CN107868181B - Climbazole substituted template molecularly imprinted polymer and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a climbazole substituted template molecularly imprinted polymer and a preparation method and application thereof. The preparation method comprises the following steps: dissolving the substituted template molecule, the cross-linking agent, the functional monomer and the initiator in a pore-forming solvent to prepare a prepolymerization solution, and carrying out polymerization reaction for 24-48h at 55-75 ℃. Grinding, screening and settling the white block polymer generated by the polymerization reaction to obtain white polymer particles with the particle size of 30-60 mu m. And sequentially adopting methanol/acetic acid and methanol as extraction solvents to perform Soxhlet extraction on the obtained polymer particles, and removing the substituted template molecules and unreacted substances to obtain the substituted template molecularly imprinted polymer. The template-substituted molecularly imprinted polymer provided by the invention can be used as a solid phase extraction material, is applied to enrichment and purification of the climbazole in environmental samples, foods and personal care products, has the advantages of strong selectivity, large adsorption capacity and no template leakage, and has important significance for human health and environmental monitoring.
Description
Technical Field
The invention relates to a substituted template molecularly imprinted polymer for enriching and purifying a carbenoxolone antifungal agent with high selectivity, and preparation and application thereof, and belongs to the field of environmental monitoring and new materials.
Background
The galangin is an azole bactericide, and is widely applied to various products containing antifungal active ingredients, especially medicines and personal care products, such as shampoo, skin cream, soap, toothpaste, bath lotion and the like. The annual production of galangin as a second generation antifungal agent is increasing (environmental International,84(2015) 142). In recent years, it has been found that it is a new type of pollutant, potentially harmful to the environment, living beings and humans, and it shows reproductive toxicity to different types of organisms such as microorganisms, cells, higher animals and their embryos, plants and seeds (Journal of Hazardous materials,318(2016) 794). For example, Richter et al in 2013 found that the EC50 (half lethal concentration) of the galangin on zebrafish for 48 hours is 8.2mg/L, and the galangin has high embryonic lethality on fish (Environmental Toxicology & Chemistry,32(2013) 2816). Therefore, the analysis and detection of the galangin in the environment are powerful guarantees for reducing or eliminating the hazardous influence of the galangin.
The conventional solid phase extraction adsorbent is used for retaining a compound through nonspecific hydrophobic effect or polar effect, so that the specificity and the retention capability are poor, and the solid phase extraction adsorbent adsorbs an interferent while adsorbing the to-be-detected substance to a certain extent, thereby causing detection interference or reducing the recovery rate. The molecular imprinting-solid phase extraction (MISPE) technology established by applying the molecular imprinting polymer to solid phase extraction can overcome the defects, can effectively remove impurities while retaining a target object, and obtains 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.
A Molecularly Imprinted Polymer (MIP) refers to a method for preparing a polymer having a specific selectivity for a specific target molecule by using the molecule as a template. No study on the climbazole substituted template molecularly imprinted polymer is reported at present. The invention adopts advanced template-replacing molecular imprinting technology, uses miconazole or conazole ketone as a template molecule to prepare the climbazole molecular imprinting polymer by a self-assembly method, and uses the climbazole molecular imprinting polymer as a novel solid phase extraction material. The material has better selectivity than an imprinted polymer prepared by taking the climbazole as a template, and solves the problem of inaccurate result caused by template leakage. Has the ability to selectively enrich and purify bisphenol endocrine disruptors in environmental, personal care and food samples.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a substitutive template molecularly imprinted polymer, which is used for enriching and detecting the antifungal property of the climbazole in environmental samples, personal care products and food samples. Aiming at the problem of template leakage commonly existing in non-covalent molecularly imprinted materials, miconazole or ketoconazole is adopted as a substitute template to prepare the climbazole molecularly imprinted material. The miconazole or ketoconazole has higher matching degree with the climbazole in the molecular space structure, so the molecularly imprinted polymer prepared by adopting the miconazole or ketoconazole as the template also has higher imprinting selectivity on the climbazole, does not leak climbazole molecules, and can greatly improve the reliability of data during trace sample analysis.
