CN101914066B - Method for purifying and detecting pirimicarb by utilizing molecularly imprinted polymer (MIP) - Google Patents
Method for purifying and detecting pirimicarb by utilizing molecularly imprinted polymer (MIP) Download PDFInfo
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Abstract
The invention provides a method for purifying and detecting pirimicarb by utilizing a molecularly imprinted polymer (MIP), belonging to the biochemical technical field. The method comprises the following steps: mixing and dissolving pirimicarb template molecules, a functional monomer of trifluoromethyl acrylic acid and a cross-linking agent of ethylene glycol dimethacrylate in heptane, and adding an initiator of 4,4'-azo-2(4-cyanovaleric acid)-silica gel to the obtained mixed solution; filling up nitrogen for 5-10 minutes, sealing an ampoule under protection of the nitrogen, carrying out water bath and heat preservation at 65-70 DEG C for reacting for 20-30 hours, and then removing the template molecules through soxhlet extraction; drying the polymer without the template molecules at 60 DEG C for staying overnight to obtain the MIP of the pirimicarb; filling the MIP of the pirimicarb into a solid-phase extraction column tube; and activating a solid-phase extraction column, adding sample fruit and vegetable extracting solution, washing the solid-phase extraction column, eluting, purifying and finally collecting the pirimicarb. The method of the invention can make up the pretreatment disadvantage for detecting the pirimicarb in the existing fruit and vegetable environment, simply, rapidly, specifically and efficiently enrich and purify a trace amount of the pirimicarb, and improve the existing detection sensitivity.
Description
Technical field
What the present invention relates to is the method in a kind of biochemical technology field, specifically is a kind of method of utilizing molecularly imprinted polymer to purify and detect PP-062.
Background technology
PP-062 is a kind of carbamate (carbamate) insecticides, and English name primicarb, chemical name are 5,6-dimethyl--2-dimethylin-4-pyrimidyl-dimethylcarbamate.This medicine can be prevented and treated organic phosphorous insecticide is produced all aphids resistance, except that cotton aphid, is usually used in the control of aphid in the fruits and vegetables.Because the amount of transfiniting of PP-062 and ultra scope are used, make the pressure that causes thus become and become increasingly conspicuous environment and food safety.Carbamate chemicals for agriculture toxic action mechanism is similar with organophosphorus pesticide, mainly is to suppress cholinesterase activity, and the hydroxyl that makes the enzyme active center Serine is by carbamylization, thereby loses the hydrolysis ability of enzyme to vagusstoff.In order to ensure people health, countries in the world are to the use of carbamate chemicals for agriculture and residually all done strict regulation and formulated corresponding standard, and wherein China is 1.0mg/kg to the limit standard of PP-062 in the pollution-free vegetable.For measuring PP-062 in the fruits and vegetables, the general methods such as vapor-phase chromatography (GB/T5009.104-2003), liquid phase chromatography that adopt more.Because the matrix of fruits and vegetables is complicated, and often trace existence of PP-062, so be necessary PP-062 is carried out pre-treatment, thus the sensitivity that detects improved.The pre-treating process that adopts at present has distributions of liquid liquid, SPE etc., and wherein solid phase extraction techniques is simple to operate because of it, and saving reagent can be handled a plurality of samples simultaneously and is used widely.But because solid phase extraction filler commonly used at present all is nonspecific with the effect of adsorbing target compound, the selectivity of stationary phase is low, is subject to the interference of complex matrices, has limited this The Application of Technology.Molecular imprinting is based on a kind of functional polymer technology of preparing on the molecular recognition basis; This polymkeric substance adopts molecules of interest or analogue as template when synthetic, and with the template wash-out, polymkeric substance has kept and molecules of interest complementary space structure and group after synthesizing; Has " memory " function; Can be special with the template molecule effect, and through corresponding mode wash-out, to reach the effect of purifying and enrichment molecules of interest.Molecularly imprinted polymer has the advantage of severe environment such as opposing soda acid, and is reusable, is with a wide range of applications.
