CN108164644B - Molecularly imprinted polymer and preparation and application thereof - Google Patents
Molecularly imprinted polymer and preparation and application thereof Download PDFInfo
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- CN108164644B CN108164644B CN201611115303.3A CN201611115303A CN108164644B CN 108164644 B CN108164644 B CN 108164644B CN 201611115303 A CN201611115303 A CN 201611115303A CN 108164644 B CN108164644 B CN 108164644B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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Abstract
The invention provides a method for preparing a high-selectivity bisphenol type substitution template molecularly imprinted polymer by adding a steric hindrance monomer and application of the polymer. The material is prepared by the following steps: dissolving the substituted template molecule, the cross-linking agent, the functional monomer, the steric hindrance monomer and the initiator in the pore-foaming agent to form a uniform prepolymerization solution, and after the solution is placed for a period of time under the condition of low temperature, carrying out polymerization reaction for 20-48h at the temperature of 50-70 ℃. And grinding, screening and settling the white block polymer generated by the polymerization reaction to obtain polymer particles with the particle size of 38-63 um. And performing Soxhlet extraction on the obtained particles by using a methanol/acetic acid mixed solution or methanol as an extracting agent, and removing the substituted template and unreacted substances in the polymer to obtain the molecularly imprinted polymer. The added steric hindrance monomer enhances the specific selectivity and enrichment capacity of the polymer to bisphenol compounds, and simultaneously improves the anti-interference capacity of the material to interferents.
Description
Technical Field
The invention relates to a molecularly imprinted polymer for improving the performance of enriching and purifying bisphenol compounds by using steric hindrance monomers (site-restricted access performance is enhanced by using the steric hindrance monomers) and preparation and application thereof, belonging to the field of environmental monitoring and new materials.
Background
The bisphenol compound has stable chemical property, high temperature resistance, heat resistance, good ductility, simple production process and low cost, and is a raw material and an additive which are widely used in high polymer materials. However, the structure of the compound is similar to that of estradiol, the compound has potential endocrine disrupting effects and toxic effects on human bodies, and bisphenol A (BPA) widely exists in the environment, has the characteristics of small dosage, long incubation period, easiness in enrichment, frequent contact and the like, and is an environment pollutant with great harm. Among them, BPA belongs to endocrine disruptors, has estrogenic activity, and trace or even trace concentrations may have adverse effects on animal physiological conditions, reproductive systems, and fetal development. BPA is a typical environmental endocrine disruptor and is restricted in many countries for its use in many areas due to its increasingly defined estrogenic activity, toxicological effects and serious pollution. Based on this situation, BPS, BPF, BPB, BPAF, TCBPA and TBBPA are widely used as major substitutes for BPA. However, since BPS, BPF, BPB, BPAF, TCBPA and TBBPA are similar in chemical nature and structure to BPA, numerous studies have shown that they, like BPA, are able to mimic estrogens, binding to estrogen receptors, inducing a range of estrogenic effects. In addition, they exhibit toxic effects of varying intensity in reproduction, development, genetics and neurology
In recent years, although the risk assessment results in most countries show that dietary exposure levels of bisphenols do not pose health risks, strict regulatory measures have been taken in some countries, taking into account the potential low dose effects of BPA and the uncertainty of animal experiments. Moreover, due to the fact that the usage amount of the bisphenol substances is large, the bisphenol substances can be continuously accumulated in the environment, the content of the bisphenol substances in the environment is increased year by year, the environment ecological burden can be caused, and the health of human beings is further damaged, so that the rapid and accurate detection of the bisphenol substances is particularly important.
The conventional solid phase extraction adsorbent is used for retaining compounds through nonspecific hydrophobic effect or polar effect, so that specificity and retention capacity are poor, and certain adsorption is performed on interferents while the to-be-detected substances are adsorbed, so that detection interference or recovery rate is reduced. The molecular imprinting-solid phase extraction technology (MISPE) established by applying the molecular imprinting polymer to solid phase extraction can overcome the defects, effectively remove impurities while retaining a target object, and obtain high sensitivity and low background interference. Meanwhile, the problem of template leakage in trace analysis can be effectively solved by adopting a substitute template molecular imprinting technology. However, the matrix in which the bisphenols are distributed is usually complicated, so that it is also necessary to improve the interference resistance of the material. A Molecularly Imprinted Polymer (MIP) refers to a method for preparing a polymer having specific selectivity for a specific target molecule by using the molecule as a template, and has a binding site completely matched with the template molecule in space structure and binding site. The matching of the molecular imprinting binding sites is greatly related to the used template and the used monomer, and some works are to increase the imprinting effect of the material through the joint action of a plurality of functional monomers and the template molecules, however, the method can also increase the action of the material and the interferent, so that the binding sites of the imprinting material are limited and protected by adding the steric hindrance monomer which does not form interaction force with the template molecules, and thus, the retention of the material to a target object can be increased, and the adsorption effect of the material to the interferent is reduced. The imprinted polymer prepared by adding different steric hindrance monomers has better selectivity than the imprinted polymer prepared without adding the steric hindrance monomers, and has good ability of selectively enriching and purifying bisphenol endocrine disruptors in environmental, biological and food samples.
