CN109354649B - Preparation method and application of kresoxim-methyl molecularly imprinted polymer - Google Patents
Preparation method and application of kresoxim-methyl molecularly imprinted polymer Download PDFInfo
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Abstract
The invention relates to the field of compound extraction and separation and purification, and particularly relates to a preparation method and application of kresoxim-methyl molecularly imprinted polymer. The preparation method comprises the steps of carrying out polymerization reaction by using kresoxim-methyl and pyraclostrobin as template molecules, methacrylic acid as a functional monomer and trimethylolpropane trimethacrylate as a cross-linking agent, and removing unpolymerized functional monomers, cross-linking agents and template molecules in polymers to obtain the polymer. The kresoxim-methyl molecularly imprinted polymer is prepared by a precipitation polymerization method, and can realize specific identification on kresoxim-methyl and pyraclostrobin, so that separation, enrichment and purification of kresoxim-methyl and pyraclostrobin are realized, and a purification method is provided for residue detection of kresoxim-methyl and pyraclostrobin in environment and agricultural products.
Description
Technical Field
The invention relates to the field of compound extraction and separation and purification, and particularly relates to a preparation method and application of kresoxim-methyl molecularly imprinted polymer.
Background
The methoxy acrylic ester bactericide is found on the basis of a natural product beta-methoxy acrylic ester. Through intensive research on methoxy acrylate bactericides, the action mechanism of the bactericides is found to play a role in sterilizing by interfering the respiration of pathogenic fungi, and the bactericides are fungal cytochrome bc1 respiration inhibitors. As the usage amount and the residual amount of the strobilurin bactericide are continuously increased, the problem of the residual amount of the bactericide causes the attention of relevant management departments of all countries around the world, and a plurality of countries and relevant organizations define the residual limit amount of the bactericide.
Kresoxim-methyl, a methoxy acrylate fungicide with higher activity, was developed in 1989 by BASF corporation, and is also commercialized in 1996, and European patent number is EP 0253213. Kresoxim-methyl is also known as phenoxy kresoxim-methyl, phenoxy polyester and kresoxim-methyl, and has the chemical name of (E) -2-methoxyimino- [2- (o-methyl phenoxymethyl) phenyl ] acetic acid methyl ester.
Pyraclostrobin is a strobilurin fungicide with pyrazole structure developed by Bass in 1993 and was registered and marketed in 2001. It has a broad bactericidal spectrum and is widely used for diseases caused by almost all types of fungal pathogens, such as basidiomycetes, deuteromycetes, ascomycetes and oomycetes. The bactericidal composition is mainly used for preventing and treating powdery mildew and rust disease of wheat, barley leaf rust disease, grape powdery mildew and downy mildew, black leaf streak of banana, early and late blight of tomato and the like.
Molecular imprinting is a high-end technique based on the molecular level, which enables the formation of sites in a polymer matrix with specific recognition capabilities for template molecules or template analogs. Molecularly Imprinted Polymers (MIPs) are materials that form three-dimensional polymers around template molecules, which are eluted to leave specific cavities in the template molecules, forming specific adsorption materials for the template molecules. Molecular imprinting techniques have advanced to a certain level, making great progress in all respects. However, MIPs are mostly imprinted single templates, and only have high selectivity to the templates themselves, so that the use of MIPs is limited.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a kresoxim-methyl molecularly imprinted polymer, the prepared kresoxim-methyl molecularly imprinted polymer microsphere and a solid-phase extraction column prepared by using the kresoxim-methyl molecularly imprinted polymer microsphere as a filling material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of kresoxim-methyl molecularly imprinted polymer comprises the steps of carrying out polymerization reaction by using kresoxim-methyl and pyraclostrobin as template molecules, methacrylic acid as a functional monomer and trimethylolpropane trimethacrylate as a cross-linking agent, and removing unpolymerized functional monomer, cross-linking agent and template molecules in the polymer.
The kresoxim-methyl molecularly imprinted polymer microsphere prepared by the preparation method of the kresoxim-methyl molecularly imprinted polymer.
The solid-phase extraction column takes the kresoxim-methyl molecularly imprinted polymer microspheres as a filler.
