CN101559352A - Molecularly imprinted polymers (MIPs) for inspecting melamine and preparation method thereof - Google Patents
Molecularly imprinted polymers (MIPs) for inspecting melamine and preparation method thereof Download PDFInfo
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Abstract
The invention discloses molecularly imprinted polymers (MIPs) for detecting melamine and a preparation method thereof. The MIPs are prepared by the steps as follows: cyromazine is used as a virtual moulding board and is polymerized with a functional monomer, a cross linker agent, a pore-foaming agent and an initiator at the temperature from 50 to 80 DEG C to obtain a bulk polymer; and after being processed by the operations of pulverization, screen separation, moulding board removal by acetic acid methanol and methanol, the bulk polymer is processed by vacuum drying to prepare the MIPs which have high cross reaction and outstanding selectivity to melamine. The invention selects the cyromazine as the virtual moulding board to prepare the MIPs, and avoids the problem that the melamine is hard to dissolve in a polymerization system and the problem that when the MIPs prepared by using the melamine as the moulding board is used for solid phase extraction of fill materials, moulding board leakage can lead to an inaccurate result; the invention selects the mixed system of methanol and water as the pore-foaming agent, and the prepared MIPs have high compatibility with the melamine in an aqueous solution; and used as a sample pre-processing material for analyzing the melamine, the prepared MIPs have broad application prospect.
Description
Technical field
The present invention relates to material chemistry technical field, be specifically related to a kind of molecularly imprinted polymer of detecting melamine and preparation method thereof that is used to.
Background technology
Melamine (melamine) claims melamine, cyanuramide, three polyamide, extract of protein again, and chemical name is 2,4,6-triamido-1,3, the 5-triazine is a kind of important Organic Chemicals, is widely used in the production of plastics, coating, adhesive and packaging material for food.Because the melamine nitrogen content is up to 66%, compare and contain more a high proportion of nitrogen-atoms with protein (average nitrogen content 16%), so utilized by some fake producers, be added in feed and the food causing the higher illusion of protein content, thereby cause such as serious food security accidents such as U.S.'s pet food contamination accident in 2007 and Chinese malicious milk powder case in 2008, malicious egg incidents.
At above-mentioned situation, China relevant departments strictly tackle, the positive tissue personnel carry out methodological study, and standard promulgations such as existing at present NY/T 1372-2007, GB/T 22388-2008 and GB/T 22400-2008 are for melamine detection and monitoring in feed, the food provide abundant assurance.But the pre-treating method that existing all melamines detect all is to adopt traditional solid phase extraction column (as C
18, MCX etc.) purify, lack selectivity, specificity is not strong, thereby influences the sensitivity of whole detection method and accurately quantitatively, the pillar use of yet cannot regenerating.
Molecular engram solid phase extraction technology based on similar antigen-antibody reaction has high selectivity and specificity, is a kind of SPE material with wide application prospect.If can be as antibody, the isolation medium that melamine is had a high selectivity of synthetic some similar antibody then can improve sensitivity and the accuracy that melamine detects greatly.
Molecular engram (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 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 reversible compound on every side by interacting on (covalently or non-covalently key) with template molecule;
2, copolymerization generation high polymer takes place in function monomer and excessive crosslinking agent in the presence of pore-foaming agent;
3, template molecule is dissociated out from high polymer, in polymer, just formed can the recognition template molecule binding site.
This imprinted polymer can be used as the sensing element of fixedly phase, catalysts selective, chemical sensor of liquid chromatogram and solid extracting agent etc., also is widely used in the clinical medicine analysis.
Suitable template is to prepare the key that melamine is had the molecularly imprinted polymer of high specific.Melamine is a kind of water-soluble polar substances, this detects melamine pre-treatment molecularly imprinted polymer as the template preparation with melamine, on the one hand, there is not suitable pore-foaming agent, on the other hand, have the template leakage problem, the molecularly imprinted polymer that melamine is had high specific is difficult to obtain.Therefore, it is similar to seek a kind of and melamine molecule structure, and the relatively littler template molecule of polarity is extremely important.