In order to realize the purpose, the invention discloses a climbazole substituted template molecularly imprinted polymer which can be prepared by the following steps:
(1) mixing the substituted template molecules, the functional monomer, the cross-linking agent, the initiator and the pore-foaming agent to prepare a homogeneous system; the proportions are as follows: substitution of template molecules: functional monomer: a crosslinking agent: initiator: the mol ratio of the pore-foaming agent is 1: 2-8: 10-30: 0.2-0.3: 18-22; wherein the substitute template molecule is at least one of miconazole or ketoconazole; the functional monomer is at least one of methacrylic acid, acrylic acid, trifluoromethyl acrylic acid or hydroxyethyl methacrylate; the cross-linking agent is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or divinylbenzene; the initiator is azobisisobutyronitrile; the pore-foaming agent is at least one of acetonitrile, chloroform, methanol or toluene;
(2) placing the pre-polymerization solution in ice water bath, ultrasonic degassing for 5-15min, introducing nitrogen to remove oxygen for 5-15min, removing oxygen molecules, sealing, and standing at 4 deg.C for 2 h;
(3) putting the sealed and refrigerated prepolymerization solution into a water bath at the temperature of 55-75 ℃ for bulk polymerization for 6-48h to generate a white block polymer;
(4) crushing, grinding, screening and settling the white massive polymer to obtain a white powdery polymer with the granularity of 30-60 mu m;
(5) sequentially adopting a methanol/acetic acid mixed solution and methanol as extraction solvents to carry out Soxhlet extraction, and removing template molecules and interfering substances;
(6) and after extraction is finished, the polymer is placed in a vacuum drying oven to be dried for 12-24h at the temperature of 55-75 ℃, and the substitute template molecularly imprinted polymer is obtained.
The solvent used for sedimentation in the step (4) is acetone;
in the step (5), the volume ratio of methanol to acetic acid in the methanol/acetic acid mixed solution adopted by the Soxhlet extraction is 9: 1-3; the extraction temperature of the methanol/acetic acid mixed solution and the extraction time of the methanol are both 80-120 ℃, and the extraction time is 12-24 h.
The preparation method of the imprinted polymer can be prepared by the following steps:
(1) mixing the substituted template molecules, the functional monomer, the cross-linking agent, the initiator and the pore-foaming agent to prepare a homogeneous system; the proportions are as follows: substitution of template molecules: functional monomer: a crosslinking agent: initiator: the mol ratio of the pore-foaming agent is 1: 2-8: 10-30: 0.2-0.3: 18-22;
wherein the substitute template molecule is at least one of miconazole or ketoconazole; the functional monomer is at least one of methacrylic acid, acrylic acid, trifluoromethyl acrylic acid or hydroxyethyl methacrylate; the cross-linking agent is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or divinylbenzene; the initiator is azobisisobutyronitrile; the pore-foaming agent is at least one of acetonitrile, chloroform, methanol or toluene;
(2) placing the pre-polymerization solution in ice water bath, ultrasonic degassing for 5-15min, introducing nitrogen to remove oxygen for 5-15min, removing oxygen molecules, sealing, and standing at 4 deg.C for 2 h;
(3) putting the sealed and refrigerated prepolymerization solution into a water bath at the temperature of 55-75 ℃ for bulk polymerization for 6-48h to generate a white block polymer;
(4) crushing, grinding, screening and settling the white massive polymer to obtain a white powdery polymer with the granularity of 30-60 mu m;
(5) sequentially adopting a methanol/acetic acid mixed solution and methanol as extraction solvents to carry out Soxhlet extraction, and removing template molecules and interfering substances;
(6) and after extraction is finished, the polymer is placed in a vacuum drying oven to be dried for 12-24h at the temperature of 55-75 ℃, and the substitute template molecularly imprinted polymer is obtained.
The solvent used for sedimentation in the step (4) is acetone;
in the step (5), the volume ratio of methanol to acetic acid in the methanol/acetic acid mixed solution adopted by the Soxhlet extraction is 9: 1-3; the extraction temperature of the methanol/acetic acid mixed solution and the extraction time of the methanol are both 80-120 ℃, and the extraction time is 12-24 h.
An application of a molecularly imprinted polymer as a high-selectivity adsorbent in enriching and purifying a galangin antifungal agent in a liquid sample.
The molecularly imprinted polymer is used as a filler of a matrix dispersion solid phase extraction or solid phase extraction column for enriching and purifying the carbenoxolone antifungal agent in drinking water, shower gel, shampoo, cosmetics, milk or sewage and the like, or soil, bottom mud, fresh meat or canned food and the like.
The molecularly imprinted polymer is used as a filler of a solid phase extraction column for enriching and purifying the climbazole, and has strong selective enrichment capacity on the trace climbazole in a complex matrix; due to the adoption of the alternative template, the problems of inaccurate quantification, poor reproducibility and the like caused by template leakage in trace analysis can be avoided; meanwhile, the alternative template molecularly imprinted polymer has higher imprinting factor than an imprinting material prepared by taking the climbazole as a template.
