CN110665477B - Method for preparing molecularly imprinted polymer - Google Patents
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- CN110665477B CN110665477B CN201810715136.9A CN201810715136A CN110665477B CN 110665477 B CN110665477 B CN 110665477B CN 201810715136 A CN201810715136 A CN 201810715136A CN 110665477 B CN110665477 B CN 110665477B
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Abstract
The invention relates to a method for preparing a molecularly imprinted polymer, which comprises a) adding aminopropyl-3-methylimidazole bromine salt into a prepolymerization reaction system when a template molecule and a functional monomer are prepolymerized; b) Adding a cross-linking agent and an initiator into the prepolymerized system to carry out polymerization reaction to obtain a polymer; c) Eluting the template molecules in the polymer to obtain the molecularly imprinted polymer. By utilizing the good adsorption performance of the aminopropyl-3-methylimidazole bromine salt, the synthesis of the molecularly imprinted polymer can be accelerated, the spatial configuration of the molecularly imprinted polymer can be changed, and holes with multiple action points can be formed, and the drug can be selectively identified, so that the molecularly imprinted polymer has better inclusion complexation capability and chemical stability.
Description
Technical Field
The invention relates to the field of molecularly imprinted polymers, and particularly relates to a method for preparing a molecularly imprinted polymer.
Background
The Molecular Imprinting (MIP) technology is to pre-assemble target molecules to be separated and functional monomers through covalent or non-covalent interaction and copolymerize the target molecules and the functional monomers with a cross-linking agent to prepare polymers. After the target molecules are removed, a cavity which is complementary with the space of the target molecules and has preset multiple action sites is formed in the polymer, so that the polymer has a memory effect on the space structure of the target molecules and can be used for recognizing the imprinted molecules in a complex sample with high selectivity. The preparation of the molecular imprinting material mainly uses methacrylic acid and acrylamide as polymers of monomers.
The ionic liquid is organic low-temperature molten salt completely composed of organic cations and inorganic or organic anions with asymmetric structures, has the characteristics of low vapor pressure, wide viscosity range, high conductivity, high ionic strength and the like, and the physical and chemical properties of polarity, solubility, hydrophobicity, hydrophilicity and the like can be adjusted through group modification and the like. Has the advantages of difficult volatilization, good solubility, strong stability, modifiable and modulated anion and cation structure, recycling use and the like. The ionic liquid is easy to form hydrogen bonds, easy to perform free radical polymerization reaction, has the performances of hydrophobicity, pi-pi bonds, electrostatic and anion exchange interaction and the like, is used for preparing the molecularly imprinted polymer as a monomer and an auxiliary agent, is used for preparing the molecularly imprinted polymer as a functional monomer and a solvent, and can improve the selectivity and the adsorption capacity of the polymer.
Aminopropyl 3-methylimidazole bromine salt, the English name is 1-aminopropyl-3-methylimidazolium Bromide, the molecular formula is C7H14N3Br, and the chemical structural formula is shown in formula I.
Aminopropyl 3-methylimidazole bromine salt is a synthetic functional ionic liquid, and is currently found to react with CO 2 Has good absorption performance, and can realize high-efficiency absorption and desorption circulation processes by using aqueous solution in industry, but the application of the aqueous solution on molecular imprinting materials is not reported.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for synthesizing molecularly imprinted polymer microspheres by using aminopropyl-3-methylimidazole bromide, and the prepared aminopropyl-3-methylimidazole bromide molecularly imprinted polymer microspheres can be used for directly and selectively separating enriched drugs and achieving rapid and simple separation.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention relates to a method for preparing a molecularly imprinted polymer, which comprises the following steps:
a) Adding the aminopropyl-3-methylimidazole bromine salt into a prepolymerization reaction system when the template molecules and the functional monomers are prepolymerized;
b) Adding a cross-linking agent and an initiator into the prepolymerized system to carry out polymerization reaction to obtain a polymer;
c) Eluting the template molecules in the polymer to obtain the molecularly imprinted polymer.
