CN104387532A - Preparation method of pyraclostrobin molecularly-imprinted polymer - Google Patents
Preparation method of pyraclostrobin molecularly-imprinted polymer Download PDFInfo
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- CN104387532A CN104387532A CN201410688522.5A CN201410688522A CN104387532A CN 104387532 A CN104387532 A CN 104387532A CN 201410688522 A CN201410688522 A CN 201410688522A CN 104387532 A CN104387532 A CN 104387532A
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Abstract
The invention relates to a preparation method of a pyraclostrobin molecularly-imprinted polymer. The preparation method comprises the following steps of: mixing and dissolving template molecule pyraclostrobin, functional monomer MAA (Methacrylic Acid) and cross-linking agent EDMA (Ethylene Glycol Dimethacrylate) according to the mole ratio of the module molecule to the functional monomer to the cross-linking agent of 1 to 4 to 20 in pore-foaming agent acetonitrile; adding initiating agent azobisisobutyronitrile, and carrying out water bath reaction at 60-65 DEG C through nitrogen protection to obtain a template molecule polymer; after further vacuum drying and grinding, removing the module molecule through Soxhlet extraction, and carrying out vacuum drying at 60 DEG C to constant weight so as to finally obtain the pyraclostrobin molecularly-imprinted polymer. The pyraclostrobin molecularly-imprinted polymer prepared through the method disclosed by the invention is capable of effectively separating and gathering pyraclostrobin contained in a complex substrate and detecting a trace amount of pyraclostrobin contained in the environment and food by being combined with the traditional detection method (HPLC), thereby improving the detection efficiency and sensitivity of pyraclostrobin.
Description
Technical field
The present invention relates to a kind of preparation method of technical field of biochemistry, be specifically related to the preparation method of a kind of pyraclostrobin molecularly imprinted polymer (molecularly imprinted polymer, MIP).
Background technology
Pyraclostrobin is a kind of New-type wide-spectrum methoxy acrylic bactericide, by direct failure line mitochondrial respiratory chain, control the expansion of the fungal pathogen bacterium such as Ascomycetes, Basidiomycetes, Oomycete and deuteromycetes, thus effectively prevent and treat the various plants venereal disease evils such as downy mildew of garpe, powdery mildew of cucumber, citrus anthracnose, banana freckle and leaf spot, in the world extensively, be widely used in control of plant disease.Over nearly 10 years, pyraclostrobin sales volume is in global pesticide sales volume before rank ten.
Extensive, a large amount of, the life-time service of pyraclostrobin, adds the residual quantity of pyraclostrobin in environment and food, improves the risk of pyraclostrobin to environment and food safety.Day according to pyraclostrobin allows intake (ADI), and within 2014, China defines the maximum residue limit of pyraclostrobin on oil crops, fruits and vegetables (MRL), and has formulated corresponding standard.For evaluating pyraclostrobin to the risk of environment and food and harm, need detect pyraclostrobin residual quantity in environment and food.
Molecular imprinting is the new research field of of developing rapidly based on molecular recognition theory in recent years.Molecularly imprinted polymer can be had an effect with template molecule specifically, and by corresponding method wash-out, thus can reach the effect of purifying and enrichment molecules of interest.The present invention utilizes molecular imprinting, based on molecular recognition, take pyraclostrobin as template molecule, prepare pyraclostrobin molecularly imprinted polymer, by template molecule elution after Macroscopic single crystal, polymkeric substance after eluted template molecule remains and the space structure of template molecule complementation and group, there is " memory " function, can be special with pyraclostrobin effect, can be quick, highly selective extracts pyraclostrobin from complex environment matrix and fruits and vegetables sample, again by corresponding mode wash-out, enrichment and purifying in addition, to reach the testing requirement of instrumental analysis, thus the pyraclostrobin residual quantity in environment and food is detected.Molecularly imprinted polymer is adopted to carry out the pre-treatment of the residual sample of agriculture, can reduce the use of organic solvent, the severe environment such as opposing soda acid, and used molecularly imprinted polymer is reusable after wash-out activation, safety, economy, environmental protection, be with a wide range of applications.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of pyraclostrobin molecularly imprinted polymer, for the residue detection of pyraclostrobin in environment and agricultural-food provides purifying method.Molecularly imprinted polymer prepared by the present invention has specific binding effect to pyraclostrobin, can optionally in conjunction with pyraclostrobin, thus realize removing the impurity in medium, pyraclostrobin is concentrated, purifies, improve the object of existing detection method sensitivity.