The invention has the advantages that: the prepared alternative template molecularly imprinted polymer has specific selectivity on the climbazole and does not have the problem of template leakage. In the preferred embodiment of the invention, miconazole is used as a substitute template molecule, methacrylic acid is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, acetonitrile is used as a pore-forming agent, the polymerization is initiated under the action of an azodiisobutyronitrile 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 as to obtain the substitute template molecularly imprinted polymer with specific selectivity. The polymer has strong selectivity to the climbazole, and the imprinting factor is as high as 5.5, which is higher than the imprinting factor 3.5 obtained by using the climbazole as a template.
The template-substituted molecularly imprinted polymer has ultrahigh specific selectivity on the climbazole, does not have the problem of template leakage, and can detect the climbazole in an actual sample more quickly, sensitively, accurately and efficiently.
Drawings
FIG. 1 illustrates the imprinting factors of miconazole instead of template molecularly imprinted polymer (Mico-DMIP) for miconazole, climbazole, and bisphenol A (BPA) as a comparative material.
FIG. 2 shows the selective elution effect of the alternative template molecular imprinting solid phase extraction (DMISPE).
FIG. 3 illustrates the imprinting factor of ketoconazole on ketoconazole, climbazole and bisphenol A (BPA) as a comparative substance by replacing template molecularly imprinted polymer (Keto-DMIP).
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly and unequivocally define the scope of the present invention.
Example 1
Dissolving 1mmol of miconazole as a substitute template molecule into acetonitrile (5.6mL) containing 4mmol of functional monomer methacrylic acid, 20mmol of crosslinking agent ethylene glycol dimethacrylate and 0.04g of initiator azobisisobutyronitrile to prepare a prepolymerization solution, placing the prepolymerization solution in an ice bath, performing ultrasonic treatment for 10-15min, uniformly mixing, 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 30-60 mu m is obtained after sieving and acetone sedimentation. And sequentially carrying out Soxhlet extraction on the obtained polymer by using methanol acetic acid (9: 1, v/v) and methanol as extraction solvents to remove template molecules and other interfering substances, and drying the obtained polymer in a vacuum drying oven at 60 ℃ overnight to obtain a white miconazole substituted template molecularly imprinted polymer (Mico-DMIP). The preparation and treatment of the control non-imprinted polymer (NIP) was identical except that no template molecule was added. The specific surface area and pore volume results of the polymers are shown in Table 1.
TABLE 1 Performance determination results of alternative template molecularly imprinted polymers of the present invention
The molecular imprinting polymer is filled into a stainless steel chromatographic column with the size of 100 multiplied by 4.6mm by a chromatographic column filling machine by adopting a homogenization method, and is subjected to liquid chromatographic analysis after being washed and balanced at low flow rate. The mobile phase is acetonitrile, and the flow rate is 2mL min-1The determination wavelength was set at 220nm for the determination of galanin and the dead time (t) was determined using methanol as solvent0). According to the retention time (t) of the galangin on a molecular imprinting chromatographic column and a non-imprinting chromatographic columnR) Its capacity factor (k') and hence its Imprinting Factor (IF) were calculated to characterize its selectivity to galanin. k ═ tR-t0)/t0，IF＝k′MIP/k′NIP. Wherein, k'MIPAnd k'NIPCapacity factors of the galangin on a molecular imprinting chromatographic column and a non-imprinting chromatographic column respectively.
The result shows that the above-mentioned substituted template molecularly imprinted polymer has obvious specific selectivity for both the substituted template itself and the climbazole. The results of the blot factor assay are shown in FIG. 1.