According to one aspect of the invention, the invention also relates to the application of the molecularly imprinted polymer prepared by the method in detecting beta-receptor agonist substances.
Compared with the prior art, the invention has the beneficial effects that:
by utilizing the good adsorption performance of the aminopropyl-3-methylimidazole bromine salt, the synthesis of a molecularly imprinted polymer can be accelerated, the spatial configuration of the molecularly imprinted polymer is changed, a cavity with multiple action points is formed, and a drug can be selectively identified, so that the molecularly imprinted polymer has better inclusion complexation capacity and chemical stability.
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 scanning electron micrograph of a molecularly imprinted polymer microsphere prepared according to one embodiment of the present invention.
Detailed Description
The invention relates to a method for preparing a molecularly imprinted polymer, which comprises the following steps:
a) Adding the aminopropyl-3-methylimidazole bromine salt into a prepolymerization reaction system when the template molecules and the functional monomers are prepolymerized;
b) Adding a cross-linking agent and an initiator into the prepolymerized system to carry out polymerization reaction to obtain a polymer;
c) Eluting the template molecules in the polymer to obtain the molecularly imprinted polymer.
Preferably, in the method described above, the mass ratio of the template molecule, the aminopropyl-3-methylimidazolium bromide salt and the functional monomer is 1:2 to 10:4 to 10; it is also possible to select 1:4 to 8:6 to 8 percent; or 1:5 to 7:6 to 7; or 1.
Preferably, in the method as described above, the functional monomer is methacrylic acid.
Preferably, in the method, the temperature of the prepolymerization is 25-30 ℃ and the time is 1.0-4.0 hours;
the temperature of the prepolymerization reaction can be 27 ℃, 28 ℃ and 29 ℃, and the time can be 2.0 or 3.0 hours.
Preferably, the prepolymerization is carried out in acetonitrile, as described above.
Preferably, in the method described above, the mass ratio of the crosslinking agent to the aminopropyl-3-methylimidazolium bromide salt is 5 to 20:2 to 10; also, 7 to 18:4 to 8; or 10 to 15:6 to 7; or 6;
preferably, the mass ratio of the initiator to the aminopropyl-3-methylimidazolium bromide salt is 0.1-0.4: 2 to 10; also, 0.2 to 0.3:4 to 8 percent; or 0.2.
Preferably, in the method described above, the crosslinking agent is divinylbenzene; preferably, the initiator is azobisisobutyronitrile.
Preferably, the polymerization is carried out under a non-oxidizing atmosphere, as described above.
Preferably, in the method, the temperature of the polymerization reaction is 60-80 ℃ and the time is 8-24 hours;
the polymerization reaction temperature can also be selected from 65 ℃, 70 ℃ or 75 ℃, and the time can also be selected from 10 hours, 14 hours, 18 hours, 20 hours or 24 hours.
Preferably, in the method described above, the template molecule is p-phenylethanol.
According to one aspect of the invention, the invention also relates to application of the molecularly imprinted polymer prepared by the method in detection of beta-receptor agonist substances.
The invention tests the adsorption performance of a molecularly imprinted polymer microsphere synthesized and produced by taking a beta-receptor agonist replacing molecule as a template and adding aminopropyl-3-methylimidazole bromide salt to the beta-receptor agonist, detects the adsorption performance by using HPLC/MS/MS, and applies the beta-receptor agonist to the determination.
Preferably, for use as described above, the beta-receptor agonist is selected from one or more of chlorpropamide, cimaterol, terbutaline, sibutrol, salbutamol, zilpaterol, clenbuterol, ritodrine, phenylethanolamine a, isoclenbuterol, ractopamine, mabuterol, clenbuterol, labuterol, salmeterol, clenbuterol, tulobuterol, pentobuterol, and maprotirol.
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 conventional products which are commercially available, and are not indicated by manufacturers.