Compared with the prior art, the invention has the beneficial effects that: the invention synthesizes the kresoxim-methyl molecularly imprinted polymer by adopting double-template molecules through a precipitation polymerization method, and has good selectivity on kresoxim-methyl and pyraclostrobin. The molecular imprinting polymer microbeads have small particle size, large specific surface and strong adsorption capacity. The kresoxim-methyl molecularly imprinted polymer synthesized by the method is used as a filler of a solid-phase extraction column, and can be applied to high-selection separation and enrichment of trace kresoxim-methyl and pyraclostrobin in environment and food.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a kresoxim-methyl equilibrium adsorption curve diagram of kresoxim-methyl molecularly imprinted polymer microspheres in experimental example 2 of the invention;
fig. 2 is a graph showing the equilibrium adsorption of pyraclostrobin on kresoxim-methyl molecularly imprinted polymer microsphere in experimental example 2 of the present invention.
Detailed Description
The invention aims to provide a preparation method of a kresoxim-methyl molecularly imprinted polymer, the prepared kresoxim-methyl molecularly imprinted polymer microsphere and a solid-phase extraction column prepared by using the kresoxim-methyl molecularly imprinted polymer microsphere as a filling material.
A preparation method of kresoxim-methyl molecularly imprinted polymer comprises the steps of carrying out polymerization reaction by using kresoxim-methyl and pyraclostrobin as template molecules, methacrylic acid as a functional monomer and trimethylolpropane trimethacrylate as a cross-linking agent, and removing unpolymerized functional monomer, cross-linking agent and template molecules in the polymer.
According to the invention, the kresoxim-methyl and the pyraclostrobin are selected as template molecules, so that the molecularly imprinted polymer Microsphere (MIP) with high class specificity and selectivity is synthesized, and meanwhile, the detection of the kresoxim-methyl and the pyraclostrobin can be realized.
The selection of the functional monomer has great influence on the adsorption performance of the molecularly imprinted polymer, and needs to be selected according to the structure and basic properties of the template molecule. The invention selects methacrylic acid as a functional monomer, and can very well improve the recognition effect of a compound on a template molecule.
In order to make the generated imprinted polymer have a certain spatial network structure and stable binding sites, the degree of crosslinking required by the molecularly imprinted polymer is high. The preferable trimethylolpropane Trimethacrylate (TRIM) has high crosslinking degree (70-90%) and good solubility in a prepolymerization solution.
In some embodiments, the kresoxim-methyl molecularly imprinted polymer has a structure of microspheres; the particle size of the microsphere is less than or equal to 50 mu m.
In some embodiments, the microspheres have a specific surface area greater than 8m2/g。
The particle size and the specific surface area of the molecularly imprinted polymer are closely related to the adsorption performance of the molecularly imprinted polymer, and the molecularly imprinted polymer directly influences the adsorption performance and the recognition capability of the adsorption material on a target analyte. In general, the larger the specific surface area of the adsorbent, the smaller the pore diameter, and the larger the adsorption amount.
In some embodiments, the molar ratio of kresoxim-methyl, pyraclostrobin, methacrylic acid, trimethylolpropane trimethacrylate is (0.8-1.2): (4-8): (20-40). In some embodiments, the molar ratio may also be selected from (0.9-1.1): 4-6): 25-45, 1: 1: 6: 30, etc.
In some embodiments, the polymerization reaction is carried out in a reaction system in which acetonitrile-toluene is the solvent; the volume ratio of acetonitrile to toluene in the acetonitrile-toluene is (6-8): (2-4). In some embodiments, the volume ratio may also be 7:3, etc.
The porogen actually acts as a solvent. The selection of the solvent plays an important role in the preparation of molecular imprinting, has great influence on intermolecular acting force and MD morphology, and plays a role of a pore-forming agent. The solvent is generally chosen to have the following 3 conditions: 1) dissolving template molecules and functional monomers; 2) large circulation holes can be formed; 3) and the interference on the interaction between the template molecules and the functional monomers is small. Generally, a solvent with proper polarity is selected according to the possible acting force types between the imprinted molecules and the functional monomers, and the larger the polarity of the solvent is, the greater the interference on the molecule recognition is, and the lower the adsorption rate is. The acetonitrile-toluene adopted by the invention has moderate polarity, low dielectric constant and good solubility to a plurality of reactants.
In some embodiments, the kresoxim-methyl, the pyraclostrobin and the methacrylic acid are added into the acetonitrile-toluene, dissolved uniformly and then kept stand for 2-3 hours to form a template molecule-functional monomer complex.
In some embodiments, 2' -azobisisobutyronitrile is also added as an initiator during the polymerization of the trimethylolpropane trimethacrylate and the template molecule-functional monomer complex.
