CN110511423B - Method for simultaneously removing imidacloprid and acetamiprid in water-soluble tea extract by double-template surface molecularly imprinted material - Google Patents
Method for simultaneously removing imidacloprid and acetamiprid in water-soluble tea extract by double-template surface molecularly imprinted material Download PDFInfo
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Abstract
The invention discloses a method for simultaneously removing imidacloprid and acetamiprid in a water-soluble tea extract by using a double-template surface molecular imprinting material. The method for simultaneously removing imidacloprid and acetamiprid in the water-soluble tea extract by using the double-template surface molecularly imprinted material can specifically remove imidacloprid and acetamiprid in the water-soluble tea extract, has a small adsorption effect on tea polyphenol in the tea extract, has removal rates of imidacloprid and acetamiprid of more than 95% and 94% respectively, and has a loss of tea polyphenol in the extract of less than 14%. In addition, the adsorption column prepared by the invention can be eluted by methanol/acetic acid solution, and the eluted adsorption column can be reused, so that the adsorption column can be well applied to the preparation process of tea extract and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of food green processing, and relates to a method for removing pesticide residues in a tea extract, in particular to a method for simultaneously removing imidacloprid and acetamiprid in a water-soluble tea extract by using a double-template surface molecularly imprinted material.
Background
The chloronicotinyl insecticide mainly acts on the central nervous system of insects to achieve a good killing effect on homoptera aphids and hemiptera planthoppers. The compound pesticide has the characteristics of unique action mode, low mammalian toxicity, high insecticidal activity, low cross resistance with other types of pesticides and the like, and is widely applied to the planting process of tea and other crops. Of the chloronicotinyl insecticides commonly used, imidacloprid and acetamiprid are the most widely used and representative. Although the imidacloprid and acetamiprid have low toxicity, the application range is wide, the domestic supervision is loose, and once the imidacloprid and acetamiprid are remained in agricultural products, the imidacloprid and acetamiprid not only cause great economic loss, but also threaten the health of eaters.
The water soluble tea extract, especially tea polyphenol, is the main product in the deep processing of tea, has the functions of resisting cancer, resisting oxidation, reducing blood fat, resisting atherosclerosis, resisting HIV, etc. and has high medicinal value and health care value. However, in the process of planting tea leaves and applying imidacloprid and acetamiprid by farmers, the situation that the pesticide residue is remained due to insufficient degradation can not be avoided, and the remained pesticide is enriched in the tea extract in the process of tea leaf deep processing, so that the residual amount of the imidacloprid and the acetamiprid in the water-soluble tea extract exceeds the standard. Currently, many advances have been made in the research of pesticide removal in water and vegetables, mainly including irradiation, sonication, adsorption, extraction, oxidation, and biodegradation (CHEN C, FU X, MA T, et a1.Synthesis of polymeric silver nanostructures and formulations in the pesticide electroluminescence emission [ J].Journal of Applied Polymer Science,2014,131.MAJEED S，nERR0D，BUHR K，et al，Uhrafihration of natural organic matter from water by vertically aligned carbon nanotube membrane[J]Journal of Memberane Science,2012(403): 101.; among them, the adsorption method has been widely studied due to its advantages of good adsorption effect, good stability, high recovery rate, low cost, etc. Yuancenxia and the like introduce a large amount of sulfonic functional groups on the surface of mesoporous carbon through 1,3,6, 8-pyrenetetrasulfonic acid sodium, so that the solubility of the sulfoacid sodium in water is greatly improved, and the sulfoacid sodium shows excellent adsorption performance on hexachloro cyclohexane and dichlorodiphenyl trichloroethane in milk. The chazonolong and the like compare modified mesoporous carbon, graphene,Activated carbon, carbon nanotube, Fe3O4Nanoparticle-modified carbon nanotube composite material and Fe3O4The adsorption capacity of different adsorption materials such as nano particles on 9 organophosphorus pesticides in spinach shows that the modified carbon nano tube has the best adsorption effect, good stability and higher recovery rate, and the recovery rate reaches 93.5 percent to the maximum.
However, it is worth mentioning that the methods of ultrasound, irradiation, etc. may have some influence on the color and the properties of the sample during the processing process. Most of the currently used adsorbents, such as activated carbon, macroporous resin, mesoporous carbon, etc., all cause certain adsorption loss to other effective components in the sample. Therefore, it has become a current research focus on how to remove pesticide residues efficiently without destroying the appearance of food and minimizing the loss of effective components.