Example 1
Preparation of template molecularly imprinted polymer microspheres (MMIP)
Dissolving 0.138g of p-phenylethanol, 1.38g of MMA1 and aminopropyl-3-methylimidazolium bromide (0.552 g) in 15mL of acetonitrile, carrying out ultrasonic treatment for 15min, standing at 25 ℃ for 4h to ensure that template molecules and functional monomers fully react, then adding 1mL of divinylbenzene (calculated by the content of the divinylbenzene net being 0.69 g) and 55.2mg of AIBN, carrying out ultrasonic treatment for 10min to fully dissolve and mix the divinylbenzene and the AIBN, introducing N into the mixed solution for 2min, sealing, and carrying out water bath polymerization for 8h at 80 ℃ to obtain a solid polymer (MIP). And eluting the template molecules by using a methanol solution with 10% of acetic acid by mass fraction, washing by using methanol until no impurities exist in the washing solution, and drying at the temperature of 60 ℃ for 2 hours to obtain the template molecularly imprinted polymer (MMIP).
Example 2
Preparation of template molecularly imprinted polymer microspheres (MMIP)
Dissolving 0.138g of p-phenylethanol, 0.276g of MMA and 1.38g of aminopropyl-3-methylimidazolium bromide in 15mL of acetonitrile, carrying out ultrasonic treatment for 15min, standing at 27 ℃ for 2h to enable template molecules and functional monomers to fully react, then adding 1mL of divinylbenzene (calculated by the net content of the divinylbenzene: 2.76 g) and 13.8mg of AIBN, carrying out ultrasonic treatment for 10min to fully dissolve and mix the divinylbenzene and the AIBN, introducing N into the mixed solution for 2min, sealing, and carrying out water bath polymerization at 60 ℃ for 24h to obtain the solid polymer (MIP). And eluting the template molecules by using a methanol solution with 10% of acetic acid by mass fraction, washing by using methanol until no impurities exist in the washing solution, and drying at the temperature of 60 ℃ for 2 hours to obtain the template molecularly imprinted polymer (MMIP).
Example 3
Preparation of template molecularly imprinted polymer microspheres (MMIP)
Dissolving 0.138g of p-phenylethanol, 850mL (0.8024 g) of MMA and 0.8024g of aminopropyl-3-methylimidazolium bromide in 15mL of acetonitrile, carrying out ultrasonic treatment for 15min, standing at 30 ℃ for 1h to enable template molecules to fully react with functional monomers, then adding 1mL (20mmol, 0.919g) of divinylbenzene and 50mg of AIBN, carrying out ultrasonic treatment for 10min to fully dissolve and mix the divinylbenzene and the AIBN, introducing N2 into the mixed solution for 2min, sealing, and carrying out water bath polymerization for 12h at 70 ℃ to obtain a solid polymer (MIP). And eluting the template molecules by using a methanol solution with 10% of acetic acid by mass fraction, washing by using methanol until no impurities exist in the washing solution, and drying at the temperature of 60 ℃ for 2 hours to obtain the template molecularly imprinted polymer (MMIP).
As shown in FIG. 1, a scanning electron micrograph (5.0 kv,5.6mm,10.0 k) of the molecularly imprinted polymer microsphere prepared in this example shows that MIP prepared by adding aminopropyl-3-methylimidazolium bromide has a uniform spherical shape with an inner diameter of about 1 μm, and the uniformity and synthesis efficiency are significantly higher than MIP prepared without adding aminopropyl-3-methylimidazolium bromide and other ionic liquids. More and more stable binding sites can be generated between the template and the monomer possibly due to the electrostatic action, the ion exchange action and the like of the aminopropyl-3-methylimidazole bromine salt, so that the molecular imprinting effect is improved; accelerating the polymerization process, thereby shortening the polymerization time; reduce the shrinkage and expansion coefficients of the MIP, thereby improving the stability of the MIP.
Comparative example
For the purpose of comparing the characterization and adsorption effects of the MMIP of the present invention, a non-molecularly imprinted polymer was prepared as a control, denoted as MNIP, in substantially the same manner as in example 3, except that: in the preparation method, no template molecule p-phenylethanol is added.