Retrieval through the prior art document is found; Fung etc. are at " Analytica Chimica Acta " 2006; 576; The last article of delivering of 67-76 " Piezoelectric quartz crystal sensor for rapid analysis of pirimicarb residues using molecularly imprinted polymers as recognition elements " (it is residual to adopt molecularly imprinted polymer to be used for the rapid detection PP-062 as the piezoelectric quartz crystal sensor of discerning material) has synthesized pirimicarb molecularly imprinted polymer, and this research is attempted molecularly imprinted polymer is used for the residual detection of vegetables PP-062 first.But the polymerization method that this article adopted is a situ aggregation method, and existence will be combined in the problem of the PP-062 wash-out difficulty on the polymkeric substance.Pingarr ó n etc. are at " Analytica Chimica Acta " 2002; 451; First pirimicarb molecularly imprinted polymer is applied to solid phase extraction column stuffing in the last article of delivering of 297-304 " Molecularly imprinted polymers for on-line preconcentration by solid phase extraction of pirimicarb in water samples " (PP-062 in the method on-line preconcentration water of use molecularly imprinted polymer SPE); But this article also is to adopt situ aggregation method to prepare polymkeric substance, has the problem of PP-062 wash-out difficulty.Gao etc. are at its paper " Polymer " 2008; 49; Adopt the method for surface grafting to synthesize pirimicarb molecularly imprinted polymer in the article of delivering on 1230～1238 " Molecular imprinted material prepared by novel surface imprinting technique for selective adsorption of pirimicarb " (novel surface aggregate technology preparation has the molecularly imprinted polymer of selective adsorption effect to PP-062), compare advantage with easy wash-out target molecule with the molecularly imprinted polymer of situ aggregation method preparation.But this article just rests on the evaluation phase of polymer physics characteristic and absorption property, not practical application.Up to the present, the pirimicarb molecularly imprinted polymer solid-phase extraction column that does not also adopt the surface aggregate method to prepare is applied to the report of fruits and vegetables sample.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; A kind of method of utilizing molecularly imprinted polymer to purify and detect PP-062 is provided; The present invention adopts the surface aggregate legal system to be equipped with pirimicarb molecularly imprinted polymer, and this molecularly imprinted polymer is applied to solid phase extraction column stuffing, and PP-062 detects the drawback of pre-treatment in the existing fruits and vegetables, in the environment thereby remedy; Simply, quick, special, enrichment efficiently and purifying trace PP-062, improve the existing sensitivity that detects.
The present invention realizes through following technical scheme, the present invention includes following steps:
(1) with template molecule PP-062, function monomer trifluoromethyl acrylate and linking agent ethylene glycol dimethacrylate; Press template molecule: function monomer: linking agent mol ratio=1: 4: 20; Mixed dissolution adds initiator 4,4 '-azo-two (4-cyanopentanoic acid)-silica gel in heptane;
(2) charge into nitrogen 5-10 minute, with the ampere bottle closure, 65 ℃～70 ℃ water bath heat preservations reacted 20～30 hours under nitrogen protection;
(3) through soxhlet extraction, remove template molecule;
(4) will remove 60 ℃ of dried overnight of polymkeric substance of template molecule, obtain the molecularly imprinted polymer of PP-062;
(5) pirimicarb molecularly imprinted polymer is filled in the SPE column jecket;
(6), add the fruits and vegetables sample extracting solution, through drip washing solid-phase extraction column, wash-out, purification and collection PP-062 afterwards to the solid-phase extraction column activation.
The described SPE column jecket that is filled into, under the state of vacuumizing, with the homogenate Vestolen PP 7052 solid phase extraction column of packing into, the top of filler and bottom are loaded onto the Vilaterm sieve plate respectively.
The described SPE column jecket that is filled into is meant with methyl alcohol drip washing Vestolen PP 7052 solid phase extraction column and sieve plate, and the weighing pirimicarb molecularly imprinted polymer after methyl alcohol homogenate, is filled in commercial 1ml～6ml Vestolen PP 7052 solid phase extraction column.
Described sieve plate, the aperture of sieve plate are 20 μ m.
Described weighing pirimicarb molecularly imprinted polymer, its quality are 20mg～200mg.
Described solid-phase extraction column activation is meant the deionized water activation solid-phase extraction column with 2 times of column volumes.
Described fruits and vegetables sample extracting solution, its preparation method are after fruits and vegetables are removed non-food part, accurately weighing; Add the isopyknic deionized water of people, smash to pieces, place tool plug Erlenmeyer flask; The 10min that on electrodynamic shaker, vibrates with the centrifugal 5min of 3000r/min, draws supernatant.
Described adding sample is 2ml.
Described drip washing is meant the heptane drip washing solid-phase extraction column with 2 times of column volumes.
Described wash-out is meant mixed solution (methyl alcohol: water: acetate=7: 2: 1, volume ratio) the wash-out PP-062 with 2 times of column volumes.