Disclosure of Invention
The invention aims to provide a molecular imprinting enrichment material with ultrahigh selectivity on bisphenol endocrine disruptors in environmental, food and biological samples, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the molecularly imprinted polymer for selectively separating the bisphenol endocrine disruptors can be prepared by the following steps: (1) and carrying out ultrasonic treatment on mixed liquid of the substituted template molecules, one or more functional monomers, one or more steric hindrance monomers, a cross-linking agent, an initiator and a pore-foaming agent to prepare a homogeneous prepolymerization solution. The proportions are as follows: template molecule: functional monomer: a crosslinking agent: initiator: the mol ratio of the pore-foaming agent is 1: 1-8: 2-8: 10-30: 0.2-0.3: 18-22; wherein the substituted template molecule is 1,1, 1-tri-p-hydroxy phenyl ethane, the functional monomer is 4-vinyl pyridine, methacrylic acid, acrylamide or 2-vinyl pyridine, the steric hindrance monomer is one or more than two of olefins with 6-13 carbon atoms, the cross-linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or divinylbenzene, the initiator is azobisisobutyronitrile, and the pore-forming agent is acetonitrile, chloroform, methanol or toluene;
(2) placing the mixed solution in ice bath, ultrasonic degassing for 10-15min, introducing nitrogen into the prepolymerization solution for 5-15min to remove oxygen molecules, sealing, and standing at 0-4 deg.C for more than 1 h;
(3) putting the sealed and refrigerated prepolymerization solution into a water bath at 50-70 ℃ for bulk polymerization for 12-48h to generate a white block polymer;
(4) crushing, grinding, screening and settling the white massive polymer to obtain white powdery polymer with the particle size of 38-63 mu m;
(5) performing Soxhlet extraction by using a methanol solution of acetic acid with the volume concentration of 0-50% as an extraction solvent to remove template molecules and interfering substances which do not participate in the reaction;
(6) and after extraction is finished, the polymer is placed in a vacuum drying oven to be dried for 6-24h at the temperature of 50-70 ℃, and the molecularly imprinted polymer is obtained.
The molecularly imprinted polymer is applied to the enrichment of bisphenol endocrine disruptors.
The molecularly imprinted polymer is used as a filler of a solid phase extraction column.
The molecularly imprinted polymers are useful for detecting and/or processing bisphenol endocrine disruptors in environments, food products, and biological samples.
The optimal conditions for preparing the bisphenol-substituted template molecularly imprinted polymer are as follows: the substituted template molecule in the operation step (1) is 1,1, 1-tri-p-hydroxyphenylethane, the functional monomer is 4-vinylpyridine, the steric hindrance monomer is 3,5, 5-trimethyl-1-hexene, the cross-linking agent is ethylene glycol dimethacrylate, the initiator is azobisisobutyronitrile, and the pore-forming agent is acetonitrile, wherein the molar ratio of the pore-forming agent to the template molecule is 1: 4: 4: 20: 0.24: 20, mixing;
and (3) carrying out ultrasonic treatment on the mixed solution, introducing nitrogen, sealing, and reacting at 50-70 ℃ for 12-48 h.
The invention has the advantages that: the prepared alternative template molecularly imprinted polymer has specific selectivity on bisphenol endocrine disruptors and does not have the problem of template leakage. In the preferred embodiment of the invention, 1,1, 1-tri-p-hydroxyphenylethane is used as a substitute template molecule, 4-vinylpyridine is used as a functional monomer, 3,5, 5-trimethyl-1-hexene is used as a steric hindrance monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, acetonitrile is used as a pore-forming agent, the mixture is thermally initiated to polymerize under the action of an azobisisobutyronitrile initiator, and the obtained polymer is ground, sieved and settled, and then subjected to Soxhlet extraction to remove the template molecule and unreacted substances, so that the substitute template molecularly imprinted polymer with specific selectivity is obtained. The polymer has extremely strong selectivity to bisphenol AP, bisphenol B, bisphenol A, bisphenol AF, bisphenol Z, bisphenol E, bisphenol S, bisphenol F and tetrabromobisphenol A except for template molecule 1,1, 1-tri-p-phenylethane. The imprinting factors are respectively 43.25,19.65, 18.05, 17.30, 13.70, 11.78, 44.20, 6.85 and 53.66, which are larger than the molecular imprinting polymer material without the added steric hindrance monomer.