Molecular imprinting is a material synthesized according to the properties and structure of a target molecule and having a specific adsorption capacity for the molecule, and is considered as a novel specific affinity technology, and has predetermination, recognition and practicability. Besides good stability and long service life, the molecularly imprinted material has the characteristic of low price, and is very suitable for being used as a material for removing pesticide residues in the deep processing process of tea. There have been some studies on molecular imprinting and pesticide affinity. Philippines et al gamma- (methacryloyloxy) propyltrimethoxysilane (KH-570) -modified Fe3O4The nanometer particle is used as carrier, acetochlor (acetochlor) is used as template molecule, and surface molecular imprinting technology is adopted to prepare acetochlor magnetic molecularly imprinted polymer (Fe)3O4@SiO2@ MIP). The magnetic imprinted polymer has higher adsorption amount and good selective adsorption performance on acetochlor, and the maximum adsorption amount is 86.61 mg/g. However, at present, no study on the affinity of molecular imprinting to two pesticides, namely imidacloprid and acetamiprid, exists, and no attempt is made to apply the molecular imprinting to the aspect of pesticide removal of water-soluble tea extracts.
Disclosure of Invention
The technical problem to be solved is as follows: in order to solve the problem of pesticide residue in the existing tea extract aqueous solution and obtain a method which can efficiently remove the pesticide residue in the tea extract aqueous solution, reduce the loss of tea polyphenol as much as possible, has low cost and can be repeatedly used, the invention provides a method for simultaneously removing imidacloprid and acetamiprid in a water-soluble tea extract by using a double-template surface molecular imprinting material.
The technical scheme is as follows: the method for simultaneously removing imidacloprid and acetamiprid in the water-soluble tea extract by using the double-template surface molecularly imprinted material comprises the following steps:
step 1, preparing a modified silica gel support
2-8g of 100-mesh 600-mesh silica gel and 50-200mL of 6-10mol L-1Stirring hydrochloric acid for 18-24h, vacuum filtering and washing until the pH value is neutral, and drying in an oven at the temperature of 100 ℃ and 120 ℃ for 4-8h to obtain activated silica gel;
mixing 2-8g of activated silica gel and 20-100mL of anhydrous toluene in a three-necked flask, magnetically stirring under the protection of nitrogen, dropwise adding 3-12mL of 3-aminopropyltriethoxysilane, dropwise adding 5-10mL of pyridine, heating and refluxing the mixture at 80-120 ℃ for 12-30h, filtering the product, washing the product with toluene, acetone, diethyl ether and methanol in sequence, and drying the product in an oven at 80-120 ℃ for 4-12h to obtain amino modified silica gel;
mixing 2-8g of amino modified silica gel and 50-200mL of anhydrous toluene in a three-necked flask, magnetically stirring for 5-20min under the protection of nitrogen, dropwise adding 4-16mL of acryloyl chloride, continuously magnetically stirring for 15min, slowly dropwise adding 2-8mL of triethylamine as a catalyst, reacting for 12-30h at room temperature, filtering a product, washing with toluene, acetone, diethyl ether and methanol in sequence, and drying for 4-12h at 80-120 ℃ in an oven to obtain acyl modified silica gel;
step 2, preparing double-template surface molecular imprinting
Dissolving imidacloprid and acetamiprid in toluene, adding 2-8mmol of alpha-methacrylic acid and 400-1000mg of acyl modified silica gel, uniformly dissolving, and refrigerating at 0-4 ℃ for 6-18 h. Then continuously adding 12-28mmol of ethylene glycol dimethacrylate and 20-60mg of azobisisobutyronitrile, uniformly mixing, performing ultrasonic treatment for 10-30min, introducing high-purity nitrogen for 10-30min, sealing, polymerizing for 16-32h at 55-65 ℃ in a water bath kettle, washing the obtained solid with methanol to neutrality, and drying in a vacuum drying oven at 60 ℃. Eluting the dried molecularly imprinted powder by a Soxhlet extraction method until no template molecule is eluted, wherein an elution solvent is a mixed solution of methanol and acetic acid according to a volume ratio of 9: 1;
step 3, preparing the molecularly imprinted solid phase adsorption column