In order to compare the characterization and adsorption effects of the MMIP, other molecularly imprinted polymers are prepared as a reference and are marked as NMIP, and the preparation method is basically the same as the method of the embodiment 3, except that: in the preparation method, aminopropyl-3-methylimidazolium bromide salt is not added.
In order to compare the characterization and adsorption effects of the MMIP, other molecularly imprinted polymers are prepared as a reference, and the preparation method is basically the same as that of the embodiment 3, except that: methyl-3-methylimidazolium bromide (JMIP) and 1-vinyl-3-carboxybutylimidazolium bromide (YMIP) are added in the preparation method.
Experimental example 1
Test example analysis of aminopropyl-3-methylimidazolium bromide molecularly imprinted polymer microspheres for agonist performance
100ng/mL PBS standard solutions with pH of 8.0 of 22 structural analogs are accurately prepared respectively, 10mg molecular imprinting microspheres are added for adsorption for the same time, and HPLC-MS/MS detection is carried out.
The detection method of HPLC-MS/MS in the following examples is as follows:
1. conditions of LC-MS/MS:
a) And (3) chromatographic column: c 18 100 mm. Times.3.0 mm, particle size 1.7. Mu.m.
b) Column temperature: at 40 deg.c.
c) Sample injection amount: 10 μ L.
d) The mobile phase and flow rate are shown in table 1.
TABLE 1 mobile phase and Rate of flow
2. Mass spectrum conditions:
a) An ion source: an electrospray ion source.
b) The scanning mode is as follows: positive ion mode.
c) The detection mode is as follows: and (5) monitoring multiple reactions.
d) The desolvation gas, the taper hole gas and the collision gas are all high-purity nitrogen and other suitable gases, and the flow of each gas is adjusted before use so as to ensure that the sensitivity of the mass spectrum meets the detection requirement.
e) The voltage values of capillary voltage, taper hole voltage, collision energy and the like should be optimized to the optimal sensitivity.
f) The qualitative ion pair, the quantitative ion pair and the corresponding cone hole voltage and collision energy are shown in table 2.
TABLE 2 qualitative and quantitative ion pairs of beta-receptor agonists and reference values for the cone and collision voltages
The adsorption result is shown in table 3, and the result shows that the adsorption effect of the synthesized molecularly imprinted microspheres on zilpaterol and clenbuterol is slightly poor, and the adsorption rate is lower than 50%. The adsorption rate of the phenylethanolamine A, the maprotiron, the isoclenbuterol and the salmeterol can reach more than 99 percent, and the adsorption efficiency of other structural analogs such as ractopamine, bambuterol and the like is relatively low, but can also reach more than 70 percent. And MIPs without the addition of aminopropyl-3-methylimidazolium bromide and other ionic liquid types. Compared with the adsorption capacity, the adsorbent has better adsorption capacity and obvious adsorption capacity to the agonist.
The reason is probably that the aminopropyl of the aminopropyl-3-methylimidazole bromine salt and a specific template molecule can form strong hydrogen bonds, so that the interference of polar molecule electrostatic acting force on MIP selective recognition and the memory effect of MIP on an organic solvent are weakened, and the MIP formed by polymerization has higher selectivity. The molecular engram microsphere synthesized by the invention has higher adsorption efficiency on various agonist drugs, which indicates that MMIP can be used for extraction and treatment of agonist drugs.
TABLE 3 adsorption of MMIP for various agonists
Experimental example 2
An application example of aminopropyl-3-methylimidazolium bromide molecularly imprinted polymer microspheres in urine detection is tried.