Due to the addition of the steric hindrance monomer, the molecularly imprinted polymer has higher imprinting factor than imprinted materials prepared under other conditions, and the long chain of the steric hindrance monomer plays a role in limiting the binding sites, so that the anti-interference capability of the material is improved. The molecularly imprinted polymer has ultrahigh specific selectivity on bisphenol endocrine disruptors, does not have the problem of template leakage, and can detect the bisphenols in actual samples more quickly, sensitively, accurately and efficiently.
Drawings
FIG. 1 shows the imprinting factors of 9 bisphenols with the addition of a steric hindrance monomer and without the addition of an imprinting polymer according to the present invention.
Detailed Description
The molecular imprinting solid phase extraction material added with the steric hindrance monomer has strong specific selectivity and enrichment capacity on the bisphenol compound, solves the problems of template leakage and impurity interference reduction in trace analysis, and can be used for separating and enriching the bisphenol compound in a complex matrix.
Example 1
1) Dissolving 1mmol of substituted template molecule 1,1, 1-tris-p-hydroxyphenyl into acetonitrile (5.6mL) containing 4mmol of functional monomer 4-vinylpyridine (4-VP), 4mmol of steric energy steric monomer 3,5, 5-trimethyl-1-hexene (TMH), 20mmol of cross-linking agent ethylene glycol dimethacrylate and 0.04g of initiator azobisisobutyronitrile to prepare a prepolymerization solution, placing the prepolymerization solution in an ice bath for ultrasonic mixing for 10-15min, introducing nitrogen for 10min to remove oxygen in the system, sealing, refrigerating at 4 ℃ for 2h, and then placing at 60 ℃ for reaction for 24 h. The white block polymer generated by the reaction is crushed and ground, and the polymer with the grain diameter of 38-63 mu m is obtained after sieving and acetone sedimentation. The obtained polymer is subjected to Soxhlet extraction by using methanol acetic acid (9: 1, v/v) as an extraction solvent to remove template molecules and other interfering substances, and the obtained polymer is dried in a vacuum drying oven at 60 ℃ overnight to obtain a white molecularly imprinted polymer.
2) And the preparation and treatment of the imprinted polymer material without adding the steric hindrance monomer are the same as those in 1) above except that no steric hindrance monomer is added.
The preparation and treatment of the control non-imprinted polymer (NIP) were identical to 1) or 2), respectively, except that no template molecule was added. The specific surface area of each of the four polymers was about 400m2Pore volume of about 0.7cm3The blot factor calculated by comparing the retention of the two aggregates is reliable.
The molecularly imprinted polymer is filled into a stainless steel chromatographic column with the size of 100 multiplied by 4.6mm by a homogenization method, and aged for liquid chromatographic analysis. The mobile phase was acetonitrile, flow rate 1mL min-1, waters2478 dual wavelength UV detector, wavelength set at 220nm for bisphenol determination, and methanol as solvent for dead time determination (t 0). And calculating the capacity factor (k') of the bisphenol substances according to the retention time (tR) of the bisphenol substances on the molecular imprinting chromatographic column and the non-imprinting chromatographic column, and calculating the Imprinting Factor (IF) of the bisphenol substances so as to characterize the selectivity of the bisphenol endocrine disruptors. k ═ tR-t0)/t0IF ═ k 'MIP/k' NIP. Wherein, k 'MIP and k' NIP are capacity factors of the phthalate ester metabolite on a molecular imprinting chromatographic column and a non-imprinting chromatographic column respectively.
The added steric hindrance monomer and the non-added alternative template molecularly imprinted polymer have obvious specific selectivity on the bisphenol substances, but the comparison result shows that the steric hindrance monomer has a certain effect on improving the imprinting factor. The results of the blotting factor assay are shown in FIG. 1 (the concentrations of the standards are all 20 ppm).