Summary of the invention
The objective of the invention is to overcome the problem that the SPE material exists in the existing melamine detection pre-treating method, provide a kind of can high selectivity and high specific identification melamine, can be used for detecting the molecularly imprinted polymer of melamine.
Another object of the present invention provides a kind of method of the above-mentioned molecularly imprinted polymer of preparation simple to operate, with low cost.
Above-mentioned purpose of the present invention is achieved by following scheme:
Itself be not suitable as template at melamine and prepare molecularly imprinted polymer, and template plays a very important role to the specificity tool of molecularly imprinted polymer, so the inventor is after research and screening, find that melamine is cyclopropylamine piperazine (Cyromazine, fly eradication amine) a kind of metabolite, substituting group difference on the amino is only arranged between the two, and the cyclopropyl in the cyclopropylamine piperazine molecule has increased its hydrophobicity, help the selection of the pore-foaming agent of polymerization system, it is expected to the desirable alternate template as melamine.
The present invention selects the cyclopropylamine piperazine 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 melamine is had high specific.
In order further to improve the specificity of molecularly imprinted polymer of the present invention to melamine, 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 (cyclopropylamine piperazine), function monomer, crosslinking agent, pore-foaming agent and initator at 50～80 ℃ of polymerization 4～48h, remove template after the pulverizing, prepare molecularly imprinted polymer.
The amount ratio of above-mentioned template, function monomer, crosslinking agent, pore-foaming agent and initator 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, acrylic acid, acrylamide, 2-vinylpyridine or 4-vinylpyridine etc.
Above-mentioned crosslinking agent is ethylene glycol dimethacrylate, trimethoxy propane trimethyl acrylic ester or divinylbenzene etc.
Above-mentioned pore-foaming agent is the mixed solution of polar organic solvent and water, as the mixed solution of mixed solution, acetonitrile and the water of the mixed solution of first alcohol and water, second alcohol and water or mixed solution of acetone and water etc.
Pore-foaming agent will guarantee the abundant dissolving of template on the one hand, the pore-foaming agent consumption has material impact to molecularly imprinted polymer intensity, the surface characteristic of preparation on the other hand, and pore-foaming agent is also very relevant to the identification of imprinted polymer melamine in the working medium system simultaneously.Therefore the inventor optimizes pore-foaming agent, found that when pore-foaming agent is selected the mixed solution of first alcohol and water, can prepare the molecularly imprinted polymer that melamine is had high degree of specificity identification.
Because molecularly imprinted polymer can not have too many moisture, so the proportionate relationship of organic solvent and water is selected methyl alcohol in the pore-foaming agent mixed solution: the volume ratio of water=20: (1～4) can better realize the present invention, preferred 10: 1.
Above-mentioned initator can be selected this area any initator commonly used, and water soluble starter or oil-soluble initiator can be realized the present invention, as azodiisobutyronitrile, Ammonium Persulfate 98.5 etc.
Remove template after the above-mentioned pulverizing, can adopt 10% acetate methyl alcohol (acetate and methyl alcohol mix by 1: 9 volume ratio), methyl alcohol to remove template.
Preparation method's of the present invention preferred version is: earlier template, pore-foaming agent and function monomer are mixed with the formation prepolymer, add crosslinking agent and initator again at 50～80 ℃ of polymerization 4～48h, remove template after the pulverizing, prepare molecularly imprinted polymer.
In the said method, the concrete preparation process of prepolymer is with after cyclopropylamine piperazine and the pore-foaming 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-foaming agent and function monomer are mixed with the formation prepolymer, in prepolymer, add crosslinking agent and initator, cause photopolymerization with UV-irradiation under elder generation's low temperature (as 4 ℃), 50～80 ℃ of polymerization 4～48h again, remove template after the pulverizing, prepare molecularly imprinted polymer.
Above-mentioned photopolymerization is 4～8 ℃, polymerization 4～24h.