In the molecular imprinting polymerization reaction, free radical initiation reaction is mostly adopted, so that an initiator is required to be added in the reaction to initiate the polymerization reaction, and 2,2' -Azobisisobutyronitrile (AIBN) is preferably adopted as the initiator in the invention. The 2,2' -azobisisobutyronitrile is an oil-soluble azo initiator, and the azo initiator has stable reaction, is a first-order reaction, has no side reaction and is better controlled.
In some embodiments, the polymerization reaction is carried out in the absence of oxygen and is carried out at 65 ℃ to 75 ℃ for 20h to 28 h. In some embodiments, the anaerobic conditions may also be a reaction at 68 ℃ for 26 hours, a reaction at 70 ℃ for 24 hours, and the like.
In some embodiments, the method of forming the anaerobic conditions comprises: introducing nitrogen for 10-15 min under the condition of ice water bath. In some embodiments, the time for the nitrogen gas to be introduced may also be 12min, 13min, and the like.
In some embodiments, the method for removing unpolymerized functional monomers, crosslinkers, and template molecules from the polymer comprises centrifugation followed by soxhlet extraction with a mixed solution of acetic acid and methanol.
In some embodiments, the centrifugation is performed at 2000-4000 r/min for 5-10 min. In some embodiments, the centrifugation conditions can also be 2000r/min for 10min, 3000r/min for 8min, 4000r/min for 5min, and the like.
In some embodiments, the volume ratio of acetic acid to methanol is 1 (8-10). In some embodiments, the volume ratio may also be 1:8.5, 1:9, etc.
In some embodiments, the soxhlet extraction is further followed by methanol elution.
The invention also provides the kresoxim-methyl molecularly imprinted polymer microsphere prepared by the preparation method of the kresoxim-methyl molecularly imprinted polymer.
The invention also provides a solid-phase extraction column which takes the kresoxim-methyl molecularly imprinted polymer microsphere as a filler.
In some embodiments, the kresoxim-methyl molecularly imprinted polymer microspheres are used as chromatographic packing.
The kresoxim-methyl molecularly imprinted polymer prepared by the invention has a specific adsorption effect on kresoxim-methyl and pyraclostrobin, can be used as a filler for solid phase extraction, separates and enriches kresoxim-methyl and pyraclostrobin in environment and food, and is combined with a chromatographic detection method (HPLC method) to detect the residue of kresoxim-methyl and pyraclostrobin in environment and food. Can also be made into chromatographic packing for detecting trace kresoxim-methyl and pyraclostrobin.
The kresoxim-methyl molecularly imprinted polymer can specifically identify kresoxim-methyl and pyraclostrobin at the same time, has strong adsorption capacity, can obviously improve the detection sensitivity and detection efficiency of kresoxim-methyl and pyraclostrobin, and has great popularization and application values.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1 preparation of molecularly imprinted polymer
1. Adding 0.8mmol of kresoxim-methyl, 1.2mmol of pyraclostrobin, 8mmol of functional monomer methacrylic acid and 75mL of acetonitrile-toluene solution (7: 3, v/v) into a 100mL ground glass bottle, and standing at room temperature for 2 h;
2. adding 20mmol of trimethylolpropane trimethacrylate and 50mg of 2,2' azobisisobutyronitrile, ultrasonically mixing, introducing high-purity nitrogen for 10min under the condition of ice-water bath, sealing by using a ground glass plug, and carrying out polymerization reaction in water bath at 65 ℃ for 28 h;
3. cooling to room temperature, centrifuging at 3000r/min for 10min to obtain precipitated polymer, and performing Soxhlet extraction with mixed solution of acetic acid and methanol at volume ratio of 1:9 for 20h and 80 deg.C;
4. and (3) oscillating and eluting by using methanol, and putting the finally obtained polymer coagulated beads into a vacuum furnace for vacuum drying at 60 ℃ to constant weight to obtain kresoxim-methyl molecularly imprinted polymer microsphere coagulated bead powder.
Example 2 preparation of molecularly imprinted polymer
1. Adding 1mmol of kresoxim-methyl, 0.8mmol of pyraclostrobin, 4mmol of functional monomer methacrylic acid and 65mL of acetonitrile-toluene solution (7: 3, v/v) into a 100mL ground glass bottle, and standing at room temperature for 2.5 h;
2. adding 40mmol of trimethylolpropane trimethacrylate and 45mg of 2,2' azobisisobutyronitrile, ultrasonically mixing, introducing high-purity nitrogen for 15min under the condition of ice-water bath, sealing by using a ground glass plug, and carrying out polymerization reaction in 72 ℃ water bath for 24 h;
3. cooling to room temperature, centrifuging at 2000r/min for 8min to obtain precipitated polymer, and performing Soxhlet extraction with mixed solution of acetic acid and methanol at volume ratio of 1:8 for 24h at 85 deg.C;
4. and (3) oscillating and eluting by using methanol, and putting the finally obtained polymer coagulated beads into a vacuum furnace for vacuum drying at 60 ℃ to constant weight to obtain kresoxim-methyl molecularly imprinted polymer microsphere coagulated bead powder.
