer manual method.Molecule The general principle of engram technology is, using target molecule as template molecule, specific function monomer to be selected, in the presence of initiator Condensed together under specific initiation conditions by the effect of crosslinking agent, template molecule is then washed away with eluant, eluent can just obtain To the polymer on three dimensions with specific structure and recognition site.Compared with antibody, enzyme, biomolecule, molecular engram Polymer show it is intrinsic the characteristics of have following：The preparation of imprinted polymer is comparatively simple and economical；Polymer is shown Good physics and the stability of chemistry；The binding characteristic of its template will not be lost under extreme electrochemical conditions.In recent years, MIPs preparation achieves larger progress, has developed the preparation method of multiple polymers, and such as polymerisation in bulk, precipitation are poly- Conjunction, suspension polymerisation, surface aggregate etc., prepare various polymer.The pattern of common polymer mainly have bulk, Bar-shaped, spherical, molecular engram film and molecularly imprinted polymer nano material are such as：Nano particle, nanotube, nano wire. Molecular imprinting technology is applied in fields such as chromatographic isolation, enzyme simulation, medicine chiral separation and biomimetic sensors, Enrichment simultaneously in analytes in low concentration, course of reaction are balanced in terms of the control of transfer and the projection technologies of combinatorial chemical library 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 on the polymerization of erythrosine molecular engram The related article of thing, the meaning for having research.
The content of the invention
The invention aims to overcome the shortcomings of existing method（Complex operation step, a large amount of reagents of consumption, the rate of recovery It is low）There is provided 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 its simplified operation step reduces the use of solvent Amount, improves the rate of recovery.
In order to realize the purpose of the present invention, the present inventor is studied and persistent exploration by lot of experiments, be finally obtained as Lower technical scheme：
First using silicon dioxide microsphere as carrier, amination modification is carried out on its surface, by amidized two after the completion of amination Silica as polymerisation kernel.Template and function monomer are incubated at room temperature and then desire polymer is formed.So It is intended to polymer, crosslinking agent and initiator afterwards and is added in the reaction dissolvent containing amination silicon dioxide microsphere kernel carry out Two step polymerisations, so that silicon dioxide microsphere surface forms the molecular engram outer shell of layer.Finally using washing After de- agent removes the template of polymer surfaces, it will the trace of template molecule is left in the molecular engram thin layer of microsphere surface Hole, for being recognized mutually with template molecule, specific preparation method is as follows：
（1）The 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, then use ultrapure water elution, and the silica being base treated is again with Hcl in 90 DEG C of bars Flow back 8 h under part, and backflow is eluted to neutrality with ultra-pure water after terminating, and dries, the sodium hydroxide, the concentration of hydrochloric acid are respectively 0.25moL/L、2moL/L。
（2）The preparation of amination silicon dioxide microsphere：The silicon dioxide microsphere of activation is placed in flask, first is added Benzene, adds silane coupler, ultrasonic 15 min, and flow back 12 h at 90 DEG C, and backflow terminates rear methanol and washes away unreacted silane Coupling agent, the amination silicon dioxide granule of gained is filtered, and is dried, standby, wherein silane coupler accounts for the 5% of volume of toluene, Described silane coupler is 3- aminopropyl triethoxysilanes（APTES）,.
（3）It is intended to the preparation of polymer：Accurately weigh erythrosine to be dissolved in the mixture of methanol, water, and add function list Body, at room temperature stirring is incubated 2 h, and described function monomer is 4-vinylpyridine（4-VP）, methanol in methanol, the mixture of water, The volume ratio of water is 4:1.