Among the present invention, the synthetic pirimicarb molecularly imprinted polymer has and template molecule complementary group and conformation mutually on silica gel surface, has " memory " function, so template molecule is had very high specificity and selectivity.The molecularly imprinted polymer that adopts the present invention to prepare can be used for the pre-treatment practice of fruits and vegetables sample and water sample as the filler of solid-phase extraction column; Thereby realize removal to the fruits and vegetables matrix of Interference Detection; The PP-062 that enriched with trace is residual improves the sensitivity that detects.And the molecularly imprinted polymer of the present invention's preparation is a silica gel surface aggregate thing, has to be prone to the template molecule wash-out is got advantage.The solid phase extraction column that method of the present invention is more common has the advantages that specificity is good, capacity is high.
Embodiment
Elaborate in the face of embodiments of the invention down: present embodiment provided concrete embodiment and detailed operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1:
One, the preparation of pirimicarb molecularly imprinted polymer
With PP-062 (template molecule) 0.2mmol, function monomer trifluoromethyl acrylate (TFMAA) and linking agent ethylene glycol dimethacrylate (EDMA); Mol ratio mixing according to 1: 4: 20; Be dissolved in the 20mL perforating agent (heptane), insert in the ampere bottle prepolymerization 2 hours.Add initiator 4,4 '-azo-two (4-cyanopentanoic acid)-silica gel (ACPA-silica gel) 0.08mmol charged into nitrogen 5 minutes, vacuum seal, 65 ℃ of oil bath thermopolymerizations 24 hours.Removed template molecule in 12 hours through soxhlet extraction, extraction agent consist of methanol-water-acetate mixed solution (7: 2: 1, V/V/V).Get elutriant 20 μ l, HPLC detect wash-out fully after, with 60 ℃ of dryings of polymkeric substance 24 hours.
Two, the preparation of pirimicarb molecularly imprinted polymer solid phase extraction column
At first use washed with methanol solid phase extraction column and sieve plate, 100mg uses methyl alcohol homogenate with the synthetic molecularly imprinted polymer, is filled in the Vestolen PP 7052 solid phase extraction column, and column volume is 3ml, under the state of vacuumizing, compresses filler, adds the Vilaterm sieve plate at last.
Three, the PP-062 in pirimicarb molecularly imprinted polymer solid phase extraction column purifying, the enrichment Kidney bean is residual
Priority is with the deionized water activation solid-phase extraction column of the methyl alcohol of 2 times of column volumes, 2 times of column volumes; Attention can not make it with 2 times of column volume heptane wash pillars; The PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.Drain.Sample behind the adding 2ml water extraction with 2 times of column volume heptane wash pillars, is drained, and the PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.
After sample crossed rate with 0.22 μ m filter membrane, get appearance on the 20 μ l, with the HPLC sample separation and pass through the concentration of PP-062 in the UV-detector test sample.
Present embodiment synthetic molecularly imprinted polymer can be special the identification PP-062, adopt the method for present embodiment can be used for separation, purification and the enrichment of Kidney bean PP-062.The recovery to adding 10 μ g/g standard models in the Kidney bean is 90.3%, and other similar drugs are not had specific adsorption.
Embodiment 2:
One, the preparation of pirimicarb molecularly imprinted polymer
With PP-062 (template molecule) 0.2mmol, function monomer trifluoromethyl acrylate (TFMAA) and linking agent ethylene glycol dimethacrylate (EDMA); Mol ratio mixing according to 1: 4: 20; Be dissolved in the 20mL perforating agent (heptane), insert in the ampere bottle prepolymerization 2 hours.Add initiator 4,4 '-azo-two (4-cyanopentanoic acid)-silica gel (ACPA-silica gel) 0.08mmol charged into nitrogen 5 minutes, vacuum seal, 70 ℃ of oil bath thermopolymerizations 20 hours.Removed template molecule in 12 hours through soxhlet extraction, extraction agent consist of methanol-water-acetate mixed solution (7: 2: 1, V/V/V).Get elutriant 20 μ l, HPLC detect wash-out fully after, with 60 ℃ of dryings of polymkeric substance 24 hours.
Two, the preparation of pirimicarb molecularly imprinted polymer solid phase extraction column
At first use washed with methanol solid phase extraction column and sieve plate, 200mg uses methyl alcohol homogenate with the synthetic molecularly imprinted polymer, is filled in the Vestolen PP 7052 solid phase extraction column, and column volume is 6ml, under the state of vacuumizing, compresses filler, adds the Vilaterm sieve plate at last.
Three, the PP-062 in pirimicarb molecularly imprinted polymer solid phase extraction column purifying, the enrichment rape is residual
Priority is with the deionized water activation solid-phase extraction column of the methyl alcohol of 2 times of column volumes, 2 times of column volumes; Attention can not make it with 2 times of column volume heptane wash pillars; The PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.Drain.Sample behind the adding 2ml water extraction with 2 times of column volume heptane wash pillars, is drained, and the PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.