Molecularly imprinted polymer of the present invention, find after testing: this polymer is used for SPE purifies (200mg/ post), polymer is about 300.0 μ g/g polymer in conjunction with the adsorbance of melamine; Running water, underground and surface water and seawater add the melamine recovery test and show, in 1-50 μ g/mL added horizontal extent, the melamine rate of recovery was greater than 95%; Show that to adding the melamine recovery test in feed, milk powder and the milk rate of recovery of melamine is higher than 85%; The rate of recovery of melamine is greater than 70% in the pig urine; The rate of recovery is higher than 65% in the egg; The solid phase extraction column of molecularly imprinted polymer of the present invention filling, reuse 10 times after, the rate of recovery of melamine is still greater than 70%.
Compared with prior art, the present invention has following beneficial effect:
1. molecularly imprinted polymer of the present invention is that employing is the simulated templates preparation with the similar cyclopropylamine piperazine of melamine structure, because of melamine has identical molecular structure and amido functional group with the cyclopropylamine piperazine, synthetic polymer can optionally be discerned melamine, and melamine is had high specific;
2. molecularly imprinted polymer of the present invention adopts the cyclopropylamine piperazine as template, and on the one hand, cyclopropylamine piperazine polarity is low relatively, helps the selection of pore-foaming agent, on the other hand, can prevent " template leakage ";
3. when the present invention prepares molecularly imprinted polymer, the pore-foaming agent that adopts is the mixed system of first alcohol and water, help the dissolving of template, Zhi Bei imprinted polymer increases the specific recognition ability under water environment simultaneously, and this is just consistent with the sample medium system that melamine exists;
4. preparation method of the present invention can directly carry out 50～80 ℃ of polymerizing curables with adding crosslinking agent and initator 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 10% following acetonitrile or the methanol in water melamine is presented high compatibility 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 object itself (melamine), the present invention is the MIPs that makes of template to the height cross reaction of melamine and remarkable selectivity with the cyclopropylamine piperazine, has a wide range of applications as the sample pre-treatments material of analyzing the melamine in the matrix such as feed, dairy produce, egg and ambient water.
Description of drawings
Fig. 1 is that melamine aqueous medium is handled chromatogram through MIPs solid phase extraction column and NIPs solid phase extraction column respectively;
Wherein, 1 is that melamine aqueous medium is handled chromatographic curve through the NIPs solid phase extraction column, and 2 is that melamine aqueous medium is handled chromatographic curve through the MIPs solid phase extraction column;
Fig. 2 is for the melamine being the chromatogram that the MIPs solid phase extraction column of template and the MIPs solid phase extraction column that with the cyclopropylamine piperazine is template are handled the melamine aqueous solution respectively;
Wherein, 1 for melamine is the chromatographic curve of the MIPs solid phase extraction column processing melamine aqueous solution of template, and 2 for the cyclopropylamine piperazine being the chromatographic curve of the MIPs solid phase extraction column processing melamine aqueous solution of template;
Fig. 3 is that the melamine feed media aqueous solution is handled chromatogram through MIPs solid phase extraction column and NIPs solid phase extraction column respectively;
Wherein, 1 is that the melamine feed media aqueous solution is handled chromatographic curve through the NIPs solid phase extraction column, and 2 is that the melamine feed media aqueous solution is handled chromatographic curve through the MIPs solid phase extraction column;
Fig. 4 is that the melamine cow milk medium aqueous solution is handled chromatogram through MIPs solid phase extraction column and NIPs solid phase extraction column respectively;
Wherein, 1 is that the melamine cow milk medium aqueous solution is handled chromatographic curve through the NIPs solid phase extraction column, and 2 is that the melamine cow milk medium aqueous solution is handled chromatographic curve through the MIPs solid phase extraction column.
The specific 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.
The molecularly imprinted polymer of present embodiment, its synthetic preparation process is as follows:
(1) preparation of prepolymer
Take by weighing 0.166g (1mmol) cyromazine simulated templates in test tube, and adding 5.0mL methanol (10/1, V/V), behind the ultrasonic dissolution, add function monomer methacrylic acid 0.690mL (8mmol), ultrasonic 5min, 4 ℃ of standing over night form prepolymer;
(2) photopolymerization
In above-mentioned prepolymer, add ethylene glycol dimethacrylate 5.00mL (25mmol) and azodiisobutyronitrile 30mg, ultrasonic 5min, logical nitrogen 5min, sealing, at 4 ℃, polymerization 24h under the 365nm UV-irradiation;
(3) polymerizing curable
Above-mentioned photopolymerization product is transferred in 60 ℃ of water-baths polymerization 12h again, obtains bulk polymer, this bulk polymer is the molecularly imprinted polymer that melamine detects that is used for of present embodiment.