(4) preparation method of erythrosine molecularly imprinted polymer：In step（3）Reactant in sequentially add amination Silicon dioxide microsphere, crosslinking agent, initiator, ultrasound are mixed, and upper end installs threeway glass tube additional after magnetic agitation 10min at room temperature, Nitrogen 30-60min is passed through, to remove oxygen；And will be equipped with the closed container of reaction solution and be placed on magnetic stirring apparatus, persistently stir Mix, oil bath heating at 60-70 DEG C, be drawn off after reaction 24h, the polymer that reaction is generated after terminating is taken out with G1 sand core funnels Filter, to filter off little particle.Then eluted template is carried out with the mode of surname extraction with the methanol containing 10% ammoniacal liquor, used for the last time Methanol is eluted, and washes away the ammoniacal liquor in polymer, polymer is dried, you can be collected into molecularly imprinted polymer, described crosslinking Agent is GDMA (EGDMA), and described initiator is azo such as azodiisobutyronitrile（AIBN）, function Monomer, crosslinking agent mol ratio are 1:5, the percentage by volume 2% of function monomer, crosslinking agent in reaction system.
It using this method can obtain that there is erythrosine the core-shell type molecularly imprinted polymer of specific recognition function micro- Ball, can be identified and adsorb to erythrosine in food as a kind of sorbing material.
Compared with prior art, advantages of the present invention is：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 is：Trace Site is in polymer surfaces, and template is easily eluted from polymer；Overcome adsorption/desorption process dynamics it is slow and The shortcoming that quality is transferred the possession of.The general principle of its adsorpting pigment is by the electrostatic interaction phase between erythrosine and 4-vinylpridine Mutually identification, the hud typed imprinted polymer of preparation fast and accurately can carry out specific recognition to erythrosine.
Accompanying drawing and its explanation：
The synthetic route of the hud typed erythrosine molecular blotting polymer microspheres of Fig. 1 and its schematic diagram recognized to erythrosine.
Fig. 2 test obtained silica, amination silica, non-imprinted polymer microballoon（NIP）Infrared figure Spectrogram.
Adsorption dynamics adsorption kinetics figure of Fig. 3 .MIP/NIP microballoons to template molecule erythrosine.
Isothermal adsorption performance map of Fig. 4 .MIP/NIP microballoons to template molecule erythrosine.
Fig. 5 .MIP/ Silon marked graphs.A represents absorption stoste, and b represents color of the stoste through Silon adsorption recovery Element, c represents that the concentration that stoste adsorbs erythrosine in centrifuge tube in reclaimed pigment, figure a through MIP is respectively from left to right：0、 1st, 5,10 μ g/mL, figure b and figure c are corresponding with figure a.
Specific embodiment
The following is the specific embodiment of the present invention, technical scheme is done and is further described, but it is of the invention Protection domain be not limited to these embodiments.Every change or equivalent substitute without departing substantially from present inventive concept is included in this hair Within bright protection domain.
（One）Instrument and reagent
（1）Apparatus
C-MAG HS7 magnetic stirring apparatus（German IKA companies）；KQ5200 ultrasonic cleaners（The limited public affairs of city of Kunshan's ultrasonic instrument Department）；AL104 precise electronic assay balances（Plum Teller-support benefit Instrument Ltd.）；The full-automatic novels of ZRD -7230 are dried Case（Shanghai ZHICHENG Anaiytical Instrument Manufacturing Co., Ltd.）；UV-Lambda 35 is ultraviolet-visible spectrophotometer（Platinum Ai Ermo Company）；VP30 is filtered by vacuum pump（Beijing LabTech instrument company）；The Fourier's infrared scanners of FT-IR 2000；Electric heating is permanent Warm water tank（The upper grand experimental facilities Co., Ltd of Nereid）；TGL-16G desk centrifuges（Anting Scientific Instrument Factory, Shanghai manufactures）； The high performance liquid chromatographs of Ultimate 3000.