The present invention is achieved by the following technical solutions, and it is as follows that invention comprises step:
(1) by template molecule pyraclostrobin, function monomer methacrylic acid (MAA) and linking agent ethylene glycol dimethacrylate (EDMA), by a certain percentage, mixed dissolution, in perforating agent, adds initiator;
(2) pass into nitrogen deoxidation, after vacuum sealing tube, carry out water bath heat preservation reaction;
(3) synthetic polymkeric substance grinds after vacuum-drying, obtains template molecule polymkeric substance;
(4) by surname extraction, template molecule is removed;
(5) by the polymkeric substance of removing template molecule through vacuum-drying to constant weight, obtain the molecularly imprinted polymer of pyraclostrobin.
Template molecule: function monomer: linking agent mol ratio is 1: 4: 20.
When template molecule is 0.2mol, perforating agent volume is 20ml, and described perforating agent is acetonitrile.
Described initiator is Diisopropyl azodicarboxylate.
Grinding template Molecularly Imprinted Polymer particle diameter is 0.4 ~ 0.6 μm;
Described water bath heat preservation temperature of reaction is 60-65 DEG C, and the reaction times is 24-30 hour.
Described soxhlet extraction temperature, the time is 12 hours.
Described surname extraction bath temperature is 85-90 DEG C, and extraction solvent is methanol-acetic acid mixed solution (v:v, 9: 1).
Described soxhlet extraction, its condition is extraction 3 times, each 4 hours, finally with pure methanol wash column to 1 ~ 2 time, removes remaining acetic acid.
Molecularly imprinted polymer prepared by the present invention has specific adsorption effect to pyraclostrobin, can be used as the filler of Solid-Phase Extraction, environment is separated and enrichment with the pyraclostrobin in food, in conjunction with chromatographic detection method (HPLC method), check the pyrazoles Azoxystrobin in environment and food is residual.In addition, molecularly imprinted polymer also can be developed to chromatograph packing material, for the detection of trace pyraclostrobin.Therefore, molecularly imprinted polymer prepared by the present invention, can significantly improve pyraclostrobin detection sensitivity and detection efficiency, have larger application value.
Accompanying drawing explanation
Fig. 1 MIPs adsorption isothermal line.
Embodiment
The present embodiment is implemented under premised on technical solution of the present invention, and the bright protection domain of we includes but not limited to following embodiment.Embodiment and the specific operation process of the embodiment of the present invention are as follows:
Embodiment 1
Be dissolved in after in 10 mL acetonitriles by pyraclostrobin 0.2 mmol and MAA 0.8 mmol, add EDMA 4 mmol and mix, room temperature left standstill after 1 hour, added initiator azo two fourth acetonitrile 40 mg;
Fully shaken up by above-mentioned mixed solution, ultrasonic degasification, after 5 minutes, leads to nitrogen deoxygenation 5 minutes.Seal rapidly under nitrogen protection, 60 DEG C of water bath heat preservation initiated polymerizations 24 hours.Synthesis template molecule polymkeric substance;
Synthetic polymkeric substance grinds after vacuum-drying, crosses 200-400 mesh sieve, gets 0.5 μm of left-right template Molecularly Imprinted Polymer, within 12 hours, template molecule is removed through surname extraction, bath temperature is 85 DEG C, and extraction solvent is 150ml methanol acetic acid mixed solution (v: v, 9: 1).Finally extremely neutral with the acetic acid that methanol wash column is residual;
Remove the polymkeric substance of template molecule and be dried to constant weight at 60 DEG C, obtain the molecularly imprinted polymer of pyraclostrobin, through measuring, the molecularly imprinted polymer prepared by the present embodiment to the theoretical adsorptive capacity of pyraclostrobin as shown in Fig. 1.
Embodiment 2
Be dissolved in after in 10 mL acetonitriles by pyraclostrobin 0.2 mmol and MAA 0.8 mmol, add EDMA 4 mmol and mix, room temperature left standstill after 1 hour, added initiator azo two fourth acetonitrile 40 mg;
Fully shaken up by above-mentioned mixed solution, ultrasonic degasification, after 5 minutes, leads to nitrogen deoxygenation 5 minutes.Seal rapidly under nitrogen protection, 65 DEG C of water bath heat preservation initiated polymerizations 30 hours.Synthesis template molecule polymkeric substance;
Synthetic polymkeric substance grinds after vacuum-drying, crosses 200-400 mesh sieve, gets 0.5 μm of left-right template Molecularly Imprinted Polymer, within 12 hours, template molecule is removed through surname extraction, bath temperature is 90 DEG C, and extraction solvent is 150ml methanol acetic acid mixed solution (v: v, 9: 1).Finally extremely neutral with the acetic acid that methanol wash column is residual;
Remove the polymkeric substance of template molecule and be dried to constant weight at 60 DEG C, obtain the molecularly imprinted polymer of pyraclostrobin, through measuring, the molecularly imprinted polymer prepared by the present embodiment to the theoretical adsorptive capacity of pyraclostrobin as shown in Fig. 1.