After sample crossed rate with 0.22 μ m filter membrane, get appearance on the 20 μ l, with the HPLC sample separation and pass through the concentration of PP-062 in the UV-detector test sample.
Present embodiment synthetic molecularly imprinted polymer can be special the identification PP-062, adopt the method for present embodiment can be used for separation, purification and the enrichment of rape PP-062.The recovery to adding 100 μ g/g standard models in the rape is 92.5%, and other similar drugs are not had specific adsorption.
Embodiment 3:
One, the preparation of pirimicarb molecularly imprinted polymer
With PP-062 (template molecule) 0.2mmol, function monomer trifluoromethyl acrylate (TFMAA) and linking agent ethylene glycol dimethacrylate (EDMA); Mol ratio mixing according to 1: 4: 20; Be dissolved in the 20mL perforating agent (heptane), insert in the ampere bottle prepolymerization 2 hours.Add initiator 4,4 '-azo-two (4-cyanopentanoic acid)-silica gel (ACPA-silica gel) 0.08mmol charged into nitrogen 5 minutes, vacuum seal, 70 ℃ of oil bath thermopolymerizations 30 hours.Removed template molecule in 12 hours through soxhlet extraction, extraction agent consist of methanol-water-acetate mixed solution (7: 2: 1, V/V/V).Get elutriant 20 μ l, HPLC detect wash-out fully after, with 60 ℃ of dryings of polymkeric substance 24 hours.
Two, the preparation of pirimicarb molecularly imprinted polymer solid phase extraction column
At first use washed with methanol solid phase extraction column and sieve plate, 20mg uses methyl alcohol homogenate with the synthetic molecularly imprinted polymer, is filled in the Vestolen PP 7052 solid phase extraction column, and column volume is 1ml, under the state of vacuumizing, compresses filler, adds the Vilaterm sieve plate at last.
Three, the PP-062 in pirimicarb molecularly imprinted polymer solid phase extraction column purifying, the enrichment apple is residual
Priority is with the deionized water activation solid-phase extraction column of the methyl alcohol of 2 times of column volumes, 2 times of column volumes; Attention can not make it with 2 times of column volume heptane wash pillars; The PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.Drain.Sample behind the adding 2ml water extraction with 2 times of column volume heptane wash pillars, is drained, and the PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.
After sample crossed rate with 0.22 μ m filter membrane, get appearance on the 20 μ l, with the HPLC sample separation and pass through the concentration of PP-062 in the UV-detector test sample.
Present embodiment synthetic molecularly imprinted polymer can be special the identification PP-062, adopt the method for present embodiment can be used for separation, purification and the enrichment of apple PP-062.The recovery to adding 1 μ g/g standard model in the apple is 88.7%, and other similar drugs are not had specific adsorption.
Embodiment 4:
One, the preparation of pirimicarb molecularly imprinted polymer
With PP-062 (template molecule) 0.2mmol, function monomer trifluoromethyl acrylate (TFMAA) and linking agent ethylene glycol dimethacrylate (EDMA); Mol ratio mixing according to 1: 4: 20; Be dissolved in the 20mL perforating agent (heptane), insert in the ampere bottle prepolymerization 2 hours.Add initiator 4,4 '-azo-two (4-cyanopentanoic acid)-silica gel (ACPA-silica gel) 0.08mmol charged into nitrogen 5 minutes, vacuum seal, 65 ℃ of oil bath thermopolymerizations 30 hours.Removed template molecule in 12 hours through soxhlet extraction, extraction agent consist of methanol-water-acetate mixed solution (7: 2: 1, V/V/V).Get elutriant 20 μ l, HPLC detect wash-out fully after, with 60 ℃ of dryings of polymkeric substance 24 hours.
Two, the preparation of pirimicarb molecularly imprinted polymer solid phase extraction column
At first use washed with methanol solid phase extraction column and sieve plate, 100mg uses methyl alcohol homogenate with the synthetic molecularly imprinted polymer, is filled in the Vestolen PP 7052 solid phase extraction column, and column volume is 3ml, under the state of vacuumizing, compresses filler, adds the Vilaterm sieve plate at last.
Three, the PP-062 in pirimicarb molecularly imprinted polymer solid phase extraction column purifying, the enrichment tap water is residual
Priority is with the deionized water activation solid-phase extraction column of the methyl alcohol of 2 times of column volumes, 2 times of column volumes; Attention can not make it with 2 times of column volume heptane wash pillars; The PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.Drain.Add 500ml tap water sample, with 2 times of column volume heptane wash pillars, drain, the PP-062 of using 2 times of column volume damping fluids (methyl alcohol: water: acetate=7: 2: 1, volume ratio) will be adsorbed on the MIP-SPE post afterwards elutes.