Claims (7)
1. A method for preparing a molecularly imprinted polymer, comprising: can be prepared by the following steps,
(1) mixing the substituted template molecule, the steric hindrance monomer, the functional monomer, the cross-linking agent, the initiator and the pore-foaming agent to prepare a homogeneous prepolymerization solution; the molar ratio is as follows: substitution of template molecules: steric hindrance monomer: functional monomer: a crosslinking agent: initiator: the mol ratio of the pore-foaming agent is 1: 1-8: 2-8: 10-30: 0.2-0.3: 18-22; wherein the substituted template molecule is 1,1, 1-tri-p-hydroxy-phenyl ethane, the steric hindrance monomer is one or more than two of olefins with 6-13 carbon atoms, the functional monomer is one or more than two of 4-vinylpyridine, methacrylic acid, acrylamide or 2-vinylpyridine, the cross-linking agent is one or more than two of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or divinylbenzene, the initiator is azobisisobutyronitrile, and the pore-forming agent is one or more than two of acetonitrile, acetone, chloroform, methanol or toluene;
(2) placing the pre-polymerization solution in an ice bath at 0-4 ℃, ultrasonically degassing for 5-15min, introducing nitrogen into the pre-polymerization solution for 5-15min to remove oxygen molecules, sealing, and standing at 0-4 ℃ for more than 1 h;
(3) putting the sealed and refrigerated prepolymerization solution into a water bath at 50-70 ℃ for bulk polymerization for 12-48h to generate a white block polymer;
(4) crushing, grinding, screening and settling the white massive polymer to obtain a white powdery polymer with the particle size of 38-63 mu m;
(5) performing Soxhlet extraction by using a methanol solution of acetic acid with the volume concentration of 0-50% as an extraction solvent to remove template molecules and interfering substances which do not participate in the reaction;
(6) and after extraction is finished, the polymer is placed in a vacuum drying oven to be dried for 6-24h at the temperature of 50-70 ℃, and the substitute template molecularly imprinted polymer is obtained.
2. The method of claim 1, wherein:
the solvent used for the sedimentation in the step (4) is acetone or methanol.
3. The method of claim 1, wherein:
in the step (5), the solvent adopted for removing the template molecules by Soxhlet extraction is methanol or the volume ratio of methanol to acetic acid is 9: 1-9 of methanol acetic acid mixed solution; the extraction temperature of methanol-acetic acid mixed liquor or methanol is 70-120 ℃, and the extraction time is 12-36 h.
4. A molecularly imprinted polymer prepared by the method of any one of claims 1 to 3.
5. Use of the molecularly imprinted polymer according to claim 4 as a selective adsorbent for enriching bisphenols in a purified liquid sample.
6. Use according to claim 5, characterized in that:
the liquid sample is one or more than two of the following:
one or more than two of drinking water, beverage, milk, river water, well water, lake water, sewage, plasma, serum, blood or urine, or one or more than two of soil, bottom mud, fresh meat, canned food, or solvent extract of indoor and outdoor dust solid samples.
7. Use according to claim 5, characterized in that: the molecularly imprinted polymer is used as a filler of a solid phase extraction column for enriching and purifying bisphenol endocrine disruptors, and has strong selectivity on one or more than two of bisphenol S, bisphenol A, bisphenol F, bisphenol B, bisphenol AF, bisphenol E, bisphenol Z, bisphenol AP, tetrachlorobisphenol A or tetrabromobisphenol A.
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| CN110218325A (en) * | 2019-06-03 | 2019-09-10 | 西北师范大学 | The preparation and application of silane cadmium tellurium quantum dot molecularly imprinted polymer |
| CN110423302B (en) * | 2019-07-18 | 2021-05-28 | 南华大学 | Magnetic surface molecularly imprinted polymer and preparation method and application thereof |
| CN112898624B (en) * | 2019-12-04 | 2022-05-31 | 中国科学院大连化学物理研究所 | Alternative template imprinted polymer for specifically recognizing exosomes and application thereof |
| CN111777713A (en) * | 2020-07-23 | 2020-10-16 | 福州大学 | Metal ion coordination bifunctional monomer molecularly imprinted polymer, and preparation method and application thereof |
| CN112255356B (en) * | 2020-10-21 | 2022-07-08 | 山西省化工研究所（有限公司） | Qualitative and quantitative analysis method for bisphenol antioxidant in plastic |
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| CN104250349A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method and application of dummy template molecularly imprinted polymer |
| CN104341553A (en) * | 2013-08-02 | 2015-02-11 | 中国科学院大连化学物理研究所 | Ultra-high-selectivity bisphenol substitute template molecularly imprinted polymer and application thereof |
| CN105085813A (en) * | 2014-05-05 | 2015-11-25 | 中国科学院大连化学物理研究所 | Bisphenol type substituted template molecularly imprinted polymer and preparation therefor and application thereof |
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| CN104250349A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Preparation method and application of dummy template molecularly imprinted polymer |
| CN104341553A (en) * | 2013-08-02 | 2015-02-11 | 中国科学院大连化学物理研究所 | Ultra-high-selectivity bisphenol substitute template molecularly imprinted polymer and application thereof |
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