And (3) uniformly mixing 500-2000mg of the double-template surface molecularly imprinted powder prepared in the step 2 with 2-8mL of ultrapure water, filling the mixture into the SPE small column filled with the lower sieve plate, and pressing the mixture into the upper sieve plate after all the liquid flows out to obtain the molecularly imprinted solid phase adsorption column. Activating the adsorption column by using methanol, and placing the activated adsorption column for later use;
step 4, preparing the aqueous solution of the tea extract added with imidacloprid and acetamiprid
Preparing water soluble tea extract into 10-60 wt% water solution, adding imidacloprid and acetamiprid to make their concentrations 1-20 μ g/mL respectively-1Filtering with 0.45 μm filter membrane, and collecting filtrate;
step 5, passing through the column
Passing the tea extract aqueous solution prepared in the step 4 through the activated molecular imprinting solid phase adsorption column prepared in the step 3, adjusting and controlling the flow rate, controlling the temperature of the adsorption column at 20-30 ℃, then eluting the tea extract weakly adsorbed on the solid phase column by using ultrapure water with 2-8 times of the column volume, combining the eluent with the column passing liquid, and detecting, wherein the loss of the water-soluble tea extract is less than 14%, and the removal rates of imidacloprid and acetamiprid are respectively more than 95% and 94%;
step 6, recycling
Passing the adsorption column containing imidacloprid and acetamiprid in step 5 through 30mL mixed solvent with methanol-acetic acid volume ratio of 9:1, adjusting and controlling flow rate to 0.5-3 mL/min-1And eluting more than 95 percent of imidacloprid and more than 92 percent of acetamiprid in the adsorption column, and recycling the adsorption column.
Preferably, the tea extract is tea polyphenol or theanine.
Preferably, the imidacloprid and acetamiprid in the step 2 are 0.2-0.8 mmol.
Preferably, the amount of toluene used in step 2 is 60 to 100 mL.
Preferably, the amount of methanol used as the activating reagent in step 3 is 5-20 mL.
Preferably, the weight percentage of the water-soluble tea extract in the step 4 is 20-60 wt%.
Preferably, the concentrations of imidacloprid and acetamiprid added in the step 4 are 1-20 mug.mL respectively-1(ii) a The volume of the tea extract water solution is 5-50 mL.
Preferably, the flow rate in the 5 th step is controlled to 0.5-3 mL-min-1。
Preferably, the removal rate of imidacloprid and acetamiprid in the step 5 is more than 98% and 95%.
Preferably, more than 96% of imidacloprid and more than 94% of acetamiprid in the adsorption column in the step 6 can be eluted.
The working principle of the method for simultaneously removing imidacloprid and acetamiprid in the water-soluble tea extract by using the double-template surface molecularly imprinted material is as follows: silica gel is aminated and then is subjected to acrylation to introduce double bonds, imidacloprid and acetamiprid are used as template molecules, alpha-methacrylic acid is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, and a double-template molecularly imprinted polymer is grafted and polymerized on the surface of the silica gel. The double-template silica gel surface molecularly imprinted polymer can generate specific adsorption cavities aiming at imidacloprid and acetamiprid, and has no specific adsorption effect on tea polyphenol, so that the double-template silica gel surface molecularly imprinted polymer has good removal capacity on imidacloprid and acetamiprid in a water-soluble tea extract. In addition, the dual-template molecularly imprinted column adsorbed with imidacloprid and acetamiprid can be eluted by methanol/acetic acid solution, and the eluted adsorption column can be reused.
Has the advantages that: the method for simultaneously removing imidacloprid and acetamiprid in the water-soluble tea extract by using the double-template surface molecularly imprinted material can specifically remove imidacloprid and acetamiprid in the water-soluble tea extract, has a small adsorption effect on tea polyphenol in the tea extract, has removal rates of imidacloprid and acetamiprid of more than 98% and 95% respectively, and has a loss of tea polyphenol in the extract of less than 14%. In addition, the adsorption column prepared by the invention can be eluted by methanol/acetic acid solution, and the eluted adsorption column can be reused, so that the adsorption column can be well applied to the preparation process of tea extract and has a good application prospect.