Above-mentioned bulk polymer is ground, crosses 200 mesh sieves, with acetone repeatedly sedimentation remove fine particle, pack in 15 * 200mm tool plug glass chromatography column, remove the simulated templates cyromazine with 10% acetate methanol solution 200mL washing earlier, flow velocity is controlled at below the 1mL/min, remove acetate with the 100mL methanol wash again, particle is put dry 24h in 60 ℃ of vacuum drying chambers, put in the drier preserve standby.The granular filler for preparing is compared with synthetic bulk polymer, and yield reaches 62.4%.
The preparation of non-imprinted polymer (NIPs) is except that adding the template molecule, all prepares as stated above and handles.
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 SPE (200mg/ post), successively with 3mL methyl alcohol, the activation of 3mL water balance.
The sample of present embodiment is the melamine aqueous solution of 0.5,2,10 and 50 μ g/mL series concentration, gets sample on the sample of 2～5mL, with 3mL water, 3mL methanol wash, press dry 5% ammonification methyl alcohol 5mL wash-out.Nitrogen carefully dries up, and with flowing phased soln, high speed centrifugation detects with HPLC-UV, testing result as shown in Figure 1, the AU of ordinate is an absorbance unit among the figure, the m=milli, abscissa is represented the time, is unit with minute (min).
Provide two chromatographic curves among Fig. 1, wherein 1 is that melamine aqueous medium is handled chromatographic curve through the NIPs solid phase extraction column, 2 is that melamine aqueous medium is handled chromatographic curve through the MIPs solid phase extraction column, experimental result shows, the rate of recovery is greater than 95% on molecularly imprinted polymer (MIPs) solid phase extraction column for the melamine aqueous solution of series concentration, and the rate of recovery is less than 5% on non-imprinted polymer (NIPs) solid phase extraction column.
It is that template and cyclopropylamine piperazine are the performance measurement of the molecularly imprinted polymer of template that embodiment 3 is used to detect melamine
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 SPE (200mg/ post), successively with 3mL methyl alcohol, the activation of 3mL water balance.
The sample of present embodiment is the 0.5 and 10 μ g/mL melamine aqueous solution, gets sample on the 2mL sample, with 3mL water, 3mL methanol wash, press dry 5% ammonification methyl alcohol 5mL wash-out.Nitrogen carefully dries up, and with the phased soln that flows, high speed centrifugation, detects with HPLC-UV, and testing result as shown in Figure 2.
Provide two chromatographic curves among Fig. 2, wherein 1 for melamine is the chromatographic curve of the MIPs solid phase extraction column processing melamine aqueous solution of template, and 2 for the cyclopropylamine piperazine being the chromatographic curve of the MIPs solid phase extraction column processing melamine aqueous solution of template; Experimental result shows, under batten spare on the melamine aqueous solution 2mL of 0.5 and 10 μ g/mL, with the melamine is that template is by the synthetic MIPs of embodiment 1 method, less than 40%, the rate of recovery is greater than 95% on the cyclopropylamine piperazine solid phase extraction column to the rate of recovery of melamine for the solid phase extraction column of filling.
The molecularly imprinted polymer solid-phase extraction column of embodiment 4 preparations is used for the mensuration of feed melamine
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 SPE (200mg/ post), successively with 3mL methyl alcohol, the activation of 3mL water balance.
The sample of present embodiment be feed with 1% trichloroacetic acid extract, centrifugal after, solution is transferred pH to 7.0 through 50% ammoniacal liquor, the melamine feed substrate that is used to prepare 2,10 and 50 μ g/mL concentration extracts the aqueous solution.Get 2mL and go up sample,, press dry 5% ammonification methyl alcohol 5mL wash-out with 3mL water, 3mL methanol wash.Nitrogen carefully dries up, and with the phased soln that flows, high speed centrifugation, detects with HPLC-UV, and testing result as shown in Figure 3.