Weighing 5mL of sample into a 50mL centrifuge tube, and accurately adding 5mL of ammonium acetate solution, 50 mu L of beta-glucuronidase/arylsulfatase, 20 mu L of agonist internal standard solution and 20-50 mg of molecularly imprinted microspheres. Shaking for enzymolysis at 37 deg.C overnight (more than 16 hr), centrifuging at 8000r/min for 5min, and discarding supernatant. 2mL of 5% formic acid methanol was added, vortex mixed for 30s, the supernatant collected, blown dry at 50 ℃ with a nitrogen blower or evaporated to dryness with a rotary evaporator, dissolved in 1.0mL of sample diluent, and filtered through a 0.22 μm filter. And (4) measuring by using an HPLC-MS/MS method, and quantifying by using the corresponding deuterated internal standard as an internal standard. The method is used for determining that the recovery rate of 18 agonists in urine is more than 75 percent, and the relative deviation is less than 15 percent.
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 (9)
1. A method of making a molecularly imprinted polymer, comprising:
a) Adding aminopropyl-3-methylimidazole bromine salt into a prepolymerization reaction system when the template molecules and the functional monomers are prepolymerized;
b) Adding a cross-linking agent and an initiator into the prepolymerized system to carry out polymerization reaction to obtain a polymer;
c) Eluting the template molecules in the polymer to obtain the molecularly imprinted polymer;
the mass ratio of the template molecule to the aminopropyl-3-methylimidazole bromine salt to the functional monomer is 1:2 to 10:4 to 10;
the functional monomer is methacrylic acid; the template molecule is p-phenylethanol;
the mass ratio of the cross-linking agent to the aminopropyl-3-methylimidazolium bromide is 5-20: 2 to 10; the mass ratio of the initiator to the aminopropyl-3-methylimidazole bromine salt is (0.1-0.4): 2 to 10; the crosslinking agent is divinylbenzene; the initiator is azobisisobutyronitrile.
2. The method according to claim 1, wherein the mass ratio of the template molecule, the aminopropyl-3-methylimidazolium bromide salt and the functional monomer is 1.
3. The process according to claim 1, wherein the temperature of the prepolymerization is 25 ℃ to 30 ℃ and the time is 1.0 to 4.0 hours.
4. The process according to claim 1, characterized in that the prepolymerization is carried out in acetonitrile.
5. The method according to claim 1, wherein the mass ratio of the cross-linking agent to the aminopropyl-3-methylimidazolium bromide salt is 6;
the mass ratio of the initiator to the aminopropyl-3-methylimidazolium bromide salt is 0.2.
6. The method of claim 1, wherein the polymerization reaction is conducted in a non-oxidizing atmosphere.
7. The process according to claim 1, wherein the polymerization is carried out at a temperature of 60 to 80 ℃ for a time of 8 to 24 hours.
8. Use of the molecularly imprinted polymer prepared by the method of any one of claims 1 to 7 for detecting beta-receptor agonists.
9. The use of claim 8, wherein the beta-receptor agonist is selected from one or more of the group consisting of chlorpropamide, cimaterol, terbutaline, sibutrol, salbutamol, zilpaterol, clenbuterol, ritodrine, phenylethanolamine a, isocrosullin, ractopamine, mabuterol, clenbuterol, labuterol, formoterol, bromobutirol, bambuterol, salmeterol, clenbuterol, tulobuterol, pentoterol and maprotirol.
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| CN106084115A (en) * | 2016-06-12 | 2016-11-09 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of beta receptor activator alternate template molecular blotting polymer microsphere and preparation method and application |
| CN107179346A (en) * | 2017-05-25 | 2017-09-19 | 济南大学 | A kind of preparation method for being used to detect the molecular engram sensor of anthocyanidin |
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| CN106084115A (en) * | 2016-06-12 | 2016-11-09 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of beta receptor activator alternate template molecular blotting polymer microsphere and preparation method and application |
| CN107179346A (en) * | 2017-05-25 | 2017-09-19 | 济南大学 | A kind of preparation method for being used to detect the molecular engram sensor of anthocyanidin |
| CN107759736A (en) * | 2017-09-22 | 2018-03-06 | 河南师范大学 | A kind of preparation method of styrene divinylbenzene molecular imprinted polymer on surface for selective absorption Ciprofloxacin Hydrochloride |
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