And (3) manually filling a solid-phase extraction column (3mL column tube) by using 200mg of miconazole as a solid-phase extraction filler instead of a template imprinting material, and applying the solid-phase extraction column to enrichment, purification and detection of the climbazole in an environmental water sample. Before the solid phase extraction column is used, 3mL of acetonitrile and 3mL of water are sequentially used for balancing, 200mL of water sample is loaded to the solid phase extraction column at the speed of 5mL/min, and after the solid phase extraction column is drained for 10min, 2.0mL of acetonitrile is used for selective leaching. And finally, eluting by using 6.0mL of methanol, blowing elution liquid nitrogen, and then diluting to 1mL by using methanol-water (72:28, v/v) for liquid chromatographic analysis. The control non-imprinted polymer (NIP) was packed in a solid phase extraction column and sample processing was the same as the miconazole-substituted template molecularly imprinted polymer (Mico-DMIP) described above. The liquid chromatography conditions were as follows: agilent 1100 HPLC was equipped with a ZORBAX SB column (Agilent ZORBAX SB-C18, 250X 4.6mm id,5 μm) and an ultraviolet detector UV, with mobile phases of methanol and water (72:28, v/v); the column temperature was 25 ℃; the detection wavelength is 225 nm; the amount of sample was 20. mu.L. The recovery rate of the galangin in pure water on the imprinted and non-imprinted columns is shown in FIG. 2, and the recovery rate of the galangin in Mico-DMIP is far higher than that of the galangin in NThe recovery rate of IP and the control substance bisphenol A on Mico-DMIP and NIP is low, and the high selectivity of the imprinting material on the galangin is fully proved. The results of spiking recovery of the galangin in the river water samples are shown in Table 2, with spiking concentrations of 25 and 5 μ g L-1The recovery rate is above 85%, the Relative Standard Deviation (RSD) is within 5%, and the method has good accuracy and precision and can be used for measuring the galangin in an actual sample.
TABLE 2 examination of Ganbaosu recovery rate in river water
Example 2
Dissolving 1mmol of ketoconazole as a substitute template molecule into acetonitrile (5.6mL) containing 4mmol of functional monomer methacrylic acid, 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, performing ultrasonic treatment for 10-15min, uniformly mixing, 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 30-60 mu m is obtained after sieving and acetone sedimentation. And sequentially carrying out Soxhlet extraction on the obtained polymer by using methanol acetic acid (9: 1, v/v) and methanol as extraction solvents to remove template molecules and other interfering substances, and drying the obtained polymer in a vacuum drying oven at 60 ℃ overnight to obtain a white ketoconazole substituted template molecularly imprinted polymer (Keto-DMIP). The preparation and treatment of the control non-imprinted polymer (NIP) was identical except that no template molecule was added.
The molecular imprinting polymer is filled into a stainless steel chromatographic column with the size of 100 multiplied by 4.6mm by a chromatographic column filling machine by adopting a homogenization method, and is subjected to liquid chromatographic analysis after being washed and balanced at low flow rate. The mobile phase is acetonitrile, and the flow rate is 2mL min-1The determination wavelength was set at 220nm for the determination of galanin and the dead time (t) was determined using methanol as solvent0). According to the retention time (t) of the galangin on a molecular imprinting chromatographic column and a non-imprinting chromatographic columnR) ComputingIts capacity factor (k') and from this its Imprinting Factor (IF) was calculated to characterize its selectivity for galanin. k ═ tR-t0)/t0，IF＝k′MIP/k′NIP. Wherein, k'MIPAnd k'NIPCapacity factors of the galangin on a molecular imprinting chromatographic column and a non-imprinting chromatographic column respectively.
The result shows that the above-mentioned substituted template molecularly imprinted polymer has obvious specific selectivity for both the substituted template itself and the climbazole. The results of the blot factor assay are shown in FIG. 3.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (7)
1. A climbazole substituted template molecularly imprinted polymer is characterized in that: the preparation method comprises the following steps:
(1) mixing the substituted template molecules, the functional monomer, the cross-linking agent, the initiator and the pore-foaming agent to prepare a homogeneous system; the proportions are as follows: substitution of template molecules: functional monomer: a crosslinking agent: initiator: the mol ratio of the pore-foaming agent is 1: 2-8: 10-30: 0.2-0.3: 18-22;
wherein the substitute template molecule is at least one of miconazole or ketoconazole;
the functional monomer is at least one of methacrylic acid, acrylic acid, trifluoromethyl acrylic acid or hydroxyethyl methacrylate;
the cross-linking agent is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or divinylbenzene;
the initiator is azobisisobutyronitrile;
the pore-foaming agent is at least one of acetonitrile, chloroform, methanol or toluene;
(2) placing the pre-polymerization solution in ice water bath, ultrasonic degassing for 5-15min, introducing nitrogen to remove oxygen for 5-15min, removing oxygen molecules, sealing, and standing at 4 deg.C for 2 h;
(3) putting the sealed and refrigerated prepolymerization solution into a water bath at the temperature of 55-75 ℃ for bulk polymerization for 6-48h to generate a white block polymer;
(4) crushing, grinding, screening and settling the white massive polymer to obtain a white powdery polymer with the granularity of 30-60 mu m;
(5) sequentially adopting a methanol/acetic acid mixed solution and methanol as extraction solvents to carry out Soxhlet extraction, and removing template molecules and interfering substances;
(6) and after extraction is finished, the polymer is placed in a vacuum drying oven to be dried for 12-24h at the temperature of 55-75 ℃, and the substitute template molecularly imprinted polymer is obtained.