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FIG. 1 is a technical simulation of the method of the present invention.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1 removal of Imidacloprid and acetamiprid from aqueous tea polyphenols solution
The embodiment provides a method for removing imidacloprid and acetamiprid from a tea polyphenol aqueous solution, which is divided into 4 steps in total and respectively comprises preparation and pretreatment of the tea polyphenol aqueous solution, preparation of a molecular imprinting column, column chromatography and adsorption column recycling. The specific operation method comprises the following steps:
1) the preparation and pretreatment of the tea polyphenol aqueous solution are that 1.5g of tea polyphenol solid and 100mL of ultrapure aqueous solution are weighed and prepared into 15 g.L-1The tea polyphenol solution of (1) was added with imidacloprid and acetamiprid to a concentration of 10. mu.g/mL, respectively-1Filtered through a 0.25 μm filter membrane for use.
2) The preparation of the molecular imprinting column specifically comprises the steps of mixing the double-template surface molecular imprinting powder with 5mL of ultrapure water, filling the mixture into an SPE small column filled with a lower sieve plate by a wet method, wherein the volume of the SPE small column is about 3mL, activating the adsorption column by using 10mL of methanol, and placing the activated adsorption column for later use.
3) And then, passing 10mL of the tea polyphenol aqueous solution obtained in the step 1) through the silica gel surface molecular imprinting column prepared in the step 2), adjusting the flow rate to be 1.25mL/min, eluting the tea polyphenol remained in the adsorption column by using 10mL of ultrapure water after the tea polyphenol solution completely passes through, combining the adsorption solutions, and measuring the concentrations of imidacloprid, acetamiprid and tea polyphenol before and after adsorption. The detection result shows that the adsorption column has 99.1% of imidacloprid adsorption rate, 96.8% of acetamiprid adsorption rate and only 13.7% of tea polyphenol adsorption rate.
4) Eluting the adsorption column in 3) with 30mL of methanol-acetic acid (v/v,9:1) mixed solvent, adjusting and controlling the flow rate to be 1.25mL/min-1And combining the eluates, and detecting the imidacloprid and the acetamiprid, wherein the detection result shows that 97.2 percent of imidacloprid and 95.8 percent of acetamiprid adsorbed in the adsorption column are eluted by the eluates.
5) After the tea polyphenol aqueous solution in the step 1) is circularly adsorbed for 8 times, the adsorption rates of the tea polyphenol aqueous solution to imidacloprid and acetamiprid still reach 87.3 percent and 85.4 percent.
EXAMPLE 2 removal of Imidacloprid and acetamiprid from Large-Capacity aqueous solution of tea polyphenols
According to the method in the embodiment 1, the treatment capacity of the tea polyphenol water solution is increased, and the specific operation method is as follows:
1) the preparation and pretreatment of the tea polyphenol aqueous solution are that 1.5g of tea polyphenol solid and 100mL of ultrapure aqueous solution are weighed and prepared into 15 g.L-1The tea polyphenol solution of (1) was added with imidacloprid and acetamiprid to a concentration of 10. mu.g/mL, respectively-1Filtered through a 0.25 μm filter membrane for use.
2) The preparation of the molecular imprinting column specifically comprises the steps of mixing the double-template surface molecular imprinting powder with 5mL of ultrapure water, filling the mixture into an SPE small column filled with a lower sieve plate by a wet method, wherein the volume of the SPE small column is about 3mL, activating the adsorption column by using 10mL of methanol, and placing the activated adsorption column for later use.
3) Then, 50mL of the tea polyphenol aqueous solution obtained in the step 1) is passed through the silica gel surface molecular imprinting column prepared in the step 2), the flow rate is adjusted to be 1.25mL/min, after the tea polyphenol solution completely passes through, 10mL of ultrapure water is used for eluting the tea polyphenol remained in the adsorption column, and the concentrations of imidacloprid, acetamiprid and tea polyphenol before and after adsorption are measured after the adsorption solution is combined. The detection result shows that the adsorption column has an imidacloprid adsorption rate of 98.2%, an acetamiprid adsorption rate of 95.6% and a tea polyphenol adsorption rate of only 3.7%.
4) Mixing with 30mL of methanol-acetic acid (v/v,9:1)Eluting the adsorption column in 3) with solvent, and adjusting and controlling flow rate to 1.25mL/min-1And combining the eluates, and detecting imidacloprid and acetamiprid, wherein the detection result shows that 96.6% of imidacloprid and 94.8% of acetamiprid adsorbed in the adsorption column are eluted by the eluates.