Example 3 preparation of molecularly imprinted polymer
1. Adding 1mmol of kresoxim-methyl, 1mmol of pyraclostrobin, 6mmol of functional monomer methacrylic acid and 70mL of acetonitrile-toluene solution (7: 3, v/v) into a 100mL ground glass bottle, and standing for 3h at room temperature;
2. adding 30mmol of trimethylolpropane trimethacrylate and 55mg of 2,2' -azobisisobutyronitrile, ultrasonically mixing, introducing high-purity nitrogen for 12min under the condition of ice-water bath, sealing by using a ground glass plug, and carrying out polymerization reaction in water bath at 68 ℃ for 20 h;
3. cooling to room temperature, centrifuging at 4000r/min for 5min to obtain precipitated polymer, and performing Soxhlet extraction with mixed solution of acetic acid and methanol at volume ratio of 1:10 for 26h at 85 deg.C;
4. and (3) oscillating and eluting by using methanol, and putting the finally obtained polymer coagulated beads into a vacuum furnace for vacuum drying at 60 ℃ to constant weight to obtain kresoxim-methyl molecularly imprinted polymer microsphere coagulated bead powder.
EXAMPLE 4 preparation of a molecularly imprinted extraction column
1. Taking an empty solid phase extraction column, and filling the empty solid phase extraction column into a sieve plate;
2. respectively adding 50mg of the molecularly imprinted polymer powder prepared in the examples 1-3 into 1mL of methanol to prepare a suspension, adding the suspension into the empty solid-phase extraction column, simultaneously rinsing with methanol, and performing vacuum drying;
3. loading another sieve plate, and compacting;
4. 2mL of methanol was added to the column and the column was vacuum dried.
Experimental example 1 Kresoxim-methyl molecularly imprinted polymer microsphere with particle size and specific surface area
The kresoxim-methyl molecularly imprinted polymer microspheres prepared in the embodiments 1-3 are analyzed for particle size and specific surface area by a laser particle size analyzer. 100mg of polymer is weighed, 10mL of 95% ethanol is added, and the particle size and the specific surface area are detected by ultrasonic treatment for 5 min. Three replicates were performed.
TABLE 1 average particle diameter and specific surface area of kresoxim-methyl molecularly imprinted polymer microspheres
As can be seen from Table 1, the kresoxim-methyl molecularly imprinted polymer microspheres prepared in the embodiments 1-3 of the invention have an average particle size of less than 50 μm and a large specific surface area.
Experimental example 2 Kresoxim-methyl molecularly imprinted polymer microsphere equilibrium adsorption experiment on template molecule
2.1 Kresoxim-methyl equilibrium adsorption experiment of Kresoxim-methyl molecularly imprinted polymer microspheres
Accurately weighing 20mg of the polymer microspheres prepared in the embodiments 1-3 into a 10mL glass bottle with a screw cap, and respectively adding 2mL of kresoxim-methyl solution with the concentration of 0.2, 0.5, 1, 1.5, 2, 2.5 and 3 mg/mL. Standing in 25 deg.C water bath for 12 hr, centrifuging, collecting supernatant, determining the concentration of template molecule kresoxim-methyl by chromatography (HPLC method), calculating with formula Q ═ Ci-Cf) xV/m,
wherein Ci: initial concentration of kresoxim-methyl in solution (mg/mL);
cf: the concentration (mg/mL) of kresoxim-methyl in the solution after the adsorption balance is achieved;
v: volume of solution (mL);
m: polymer Mass (mg)
The results of the experiment are shown in FIG. 1. The result shows that the kresoxim-methyl molecularly imprinted polymer microsphere prepared by the embodiment of the invention has better adsorption effect on kresoxim-methyl, and the maximum adsorption capacity can reach about 180mg of kresoxim-methyl adsorbed by per gram of polymer.