（2）Reagent
GDMA（EGDMA）, erythrosine（Analyze pure, Aladdin）；4-vinylpridine, methanol, ammoniacal liquor, Silon（Analyze pure, Chinese medicines group chemical reagent）；Azodiisobutyronitrile（AIBN）（98%, source leaf is biological）；0.45 μm of water It is filter membrane（Acetate fiber；Sub- scavenging material factory of upper Haixing County）；0.45 μm of organic phase filter membrane（Nylon66 fiber；Tianjin is grand）；0.22 μm of water It is syringe needle filter（Polyether sulfone, rub fast science equipment Co., Ltd in Shanghai）；0.22 μm of hydrophobic phase syringe needle filter（Polytetrafluoroethylene (PTFE)； Rub fast science equipment Co., Ltd in Shanghai）；Sodium hydroxide（Analyze pure, Chemical Reagent Co., Ltd., Sinopharm Group）；Hydrochloric acid（Analysis It is pure, Kaifeng chemical reagent work of Dong great Chemical Co., Ltd.s）；3- aminopropyl triethoxysilanes（Aladdin）；Toluene（Analyze pure, Shanghai Ling Feng chemical reagent Co., Ltd）.
（Two）Experimental procedure
Example 1：Silica surface amination is modified
It is accurate to weigh 1g solid sodium hydroxides, plus the dissolving of 100mL ultra-pure waters, it is configured to the sodium hydroxide that concentration is 0.25 moL/L The aqueous solution；It is accurate to measure 6.18mL hydrochloric acid, the dilution of 93.82mL ultra-pure waters is added, the hydrochloric acid that concentration is 2moL/L is configured to water-soluble Liquid.
（1）The activation of silica：The accurate 10g silicon dioxide microspheres that weigh add 100 in 250mL round-bottomed flask mL NaOH（0.25 moL/L）, 30 min of stirring corrosion at room temperature are placed on magnetic stirring apparatus, ultrapure water elution is then used；Quilt Alkali-treated silica is flowed back 8 h with 100 mL, 2 moL/L Hcl under the conditions of 90 DEG C again, backflow terminate after with ultrapure Water elution is dried to neutrality.
（2）Silica surface amination：Silica that 10 g activated is weighed in 250 mL round-bottomed flask, plus Enter 100 mL toluene, add 5 mL 3- aminopropyl triethoxysilanes（APTES）, ultrasonic 15 min, in 90 DEG C of backflows 12 h, backflow terminates rear methanol and washes away unreacted APTES, and the amidized silicon dioxide granule of preparation is filtered, and dries, standby With.
Example 2：The preparation of erythrosine molecularly imprinted polymer and non-molecularly imprinted polymer
Accurately weighing erythrosine 0.2375mmoL is dissolved in 50 mL methanol:Water=4:1（v/v）In, and by functive 4-VP （0.95mmoL）It is added in solution, stirring at room temperature is incubated 2 h, then sequentially adds the silica that surface modification is crossed（1 g）, crosslinking agent EGDMA（4.75mmoL）, initiator A IBN（0.014 g）, it is ultrasonic to mix, it is then charged into round-bottomed flask, room temperature Upper end installs threeway glass tube additional after lower magnetic agitation 10min, is passed through nitrogen（60min）, to remove oxygen.
The closed container that will be equipped with above-mentioned reaction solution is placed on magnetic stirring apparatus, is adjusted appropriate rotating speed and is persistently stirred, and 70 It is drawn off after oil bath heating at DEG C, reaction 24h, polymerization occurs for reaction solution to prepare erythrosine molecularly imprinted polymer （MIP）, remain that the nitrogen environment of closed container, reaction polymerize after terminating in course of reaction using the balloon apparatus of three-way pipe Thing G1 sand core funnel suction filtrations, to filter off little particle, are then eluted with the methanol containing 10% ammoniacal liquor with the mode of surname extraction Template, is eluted with methanol for the last time, washes away the ammoniacal liquor in polymer.Polymer is dried, MIP is collected.Non- imprinted polymer （NIP）Preparation in addition to template is not added with, other steps are as MIP.
