CN101921370A - Method for preparing molecularly imprinted polymer used for detecting valnemulin - Google Patents
Method for preparing molecularly imprinted polymer used for detecting valnemulin Download PDFInfo
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- CN101921370A CN101921370A CN 201010250361 CN201010250361A CN101921370A CN 101921370 A CN101921370 A CN 101921370A CN 201010250361 CN201010250361 CN 201010250361 CN 201010250361 A CN201010250361 A CN 201010250361A CN 101921370 A CN101921370 A CN 101921370A
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- valnemulin
- imprinted polymer
- molecularly imprinted
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Abstract
The invention relates to the compound detection field, in particular to a method for preparing a molecularly imprinted polymer used for detecting valnemulin which is prepared by adopting a bulk polymerization method, a precipitation polymerization method, an in-situ polymerization method or a suspension polymerization method and taking a valnemulin precursor as a template; and the prepared molecularly imprinted polymer has high selectivity on the valnemulin in an aqueous solution system, can identify the valnemulin in high specificity, and has wide application prospect as a sample pretreatment material analyzing the valnemulin in the matrixes such as feeds and tissues and the like.
Description
Technical field
The present invention relates to the compound test field, be specifically related to a kind of preparation method who is used to detect the molecularly imprinted polymer of valnemulin.
Background technology
Valnemulin (valnemulin) is the semi-synthetic animal specific microbiotic of pleuromulins of new generation (pleuromutilin), belongs to two terpenes, and the Mycoplasma and the gram positive organism that are mainly used in control pig, ox, sheep, poultry infect.Valnemulin, chemistry is by name: ((2-((R)-2-amino-3-methylbutyryl amino)-1,1-dimethyl ethyl) sulfydryl) acetate, (3aS, 4R, 5S, 6S, 8R, 9R, 9aR, 10R)-octahydro-5,8-dihydroxyl-4,6,9,10-tetramethyl--6-vinyl-3a, 9-propane-3aH-encircles penta cyclooctene-1 (4H)-ketone-8-ester, and its chemical structural formula is: C
31H
52N
2O
5S; Relative molecular weight; 564.8 proterties: white crystalline powder, atomic water-soluble (160mg/L) is dissolved in methyl alcohol, ethanol, acetone, chloroform, and its hydrochloride is water-soluble, fusing point 174-177 ℃.
Because valnemulin has safety, efficient, low toxicity, be difficult for producing characteristics such as resistance, present many countries are widely-used.But because the maximum absorption of valnemulin is in the near ultraviolet region, and the interference of the various impurity near ultraviolet region is bigger, and this has increased the difficulty of its residue detection undoubtedly, therefore, does not still have a kind of publishing so far, generally acknowledged reliable and stable method for detecting residue.Set up a kind of reliable and stable method for detecting residue and just become current problem demanding prompt solution.The method of reporting for work at present is in the sample preparation process, and is not only loaded down with trivial details but also use traditional SPE filler to be mainly bonding material, as C
8, C
18And ion exchange resin etc., selectivity is not strong, and in enrichment of analyte, a large amount of matrixes and interfering substance cause still containing in the elutriant matrix and impurity also by enrichment, disturb last stratographic analysis.
Molecular engram solid phase extraction technology based on similar antigen-antibody reaction has highly selective and specificity, is a kind of Solid-Phase Extraction material with wide application prospect.If can be as antibody, the isolation medium that valnemulin is had a highly selective of synthetic some similar antibody then can improve sensitivity and the accuracy that valnemulin detects greatly.
Molecular imprinting (molecular imprinting) is a new research field that develops rapidly based on molecular recognition theory in recent years, and molecular imprinting is also referred to as the technology of manufacturing " plastics antibody ".
(molecular imprinting polymers is that a class inside has the hole of fixed size and shape and has the cross-linked high polymer of definite arranging functional group MIPs) to molecularly imprinted polymer.Because MIPs is customized according to microsphere, so it has specific molecule structure and functional group, can optionally discern microsphere.
The preparation of molecularly imprinted polymer generally will be by following three steps:
1, function monomer accumulates in template molecule and forms the reversible mixture on every side by interacting on (covalently or non-covalently key) with template molecule;
2, copolymerization generation superpolymer takes place in function monomer and excessive linking agent in the presence of pore-creating agent;
3, template molecule is dissociated out from superpolymer, in polymkeric substance, just formed can the recognition template molecule binding site.