5) After the tea polyphenol aqueous solution in the step 1) is circularly adsorbed for 8 times, the adsorption rates of the tea polyphenol aqueous solution to imidacloprid and acetamiprid still reach 89.4 percent and 85.8 percent.
Example 3 removal of Imidacloprid and acetamiprid from aqueous theanine solution
The method of example 1, which is to change the aqueous solution of tea polyphenols to the aqueous solution of theanine, is specifically performed as follows:
1) the preparation and pretreatment of the theanine aqueous solution are that 1.5g of theanine solid and 100mL of ultrapure aqueous solution are weighed to prepare 15 g.L-1 theanine solution, imidacloprid and acetamiprid are added to make the concentration of the theanine solution to be 10 mug.mL-1 respectively, and the theanine solution is filtered by a 0.25 mu m filter membrane for standby.
2) The preparation of the molecular imprinting column specifically comprises the steps of mixing the double-template surface molecular imprinting powder with 5mL of ultrapure water, filling the mixture into an SPE small column filled with a lower sieve plate by a wet method, wherein the volume of the SPE small column is about 3mL, activating the adsorption column by using 10mL of methanol, and placing the activated adsorption column for later use.
3) And then, passing 10mL of the theanine aqueous solution obtained in the step 1) through the silica gel surface molecular imprinting column prepared in the step 2), adjusting the flow rate to be 1.25mL/min, eluting the theanine remained in the adsorption column by using 10mL of ultrapure water after the theanine solution completely passes through, combining the adsorption solutions, and measuring the concentrations of the imidacloprid, the acetamiprid and the theanine before and after adsorption. The detection result shows that the adsorption column has the adsorption rate of 98.9 percent on imidacloprid, 95.8 percent on acetamiprid and only 8.6 percent on theanine.
4) And (2) eluting the adsorption column in the step 3) by using 30mL of methanol-acetic acid (v/v,9:1) mixed solvent, regulating and controlling the flow rate to be 1.25mL/min < -1 >, combining the eluent, and detecting imidacloprid and acetamiprid, wherein the detection result shows that 97.3% of imidacloprid and 95.3% of acetamiprid adsorbed in the adsorption column are eluted by the eluent.
5) After the theanine aqueous solution in the step 1) is circularly adsorbed for 8 times, the adsorption rates of the theanine aqueous solution on imidacloprid and acetamiprid still reach 88.5 percent and 86.0 percent.
Claims (1)
1. The method for simultaneously removing imidacloprid and acetamiprid in the water-soluble tea extract by using the double-template surface molecularly imprinted material is characterized by comprising the following steps of:
step 1, preparing a modified silica gel support
2-8g of 100-mesh 600-mesh silica gel and 50-200mL of 6-10mol L-1Stirring hydrochloric acid for 18-24h, vacuum filtering and washing until the pH value is neutral, and drying in an oven at the temperature of 100 ℃ and 120 ℃ for 4-8h to obtain activated silica gel;
mixing 2-8g of activated silica gel and 20-100mL of anhydrous toluene in a three-necked flask, magnetically stirring under the protection of nitrogen, dropwise adding 3-12mL of 3-aminopropyltriethoxysilane, dropwise adding 5-10mL of pyridine, heating and refluxing the mixture at 80-120 ℃ for 12-30h, filtering the product, washing the product with toluene, acetone, diethyl ether and methanol in sequence, and drying the product in an oven at 80-120 ℃ for 4-12h to obtain amino modified silica gel;
mixing 2-8g of amino modified silica gel and 50-200mL of anhydrous toluene in a three-necked flask, magnetically stirring for 5-20min under the protection of nitrogen, dropwise adding 4-16mL of acryloyl chloride, continuously magnetically stirring for 15min, slowly dropwise adding 2-8mL of triethylamine as a catalyst, reacting for 12-30h at room temperature, filtering a product, washing with toluene, acetone, diethyl ether and methanol in sequence, and drying for 4-12h at 80-120 ℃ in an oven to obtain acyl modified silica gel;
step 2, preparing double-template surface molecular imprinting
Dissolving imidacloprid and acetamiprid in toluene, adding 2-8mmol of alpha-methacrylic acid and 400-1000mg of acyl modified silica gel, uniformly dissolving, and refrigerating at 0-4 ℃ for 6-18 h;