Silica, amination silica and NIP are characterized by infrared spectrometer, as a result as shown in Fig. 2 right The silica modified than non-amination, in it can be seen from the figure that amination silica in 1500 cm-1With 685 cm-1Place has Peak occurs, and this is due to amination silica in 1500 cm-1C-N keys at left and right and in 685 cm-1The Si-C keys at place Caused by stretching vibration, illustrate silica it is amido modified up.Contrast amination silica and NIP infrared figure Spectrum, finds NIP in 1700 cm-1There is peak at left and right, and amination silica does not have, this, which is due to that C=O is flexible in crosslinking agent, shakes 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 samples accurately are weighed, are dissolved in 12mL ultra-pure waters, ultrasound is mixed, concentration are configured to for 600 μ The g/mL erythrosine aqueous solution.10 4mL centrifuge tubes and marking serial numbers are taken, the MIP microballoons that 10mg is prepared then are weighed respectively Placed wherein with NIP microsphere solids, each 5 pipe of two kinds of microballoons.It is the 600 red moss of μ g/mL that 1mL concentration is added into each centrifuge tube The red aqueous solution, ultrasound is mixed, then standing adsorption at room temperature.Adsorption time be 5,15,30,45,60 min when sample, centrifuge Supernatant is taken, spectrophotometry instrument is used（Uv-vis）Its light absorption value at 533nm is surveyed, is passed through（1）Formula calculates it Adsorbance（Q）, observe changing rule of its adsorbance with adsorption time.
Wherein, Q is adsorbance（μg/mg）；C0For the concentration of erythrosine solution before absorption（μg/mL）；C is red moss after absorption The concentration of red solution（μg/mL）；V is adsorption liquid volume（mL）；M is the quality of polymer（mg）.With adsorption time（t）Sat to be horizontal Mark, adsorbance (Q) is mapped for ordinate, studies adsorbance（Q）With the variation relation of adsorption time.As a result as shown in figure 3, MIP With NIP adsorption equilibrium is reached in 15min.
Example 4：Adsorption isotherm experiment
8mg erythrosine solid samples accurately are weighed, are dissolved in 8mL deionization pure water, ultrasound is mixed, and is configured to the red of 1mg/mL The red aqueous solution of moss.8 4mL centrifuge tubes and marking serial numbers are taken, it is respectively 50 μ g/mL, 100 μ g/mL, 150 μ g/ to be configured to concentration ML, 200 μ g/mL, 250 μ g/mL, 350 μ g/mL, 600 μ g/mL, 800 μ g/mL each 3mL of the erythrosine aqueous solution.
Then weigh respectively in MIP microballoons and NIP microsphere solids placement 4mL centrifuge tubes that 10mg is prepared, two kinds of microballoons Each 8 pipe, and concentration different 50-800 μ g/mL on mark on each centrifuge tube, are added into each centrifuge tube successively according to label 1mL concentration is the 50-800 μ g/mL erythrosine aqueous solution, after ultrasound is mixed, and microballoon concentration is 10 mg/mL, stands inhale at room temperature Attached 20min.After the completion of absorption, centrifugation（15 min, 12000 r/min）, supernatant is taken, is surveyed with spectrophotometry instrument Determine the light absorption value of erythrosine not to be adsorbed in solution at 533 nm.According to the change of light absorption value calculate erythrosine absorption before and after The change of concentration, then calculates and then draws the adsorbance of polymer by formula.As a result as shown in figure 4, MIP saturation absorption Amount is about 29 μ g/mg.
Example 5：Actual sample recovery testu
Choosing " NongFuGuoYuan fruit juice " of the yellow without any synthetic food color, beverage is as experimental subjects, in samples of juice Different amounts of erythrosine is added, spiked levels are formulated as：0、1、5、10 μg/mL.
20 mg imprinted polymers are accurately weighed respectively（MIP）With each 4 parts of Silon in 4 mL centrifuge tube, then The erythrosine juice solution of 2 mL various concentrations is added, at room temperature the min of standing adsorption 20.After the completion of standing adsorption, centrifugation （12000 r/min, 15 min）, supernatant is removed, retains the material in centrifuge tube.
Material in centrifuge tube is done into two kinds of processing, a kind of is the elution that first removal of impurities adds 2 mL in each centrifuge tube Liquid（V Water:V Formic acid:V Methanol=4:2:4）, ultrasound elution, centrifugation（12000 r/min, 15 min）, supernatant is removed, then entered with eluant, eluent Row template removal.Another method is direct progress template removal, and the middle process without elution adds 2 in centrifuge tube ML 10% ammoniated methanol solution carries out template removal, ultrasound, centrifugation（12000 r/min, 15 min）, take supernatant.