The theoretical adsorptive capacity measuring method of pyraclostrobin is as follows: mixed by the pyraclostrobin solution of MIP and 20ml different concns, be placed in 100 mL triangular flask bottles, at 30 DEG C, shaking table shakes 6 h, supernatant is got after centrifugal, adopt chromatography (HPLC method) to survey pyraclostrobin concentration in supernatant liquor, and calculate the theoretical adsorptive capacity of pyraclostrobin:
Q
e=V×(C
0-C
e)/m
Q
e---MIP is to the equilibrium adsorption capacity (mg/g) of pyraclostrobin
C
0---pyraclostrobin initial concentration solution (mg/ml)
C
e---pyraclostrobin equilibrium concentration (mg/ml)
M---MIP quality (g)
V---pyraclostrobin liquor capacity (l)
With C
efor X-coordinate, Q
efor ordinate zou draws adsorption isothermal line.
As shown in Fig. 1, the maximal absorptive capacity of this polymkeric substance is every gram of Polymer adsorption about 40 milligrams of pyraclostrobins.
Claims (9)
1. a preparation method for pyraclostrobin molecularly imprinted polymer, is characterized in that, preparation process is as follows:
(1) by template molecule pyraclostrobin, function monomer methacrylic acid (MAA) and linking agent ethylene glycol dimethacrylate (EDMA) in molar ratio 1: 4: 20 mixed dissolution in pore-creating agent, add initiator;
(2) nitrogen protection, water bath heat preservation reacts;
(3) vacuum-drying, evenly grinds;
(3) by soxhlet extraction, template molecule is removed;
(4) polymkeric substance of removing template molecule is dried to constant weight at 6 DEG C, obtains the molecularly imprinted polymer of pyraclostrobin.
2. the preparation method of pyraclostrobin molecularly imprinted polymer according to claim 1, is characterized in that, when described template molecule is 0.2 mol, pore-creating agent is 20 mL.
3. the preparation method of pyraclostrobin molecularly imprinted polymer according to claim 1 and 2, is characterized in that, described perforating agent is acetonitrile.
4. the preparation method of pyraclostrobin molecularly imprinted polymer according to claim 1, is characterized in that, described initiator is Diisopropyl azodicarboxylate.
5. according to the preparation method of the pyraclostrobin molecularly imprinted polymer described in claim 1, it is characterized in that, described nitrogen
Protect as being filled with nitrogen 5 ~ 8 minutes, under nitrogen protection by ampere bottle closure.
6. the preparation method of pyraclostrobin molecularly imprinted polymer according to claim 1, is characterized in that, described water bath heat preservation reaction refers to: 60 DEG C ~ 65 DEG C water bath heat preservations react 24 ~ 30 hours.
7. according to the preparation method of the pyraclostrobin molecularly imprinted polymer described in claim 1, it is characterized in that, described soxhlet extraction, its condition is extraction 3 times, each 4 hours, finally with pure methanol wash column to 1 ~ 2 time, removes remaining acetic acid.
8. the preparation method of the pyraclostrobin molecularly imprinted polymer according to claim 1 or 7, is characterized in that, described
Soxhlet extraction, extraction agent is methanol acetic acid mixed solution.
9. the preparation method of pyraclostrobin molecularly imprinted polymer according to claim 8, is characterized in that, described methanol acetic acid mixed solution, and its three's volume ratio is 9: 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354649A (en) * | 2018-11-06 | 2019-02-19 | 北京农学院 | A kind of preparation method and applications of kresoxim-methyl class molecularly imprinted polymer |
-
2014
- 2014-11-26 CN CN201410688522.5A patent/CN104387532A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| FRANCESC A. ESTEVE-TURRILLAS ET AL.: ""Development of immunoaffinity columns for pyraclostrobin extraction from fruit juices and analysis by liquid chromatography with UV detection"", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 殷利丹: ""嘧菌酯在大豆中的残留动态及分子印迹固相萃取研究"", 《中国优秀硕士学位论文全文数据库》 * |
| 王岩等: ""醚菌酯分子印迹聚合物的制备及表征"", 《农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354649A (en) * | 2018-11-06 | 2019-02-19 | 北京农学院 | A kind of preparation method and applications of kresoxim-methyl class molecularly imprinted polymer |
| CN109354649B (en) * | 2018-11-06 | 2021-02-02 | 北京农学院 | Preparation method and application of kresoxim-methyl molecularly imprinted polymer |
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