Provide two chromatographic curves among Fig. 3, wherein 1 is that the melamine feed media aqueous solution is handled chromatographic curve through the NIPs solid phase extraction column, and 2 is that the melamine feed media aqueous solution is handled chromatographic curve through the MIPs solid phase extraction column; Experimental result shows, goes up under the batten spare at the melamine feed extraction aqueous solution 2mL of 2,10 and 50 μ g/mL, and the rate of recovery is greater than 90% on the MIPs solid phase extraction column, and the rate of recovery is less than 10% on the NIPs solid phase extraction column.
The molecularly imprinted polymer solid-phase extraction column of embodiment 5 preparations is used for the mensuration of milk melamine
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 SPE (200mg/ post), successively with 3mL methyl alcohol, the activation of 3mL water balance.
The sample of present embodiment be milk with 1% trichloroacetic acid (mass percent) and 2% lead acetate (mass percent) extract, centrifugal after, supernatant is transferred pH to 7.0 with 50% ammoniacal liquor, is used to prepare the melamine milk substrate extraction solution of 1,5 and 20 μ g/mL concentration.Get 2mL and go up sample,, press dry 5% ammonification methyl alcohol 5mL wash-out with 3mL water, 3mL methanol wash.Nitrogen carefully dries up, and with the phased soln that flows, high speed centrifugation, detects with HPLC-UV, and testing result as shown in Figure 4.
Provide two chromatographic curves among Fig. 4, wherein 1 is that the melamine cow milk medium aqueous solution is handled chromatographic curve for the melamine cow milk medium aqueous solution through the MIPs solid phase extraction column through NIPs solid phase extraction column processing chromatographic curve 2; Experimental result shows, goes up under the batten spare at the melamine feed extraction aqueous solution 2mL of 1,5 and 20 μ g/mL, and the rate of recovery is greater than 85% on the MIPs solid phase extraction column, and the rate of recovery is less than 10% on the NIPs solid phase extraction column.
Claims (10)
1, a kind of molecularly imprinted polymer that is used to detect melamine is characterized in that this polymer is is that template preparation gets with the cyclopropylamine piperazine.
2, a kind of method for preparing the described molecularly imprinted polymer of claim 1, it is characterized in that this method is at 50～80 ℃ of polymerization 4～48h with template, function monomer, crosslinking agent, pore-foaming agent and initator, remove template after the pulverizing, prepare molecularly imprinted polymer.
3, according to the described method of claim 2, the ratio that it is characterized in that described template, function monomer, crosslinking agent, pore-foaming agent and initator is 1: 3～8: 15～40: 3～200: 10～60, and described ratio is mmol: mmol: mmol: mL: mg.
4,, it is characterized in that described function monomer is methacrylic acid, acrylic acid, acrylamide, 2-vinylpyridine or 4-vinylpyridine according to the described method of claim 2.
5,, it is characterized in that described crosslinking agent is ethylene glycol dimethacrylate, trimethoxy propane trimethyl acrylic ester or divinylbenzene according to the described method of claim 2.
6,, it is characterized in that described pore-foaming agent is the mixed solution of mixed solution, acetonitrile and water of mixed solution, second alcohol and water of first alcohol and water or the mixed solution of acetone and water according to the described method of claim 2.
7,, it is characterized in that described pore-foaming agent is that volume ratio is the mixed liquor of 20: 1～4 first alcohol and water according to the described method of claim 6.
8, according to the described method of claim 2, it is characterized in that this method is earlier template, pore-foaming agent and function monomer low-temperature mixed to be formed prepolymer, after in prepolymer, adding crosslinking agent and initator then, cause photopolymerization with UV-irradiation under the low temperature again, last 50～80 ℃ of polymerization 4～48h, remove template after the pulverizing, prepare molecularly imprinted polymer.
9, described according to Claim 8 method is characterized in that the concrete preparation process of described prepolymer is: after cyclopropylamine piperazine and pore-foaming agent dissolving mixing, add function monomer, mix the back 4～8 ℃ of standing over night, form prepolymer.
10, described according to Claim 8 method is characterized in that described photopolymerization is 4～8 ℃, polymerization 4～48 hours.
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