Obtained supernatant is crossed to 0.22 μm of organic system syringe needle filter, then will supernatant place steamed in water-bath 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 MIP rate of recovery is higher than Silon, more than 85%.The above result shows erythrosine molecular engram Polymer can be used for being selectively adsorbing and separating for erythrosine in food samples, and during do not need rinsing step to save greatly The organic solvent of amount, can be as a kind of potential SPE sorbing material.
HPLC analysis conditions：
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 is configured：1.54g ammonium acetate solid samples accurately are weighed, adds water and is dissolved to 1000mL, ultrasound makes it Fully dissolving, pH to 4 is adjusted with acetic acid, crosses 0.45 μm of organic filter membrane of water system.
The rate of recovery and accuracy of the erythrosine of table 1 in mark-on fruit juice
Note：Rinsing step is included in experimentation.
The rate of recovery and accuracy of the erythrosine of table 2 in mark-on fruit juice

Claims (2)

1. a kind of core-shell type molecularly imprinted polymer of recognizable erythrosine, it is characterised in that the molecularly imprinted polymer can be made For a kind of sorbing material, specific recognition and absorption are carried out to erythrosine in food.
2. a kind of preparation method of the core-shell type molecularly imprinted polymer of recognizable erythrosine, it is characterised in that this method includes Following steps：
（1）The 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, then use ultrapure water elution, and the silica being base treated is again with HCL in 90 DEG C of bars Flow back 8 h under part, and backflow is eluted to neutrality with ultra-pure water after terminating, and dries；
（2）The preparation of amination silicon dioxide microsphere：The silicon dioxide microsphere of activation is placed in flask, toluene is added, then Add silane coupler, ultrasonic 15 min, 90 DEG C flow back 12 h, backflow terminate rear methanol wash away it is unreacted silane coupled Agent, the amination silicon dioxide granule of gained is filtered, and is dried, standby, and wherein silane coupler accounts for the 5% of volume of toluene, described Silane coupler be 3- aminopropyl triethoxysilanes；
（3）The preparation method of erythrosine molecularly imprinted polymer：Weigh erythrosine to be dissolved in the mixture of methanol, water, and add Enter function monomer, stirring at room temperature is incubated 2 h, then sequentially adds amination silicon dioxide microsphere, crosslinking agent, initiator, surpasses Sound is mixed, 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 is taken after reacting 24h Go out, the polymer suction filtration that reaction is generated after terminating, to filter off little particle, last eluted template, ammoniacal liquor are dried polymer, i.e., Collect molecularly imprinted polymer；
Described function monomer is 4-vinylpyridine（4-VP）；
Described crosslinking agent is GDMA (EGDMA)；
Described initiator is azo such as azodiisobutyronitrile（AIBN）；
Wherein function monomer, crosslinking agent mol ratio are 1:5, the percentage by volume 2% of function monomer, crosslinking agent in reaction system；
Methanol, the volume ratio of water are 4 in the methanol, the mixture of water:1.
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CN114158607A (en) * 2021-12-06 2022-03-11 北京市农林科学院 Green preservative for controlling cold damage of green peppers and using method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114158607A (en) * 2021-12-06 2022-03-11 北京市农林科学院 Green preservative for controlling cold damage of green peppers and using method thereof
CN114158607B (en) * 2021-12-06 2024-01-16 北京市农林科学院 Green preservative for controlling cold damage of green peppers and application method thereof
CN114522445A (en) * 2022-01-04 2022-05-24 广东省科学院测试分析研究所(中国广州分析测试中心) Preparation method and application of core-shell structure composite material solid phase micro-extraction probe
CN114522445B (en) * 2022-01-04 2023-09-08 广东省科学院测试分析研究所(中国广州分析测试中心) Preparation method and application of core-shell structure composite material solid-phase microextraction probe

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