This imprinted polymer can be used as the sensing member of stationary phase, catalysts selective, chemical sensor of liquid chromatography and solid extracting agent etc., also is widely used in the clinical medicine analysis.
Suitable template is to prepare the key that valnemulin is had the molecularly imprinted polymer of high specific.Valnemulin is soluble in organic solvent, and this detects valnemulin pre-treatment molecularly imprinted polymer as the template preparation with valnemulin, has the template leakage problem, and the molecularly imprinted polymer that valnemulin is had high specific is difficult to obtain.Therefore, searching is a kind of extremely important with the similar template molecule of valnemulin molecular structure.
Summary of the invention
The objective of the invention is to that the template that exists in the detection according to valnemulin in the prior art is revealed, molecularly imprinted polymer is difficult to problems such as acquisitions, provide a kind of and have high selectivity, prevent the preparation method of molecularly imprinted polymer who is used to detect valnemulin of template leakage.
Above-mentioned purpose of the present invention is achieved by the following technical programs:
The present invention selects the valnemulin precursor as template, adopt this areas such as solution polymerization process, situ aggregation method, precipitation polymerization method or suspension polymerization to prepare molecularly imprinted polymer method commonly used, can realize the present invention, prepare the molecularly imprinted polymer that valnemulin is had high specific.
In order further to improve the specificity of molecularly imprinted polymer of the present invention to valnemulin, the inventor studies its preparation method and optimizes.
A kind of method for preparing molecularly imprinted polymer of the present invention, this method be with template (valnemulin precursor), function monomer, linking agent, pore-creating agent and initiator at 50～80 ℃ of polymerization 24～48h, remove template after the pulverizing, prepare molecularly imprinted polymer.
The amount ratio of above-mentioned template, function monomer, linking agent, pore-creating agent and initiator can be selected mmol: mmol: mmol: mL: mg=1: (3～8): (15～40): (3～200): (10～60).
The above-mentioned functions monomer is methacrylic acid, acrylamide, 2-vinylpyridine or 4-vinylpyridine etc.
Above-mentioned linking agent is ethylene glycol dimethacrylate, trimethoxy propane trimethyl acrylic ester or divinylbenzene etc.
Above-mentioned pore-creating agent is a polar organic solvent, as methyl alcohol, ethanol, acetonitrile, acetone or its corresponding solution etc.
Pore-creating agent will guarantee the abundant dissolving of template on the one hand, the pore-creating agent consumption has material impact to molecularly imprinted polymer intensity, the surface property of preparation on the other hand, and pore-creating agent is also very relevant to the identification of imprinted polymer valnemulin in the working medium system simultaneously.Therefore the inventor optimizes pore-creating agent, found that when pore-creating agent is selected acetonitrile, can prepare the molecularly imprinted polymer that valnemulin is had high degree of specificity identification.
Above-mentioned initiator can be selected this area any initiator commonly used, and water soluble starter or oil-soluble initiator can be realized the present invention, as Diisopropyl azodicarboxylate, ammonium persulphate etc.
Remove template after the above-mentioned pulverizing, can adopt 10% acetate methyl alcohol, methyl alcohol to remove template.
Preparation method's of the present invention preferred version is: earlier template, pore-creating agent and function monomer are mixed with the formation prepolymer, add linking agent and initiator again at 50～80 ℃ of polymerization 24～48h, remove template after the pulverizing, prepare molecularly imprinted polymer.
In the aforesaid method, the concrete preparation process of prepolymer is with after valnemulin precursor and the pore-creating agent dissolving mixing, adds function monomer, mixes back 4 ℃～8 ℃ standing over night, forms prepolymer.
Preparation method's of the present invention further preferred version is: earlier template, pore-creating agent and function monomer are mixed with the formation prepolymer, in prepolymer, add linking agent and initiator, elder generation's low temperature (as 4 ℃) prepolymerization down, 50～80 ℃ of polymerization 24～48h again, remove template after the pulverizing, prepare molecularly imprinted polymer.
Above-mentioned pre-polymerization is combined into 4～8 ℃, thermopolymerization 24～48h.