2. The carbenoxolone substituted template molecularly imprinted polymer of claim 1, wherein:
the solvent used for sedimentation in the step (4) is acetone;
in the step (5), the volume ratio of methanol to acetic acid in the methanol/acetic acid mixed solution adopted by the Soxhlet extraction is 9: 1-3; the extraction temperature of the methanol/acetic acid mixed solution and the extraction time of the methanol are both 80-120 ℃, and the extraction time is 12-24 h.
3. A method for preparing the carbenoxolone substitute template molecularly imprinted polymer as claimed in claim 1 or 2, which is characterized in that: the preparation method comprises the following steps:
(1) mixing the substituted template molecules, the functional monomer, the cross-linking agent, the initiator and the pore-foaming agent to prepare a homogeneous system; the proportions are as follows: substitution of template molecules: functional monomer: a crosslinking agent: initiator: the mol ratio of the pore-foaming agent is 1: 2-8: 10-30: 0.2-0.3: 18-22;
wherein the substitute template molecule is at least one of miconazole or ketoconazole;
the functional monomer is at least one of methacrylic acid, acrylic acid, trifluoromethyl acrylic acid or hydroxyethyl methacrylate;
the cross-linking agent is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or divinylbenzene;
the initiator is azobisisobutyronitrile;
the pore-foaming agent is at least one of acetonitrile, chloroform, methanol or toluene;
(2) placing the pre-polymerization solution in ice water bath, ultrasonic degassing for 5-15min, introducing nitrogen to remove oxygen for 5-15min, removing oxygen molecules, sealing, and standing at 4 deg.C for 2 h;
(3) putting the sealed and refrigerated prepolymerization solution into a water bath at the temperature of 55-75 ℃ for bulk polymerization for 6-48h to generate a white block polymer;
(4) crushing, grinding, screening and settling the white massive polymer to obtain a white powdery polymer with the granularity of 30-60 mu m;
(5) sequentially adopting a methanol/acetic acid mixed solution and methanol as extraction solvents to carry out Soxhlet extraction, and removing template molecules and interfering substances;
(6) and after extraction is finished, the polymer is placed in a vacuum drying oven to be dried for 12-24h at the temperature of 55-75 ℃, and the substitute template molecularly imprinted polymer is obtained.
4. The method for preparing the carbenoxolone substitute template molecularly imprinted polymer as claimed in claim 3, wherein the method comprises the following steps:
the solvent used for sedimentation in the step (4) is acetone;
in the step (5), the volume ratio of methanol to acetic acid in the methanol/acetic acid mixed solution adopted by the Soxhlet extraction is 9: 1-3; the extraction temperature of the methanol/acetic acid mixed solution and the extraction time of the methanol are both 80-120 ℃, and the extraction time is 12-24 h.
5. An application of the carbenoxolone substituted template molecularly imprinted polymer as defined in claim 1 or 2 as a high selectivity adsorbent in enriching and purifying liquid samples.
6. Use according to claim 5, characterized in that:
the molecularly imprinted polymer is used as a filler of a matrix dispersion solid phase extraction or solid phase extraction column for enriching and purifying drinking water, shower gel, shampoo, cosmetics, milk or sewage, or a climbazole antifungal agent in soil, bottom mud, fresh meat or canned food.
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 the climbazole, and has strong selective enrichment capacity on the trace climbazole in a complex matrix;
due to the adoption of the alternative template, the problems of inaccurate quantification and poor reproducibility caused by template leakage in trace analysis are solved; meanwhile, the alternative template molecularly imprinted polymer has higher imprinting factor than an imprinting material prepared by taking the climbazole as a template.
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| DE102010012199A1 (en) * | 2010-03-19 | 2011-09-22 | Fresenius Medical Care Deutschland Gmbh | Molecularly imprinted polymers for the elimination of metabolites |
| 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 |
| CN106317325B (en) * | 2016-09-14 | 2019-06-07 | 中国农业科学院农业质量标准与检测技术研究所 | Triazole pesticide molecular blotting polymer microsphere, solid-phase extraction column and its application |
| CN106496416B (en) * | 2016-11-10 | 2018-10-02 | 河北科技大学 | Mix the preparation method and applications of four template magnetic imprinted polymers |
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