then continuously adding 12-28mmol of ethylene glycol dimethacrylate and 20-60mg of azobisisobutyronitrile, uniformly mixing, performing ultrasonic treatment for 10-30min, introducing high-purity nitrogen for 10-30min, sealing, polymerizing for 16-32h at 55-65 ℃ in a water bath kettle, washing the obtained solid with methanol to neutrality, and drying in a vacuum drying oven at 60 ℃;
eluting the dried molecularly imprinted powder by a Soxhlet extraction method until no template molecule is eluted, wherein an elution solvent is a mixed solution of methanol and acetic acid according to a volume ratio of 9: 1;
step 3, preparing the molecularly imprinted solid phase adsorption column
Uniformly mixing 500-2000mg of the double-template surface molecularly imprinted powder prepared in the step 2 with 2-8mL of ultrapure water, filling the mixture into an SPE small column filled with a lower sieve plate, and pressing the mixture into an upper sieve plate after all liquid flows out to obtain a molecularly imprinted solid phase adsorption column; activating the adsorption column by using methanol, and placing the activated adsorption column for later use;
step 4, preparing the aqueous solution of the tea extract added with imidacloprid and acetamiprid
Preparing water soluble tea extract into 20-60wt% water solution, adding imidacloprid and acetamiprid to make their concentrations 1-20 μ g/mL respectively-1Filtering with 0.45 μm filter membrane to obtain tea extract water solution with volume of 5-50mL, and collecting filtrate;
step 5, passing through the column
Passing the tea extract water solution prepared in step 4 through the activated molecularly imprinted solid phase adsorption column prepared in step 3, adjusting and controlling the flow rate at 0.5-3 mL/min-1Controlling the temperature of the adsorption column at 20-30 ℃, then eluting the tea extract weakly adsorbed on the solid phase column by ultrapure water with 2-8 times of the column volume, combining the eluent with the column-passing liquid and detecting, wherein the loss of the water-soluble tea extract is less than 14 percent, and the removal rates of imidacloprid and acetamiprid are respectively more than 98 percent and 95 percent;
step 6, recycling
Passing the adsorption column containing imidacloprid and acetamiprid in step 5 through 30mL mixed solvent with methanol-acetic acid volume ratio of 9:1, adjusting and controlling flow rate to 0.5-3 mL/min-1Eluting more than 96% of imidacloprid and more than 94% of acetamiprid in the adsorption column, and recycling the adsorption column;
wherein the tea extract is tea polyphenol or theanine; in the step 2, the imidacloprid and the acetamiprid are 0.2 to 0.8mmol, and the dosage of the toluene is 60 to 100 mL; the amount of methanol used as the activating reagent in the step 3 is 5-20 mL.
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| CN104892868A (en) * | 2015-05-14 | 2015-09-09 | 江苏科技大学 | Silica gel surface molecularly imprinted polymer with specific adsorption of DEHP and preparation method and application thereof |
| CN105348437A (en) * | 2015-10-27 | 2016-02-24 | 成都市食品药品检验研究院 | Dual-template molecularly imprinted polymer, and preparation method and application thereof |
| CN106914227A (en) * | 2017-04-12 | 2017-07-04 | 中国农业科学院蔬菜花卉研究所 | The preparation method and method of evaluating performance of anabasine pesticide fluorescence molecule imprinted polymer microballoon |
| CN107552018A (en) * | 2017-09-12 | 2018-01-09 | 华南农业大学 | A kind of Acetamiprid molecularly imprinted solid phase extraction column and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104892868A (en) * | 2015-05-14 | 2015-09-09 | 江苏科技大学 | Silica gel surface molecularly imprinted polymer with specific adsorption of DEHP and preparation method and application thereof |
| CN105348437A (en) * | 2015-10-27 | 2016-02-24 | 成都市食品药品检验研究院 | Dual-template molecularly imprinted polymer, and preparation method and application thereof |
| CN106914227A (en) * | 2017-04-12 | 2017-07-04 | 中国农业科学院蔬菜花卉研究所 | The preparation method and method of evaluating performance of anabasine pesticide fluorescence molecule imprinted polymer microballoon |
| CN107552018A (en) * | 2017-09-12 | 2018-01-09 | 华南农业大学 | A kind of Acetamiprid molecularly imprinted solid phase extraction column and its preparation method and application |
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