Molecularly imprinted polymer of the present invention, find after testing: this polymkeric substance is used for Solid-Phase Extraction purifies (150mg/ post), polymkeric substance is about 1000 μ g/g polymkeric substance in conjunction with the adsorptive capacity of valnemulin; Feed is added the valnemulin recovery test show that recovery test shows, in 1-50 μ g/mL added horizontal extent, the valnemulin rate of recovery was greater than 90%.
Compared with prior art, the present invention has following beneficial effect:
1. molecularly imprinted polymer of the present invention is that the valnemulin precursor of employing and valnemulin similar is the simulated templates preparation, because of valnemulin has similar molecular structure to the valnemulin precursor, the synthetic polymkeric substance can optionally be discerned valnemulin, and valnemulin is had high specific;
2. molecularly imprinted polymer of the present invention adopts the valnemulin precursor as template, and on the one hand, valnemulin precursor water-absorbent is stronger, helps the selection of pore-creating agent, on the other hand, can prevent " template leakage ";
3. when the present invention prepared molecularly imprinted polymer, the pore-creating agent of employing was an acetonitrile solvent, helped the dissolving of template, and the hardness of synthetic polymer is good simultaneously;
4. preparation method of the present invention can directly carry out 60 ℃ of polymerizing curables with adding linking agent and initiator in the prepolymer then, can also carry out earlier carrying out 50～80 ℃ of polymerizing curables again after the low temperature photopolymerization, can further improve the specificity of molecularly imprinted polymer like this;
5. molecularly imprinted polymer of the present invention is at water and contain in the solution of acetonitrile valnemulin is presented high affinity and selectivity, and the rate of recovery is greater than 90%;
6. the present invention adopts the simulated templates legal system to be equipped with MIPs, overcome when being used for solid phase extraction filler for the MIPs of template preparation because the inaccurate problem of result that the template leakage causes with target compound itself (valnemulin), the present invention is the MIPs that makes of template to the height cross reaction of valnemulin and remarkable selectivity with the valnemulin precursor, has a wide range of applications as the sample pre-treatments material of analyzing the valnemulin in the matrix such as feed, tissue.
Description of drawings
Fig. 1 is that the valnemulin acetonitrile solution is handled the comparison colours spectrogram through MIP and NIP, and wherein, a is that NIP handles, and b is that MIP handles;
Fig. 2 handles the comparison colours spectrogram for the valnemulin feed extracts the matrix acetonitrile solution through MIP and NIP, and wherein, a is that NIP handles, and b is that MIP handles.
Embodiment
Below in conjunction with specific embodiment the present invention is done to describe further, but specific embodiment is not done any qualification to the present invention.
Embodiment 1 is used to detect the molecularly imprinted polymer of valnemulin
The molecularly imprinted polymer of present embodiment, its synthetic preparation process is as follows:
(1) preparation of prepolymer
Take by weighing 0.464g (1mmol) valnemulin precursor simulated templates in test tube, add the 6.0ml acetonitrile, behind the ultrasonic dissolution, add function monomer methacrylic acid 0.342mL (8mmol), ultrasonic 5min, 4 ℃ of standing over night form prepolymer.
(2) thermopolymerization
In above-mentioned prepolymer, add ethylene glycol dimethacrylate 4.0mL (20mmol) and Diisopropyl azodicarboxylate 30mg, ultrasonic 5min, logical nitrogen 5min, sealing, at 60 ℃, water-bath vibration polymerization 24h;
Behind the thermopolymerization 24h, obtain bulk polymer, this bulk polymer is the molecularly imprinted polymer that valnemulin detects that is used for of present embodiment.
Above-mentioned bulk polymer is ground, crosses 200 mesh sieves, with methyl alcohol repeatedly sedimentation remove fine particle, pack in 15 * 200mm tool plug glass chromatography column, remove simulated templates valnemulin precursor with 10% acetate methanol solution 200mL washing earlier, flow rate control is below 1mL/min, remove acetate with the 100mL methanol wash again, particle is put dry 24h in 60 ℃ of vacuum drying ovens, put in the moisture eliminator preserve standby.The granular filler for preparing is compared with the synthetic bulk polymer, and yield reaches 70%.