2.2 pyraclostrobin equilibrium adsorption experiment of kresoxim-methyl molecularly imprinted polymer microspheres
Accurately weighing 20mg of the polymer microspheres prepared in the examples 1-3 into a 10mL glass bottle with a screw cap, and respectively adding 2mL of 20, 40, 80, 120, 160, 200, 250 and 300mg/L pyraclostrobin solution. Standing in 25 deg.C water bath for 12h, centrifuging, collecting supernatant, determining concentration of template molecule pyraclostrobin by chromatography (HPLC method), calculating with formula Q ═ Ci-Cf) xV/m,
wherein Ci: initial concentration of pyraclostrobin in solution (mg/L);
cf: the concentration (mg/L) of the pyraclostrobin in the solution after the adsorption balance is achieved;
v: volume of solution (mL);
m: polymer Mass (mg)
The results of the experiment are shown in FIG. 2. The result shows that the kresoxim-methyl molecularly imprinted polymer microsphere prepared by the embodiment of the invention has better adsorption effect on pyraclostrobin, and the maximum adsorption capacity can reach about 130mg of pyraclostrobin adsorbed by each gram of polymer.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (13)
1. A preparation method of kresoxim-methyl molecularly imprinted polymer is characterized in that kresoxim-methyl and pyraclostrobin are used as template molecules, methacrylic acid is used as a functional monomer, trimethylolpropane trimethacrylate is used as a cross-linking agent to carry out polymerization reaction, and then unpolymerized functional monomer, cross-linking agent and template molecules in the polymer are removed to obtain the kresoxim-methyl molecularly imprinted polymer;
the molar ratio of the kresoxim-methyl to the pyraclostrobin to the methacrylic acid to the trimethylolpropane trimethacrylate is (0.8-1.2) to (4-8) to (20-40).
2. The preparation method according to claim 1, wherein the kresoxim-methyl molecularly imprinted polymer has a structure of microspheres; the particle size of the microsphere is less than or equal to 50 mu m.
3. The production method according to claim 1, wherein the polymerization reaction is carried out in a reaction system in which acetonitrile-toluene is a solvent; the volume ratio of acetonitrile to toluene in the acetonitrile-toluene is (6-8): (2-4).
4. The preparation method according to claim 3, wherein the kresoxim-methyl, the pyraclostrobin and the methacrylic acid are added into the acetonitrile-toluene, uniformly dissolved and then kept stand for 2-3 hours to form the template molecule-functional monomer complex.
5. The method according to claim 4, wherein 2,2' -azobisisobutyronitrile is further added as an initiator during the polymerization of the trimethylolpropane trimethacrylate and the template molecule-functional monomer complex.
6. The preparation method according to any one of claims 1 to 5, wherein the polymerization reaction is carried out under an oxygen-free condition, and the reaction is carried out at 65 ℃ to 75 ℃ for 20h to 28 h.
7. The method of claim 6, wherein the method of forming the oxygen-free condition comprises: introducing nitrogen for 10-15 min under the condition of ice water bath.
8. The method of claim 1, wherein the removing of unpolymerized functional monomers, crosslinking agents and template molecules from the polymer comprises centrifugation followed by Soxhlet extraction with a mixed solution of acetic acid and methanol.
9. The method according to claim 8, wherein the centrifugation is carried out at 2000-4000 r/min for 5-10 min.
10. The preparation method according to claim 8, wherein the volume ratio of the acetic acid to the methanol is 1 (8-10).
11. The method of claim 8, further comprising methanol elution after said soxhlet extraction.
12. The kresoxim-methyl molecularly imprinted polymer microsphere prepared by the method for preparing the kresoxim-methyl molecularly imprinted polymer according to any one of claims 1 to 11.
13. A solid phase extraction column, which takes the kresoxim-methyl molecularly imprinted polymer microsphere of claim 12 as a filler.
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| CN103570870A (en) * | 2013-10-21 | 2014-02-12 | 南京医科大学 | Multi-template monodisperse active notoginsenoside molecular imprinted polymer and preparation method thereof |
| CN104387532A (en) * | 2014-11-26 | 2015-03-04 | 北京农学院 | Preparation method of pyraclostrobin molecularly-imprinted polymer |
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| CN103570870A (en) * | 2013-10-21 | 2014-02-12 | 南京医科大学 | Multi-template monodisperse active notoginsenoside molecular imprinted polymer and preparation method thereof |
| CN104387532A (en) * | 2014-11-26 | 2015-03-04 | 北京农学院 | Preparation method of pyraclostrobin molecularly-imprinted polymer |
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