The preparation of non-imprinted polymer (NIPs) is except that adding the template molecule, all prepares as stated above and handles.
Embodiment 2 is used to detect the performance measurement of the molecularly imprinted polymer of valnemulin
Present embodiment selects the molecularly imprinted polymer (granularity is 38.5 μ m～75 μ m) of embodiment 1 preparation to fill in the empty pillar of 3mL Solid-Phase Extraction (150mg/ post), successively with 3mL methyl alcohol, the activation of 3mL water balance.
The sample of present embodiment is the valnemulin acetonitrile solution of 1,5,10 and 50 μ g/mL series concentration, gets sample on the sample of 2～5mL, with 3mL water, the washing of 3mL acetonitrile, press dry 5% ammonification methyl alcohol 5mL wash-out.Nitrogen carefully dries up, and with the moving phase dissolving, crosses the syringe needle filter membrane, detects with HPLC-UV.Detected result as shown in Figure 1, the AU of ordinate zou is an absorbance unit among the figure, X-coordinate is represented the time, is unit with minute (min).Provide two chromatographic curves among Fig. 1, wherein a is that the valnemulin acetonitrile solution is handled chromatographic curve through the NIP solid phase extraction column, and b is that the valnemulin acetonitrile solution is handled chromatographic curve through the MIP solid phase extraction column.Experimental result shows that the rate of recovery is greater than 95% on molecularly imprinted polymer (MIPs) solid phase extraction column for the valnemulin acetonitrile solution of series concentration, and the rate of recovery is less than 25% on non-imprinted polymer (NIPs) solid phase extraction column.
The molecularly imprinted polymer solid-phase extraction column of embodiment 3 preparations is used for the mensuration of feed valnemulin
Present embodiment selects the molecularly imprinted polymer (granularity is 38.5 μ m～75 μ m) of embodiment 1 preparation to fill in the empty pillar of 3mL Solid-Phase Extraction (150mg/ post), successively with 3mL methyl alcohol, the activation of 3mL water balance.
The sample of present embodiment be feed with organic solvent extraction after, dry up, with acetonitrile dissolving, the valnemulin feed substrate acetonitrile solution of preparation 10 and 50 μ g/mL concentration.Get 2mL and go up sample,, press dry 5% ammonification methyl alcohol 5mL wash-out with 3mL water, the washing of 3mL acetonitrile.Nitrogen carefully dries up, and with the moving phase dissolving, crosses the syringe needle filter membrane, detects for HPLC-UV.Detected result as shown in Figure 2, the AU of ordinate zou is an absorbance unit among the figure, X-coordinate is represented the time, is unit with minute (min).Provide two chromatographic curves among Fig. 2, wherein a is that valnemulin feed substrate acetonitrile solution is handled chromatographic curve through the NIP solid phase extraction column, and b is that valnemulin feed substrate acetonitrile solution is handled chromatographic curve through the MIP solid phase extraction column.Experimental result shows, valnemulin feed substrate acetonitrile solution, and the rate of recovery is greater than 85% on the MIPs solid phase extraction column, and the rate of recovery is less than 20% on the NIPs solid phase extraction column.
Claims (9)
1. preparation method who is used to detect the molecularly imprinted polymer of valnemulin, it is characterized in that described method is is template with the valnemulin precursor, prepares Molecularly Imprinted Polymer by mass polymerization, precipitation polymerization method, situ aggregation method or suspension polymerization.
2. the preparation method who is used to detect the molecularly imprinted polymer of valnemulin according to claim 1, it is characterized in that described method is at 50～80 ℃ of polymerization 24～48h with template, function monomer, linking agent, pore-creating agent and initiator, remove template after the pulverizing, prepare molecularly imprinted polymer.
3. the preparation method who is used to detect the molecularly imprinted polymer of valnemulin according to claim 2, it is characterized in that described method is template, pore-creating agent and function monomer to be mixed to form prepolymer earlier, after in prepolymer, adding linking agent and initiator then, last 50～80 ℃ of polymerization 24～48h, remove template after the pulverizing, prepare molecularly imprinted polymer.
4. the preparation method who is used to detect the molecularly imprinted polymer of valnemulin according to claim 3, the preparation method who it is characterized in that described prepolymer is: after valnemulin precursor and pore-creating agent dissolving mixing, add function monomer, mix the back 4～8 ℃ of standing over night, form prepolymer.
5. the preparation method who is used to detect the molecularly imprinted polymer of valnemulin according to claim 4, the ratio that it is characterized in that described template, function monomer, linking agent, pore-creating agent and initiator is 1: 3～8: 15～40: 3～200: 10～60 (mmol: mmol: mmol: mL: mg).
6. according to the described preparation method who is used to detect the molecularly imprinted polymer of valnemulin of any claim in the claim 1～4, it is characterized in that described function monomer is methacrylic acid, acrylamide, 2-vinylpyridine or 4-vinylpyridine.
7. according to the described preparation method who is used to detect the molecularly imprinted polymer of valnemulin of any claim in the claim 1～4, it is characterized in that described linking agent is ethylene glycol dimethacrylate, trimethoxy propane trimethyl acrylic ester or divinylbenzene.
8. according to the described preparation method who is used to detect the molecularly imprinted polymer of valnemulin of any claim in the claim 1～4, it is characterized in that described pore-creating agent is acetonitrile, methyl alcohol, ethanol, acetone or its solution.
According to Claim 8 in the described preparation method who is used to detect the molecularly imprinted polymer of valnemulin of any claim, it is characterized in that described pore-creating agent is that volume ratio is 20: 1～4 acetonitrile solution.
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| CN102504101A (en) * | 2011-11-09 | 2012-06-20 | 华南农业大学 | Molecularly imprinted polymer for detecting methyl-2-acetyl-N-1,4-dioxyquioxaline and preparation method thereof |
| CN102698720A (en) * | 2012-05-28 | 2012-10-03 | 河海大学 | Method for preparing extraction probe by means of micro-solid phase extraction based on polymer (methacrylic acid-ethyl glycol dimethacrylate) |
| CN105218746A (en) * | 2014-06-13 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of molecularly imprinted polymer and its preparation method and application |
| CN114029037A (en) * | 2021-11-17 | 2022-02-11 | 赣江中药创新中心 | Reversed phase chromatographic stationary phase and preparation method and application thereof |
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| CN101665551A (en) * | 2009-10-16 | 2010-03-10 | 江苏大学 | Method for preparing apiolin molecularly imprinted polymer |
| CN101768238A (en) * | 2010-01-15 | 2010-07-07 | 中国科学院生态环境研究中心 | Citrinin molecular engram material and preparation method as well as application thereof |
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| CN101565485A (en) * | 2009-05-22 | 2009-10-28 | 南京医科大学 | Method for preparing molecularly imprinted polymers of ethinylestradiol analogue |
| CN101665551A (en) * | 2009-10-16 | 2010-03-10 | 江苏大学 | Method for preparing apiolin molecularly imprinted polymer |
| CN101768238A (en) * | 2010-01-15 | 2010-07-07 | 中国科学院生态环境研究中心 | Citrinin molecular engram material and preparation method as well as application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504101A (en) * | 2011-11-09 | 2012-06-20 | 华南农业大学 | Molecularly imprinted polymer for detecting methyl-2-acetyl-N-1,4-dioxyquioxaline and preparation method thereof |
| CN102504101B (en) * | 2011-11-09 | 2014-02-19 | 华南农业大学 | Molecularly imprinted polymer for detecting methyl-2-acetyl-N-1,4-dioxyquioxaline and preparation method thereof |
| CN102698720A (en) * | 2012-05-28 | 2012-10-03 | 河海大学 | Method for preparing extraction probe by means of micro-solid phase extraction based on polymer (methacrylic acid-ethyl glycol dimethacrylate) |
| CN105218746A (en) * | 2014-06-13 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of molecularly imprinted polymer and its preparation method and application |
| CN105218746B (en) * | 2014-06-13 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of molecularly imprinted polymer and its preparation method and application |
| CN114029037A (en) * | 2021-11-17 | 2022-02-11 | 赣江中药创新中心 | Reversed phase chromatographic stationary phase and preparation method and application thereof |
| CN114029037B (en) * | 2021-11-17 | 2023-05-09 | 赣江中药创新中心 | Reversed phase chromatographic stationary phase and preparation method and application thereof |
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Application publication date: 20101222 |