After sample crossed rate with 0.22 μ m filter membrane, get appearance on the 20 μ l, with the HPLC sample separation and pass through the concentration of PP-062 in the UV-detector test sample.
Present embodiment synthetic molecularly imprinted polymer can be special the identification PP-062, adopt the method for present embodiment can be used for separation, purification and the enrichment of tap water PP-062.The recovery to adding 1 μ g/g standard model in the tap water is 103.2%, and other similar drugs are not had specific adsorption.
Claims (10)
1. a method of utilizing molecularly imprinted polymer to purify and detect PP-062 is characterized in that, comprises the steps:
(1) with template molecule PP-062, function monomer trifluoromethyl acrylate and linking agent ethylene glycol dimethacrylate; Press template molecule: function monomer: linking agent mol ratio=1: 4: 20; Mixed dissolution adds initiator 4,4 '-azo-two (4-cyanopentanoic acid)-silica gel in heptane;
(2) charge into nitrogen 5-10 minute, with the ampere bottle closure, 65 ℃～70 ℃ water bath heat preservations reacted 20～30 hours under nitrogen protection;
(3) through soxhlet extraction, remove template molecule;
(4) will remove 60 ℃ of dried overnight of polymkeric substance of template molecule, obtain the molecularly imprinted polymer of PP-062;
(5) pirimicarb molecularly imprinted polymer is filled in the SPE column jecket;
(6), add the fruits and vegetables sample extracting solution, through drip washing solid-phase extraction column, wash-out, purification and collection PP-062 afterwards to the solid-phase extraction column activation.
2. the method for utilizing molecularly imprinted polymer to purify and detect PP-062 according to claim 1; It is characterized in that the described SPE column jecket that is filled into is under the state of vacuumizing; With the homogenate Vestolen PP 7052 solid phase extraction column of packing into, the top of filler and bottom are loaded onto the Vilaterm sieve plate respectively.
3. according to claim 1 or the 2 described methods of utilizing molecularly imprinted polymer to purify and detect PP-062; It is characterized in that; The described SPE column jecket that is filled into is meant with methyl alcohol drip washing Vestolen PP 7052 solid phase extraction column and sieve plate, weighing pirimicarb molecularly imprinted polymer; After methyl alcohol homogenate, be filled in commercial 1ml～6ml Vestolen PP 7052 solid phase extraction column.
4. the method for utilizing molecularly imprinted polymer to purify and detect PP-062 according to claim 3 is characterized in that, described sieve plate, and the aperture of sieve plate is 20 μ m.
5. the method for utilizing molecularly imprinted polymer to purify and detect PP-062 according to claim 3 is characterized in that, described weighing PP-062 molecule seal polymkeric substance, and its quality is 20mg～200mg.
6. the method for utilizing molecularly imprinted polymer to purify and detect PP-062 according to claim 1 is characterized in that described solid-phase extraction column activation is meant the deionized water activation solid-phase extraction column with 2 times of column volumes.
7. the method for utilizing molecularly imprinted polymer to purify and detect PP-062 according to claim 1 is characterized in that described fruits and vegetables sample extracting solution; Its preparation method is for after removing fruits and vegetables non-food part, and accurately weighing adds isopyknic deionized water; Smash to pieces, place tool plug Erlenmeyer flask, 10min vibrates on electrodynamic shaker; With the centrifugal 5min of 3000r/min, draw supernatant.
8. according to claim 1 or the 7 described methods of utilizing molecularly imprinted polymer to purify and detect PP-062, it is characterized in that described adding sample is 2ml.
9. the method for utilizing molecularly imprinted polymer to purify and detect PP-062 according to claim 1 is characterized in that described drip washing is meant the heptane drip washing solid-phase extraction column with 2 times of column volumes.
10. the method for utilizing molecularly imprinted polymer to purify and detect PP-062 according to claim 1; It is characterized in that; Described wash-out is meant the mixed solution wash-out PP-062 with 2 times of column volumes, and said mixed solution is a methyl alcohol: water: acetate volume ratio=7: 2: 1.
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| CN105348437B (en) * | 2015-10-27 | 2017-11-24 | 成都市食品药品检验研究院 | A kind of double-template molecularly imprinted polymer and preparation method and application |
| CN107051403A (en) * | 2017-03-31 | 2017-08-18 | 邵秋荣 | The preparation method of XDI molecularly imprinted solid phase extraction column packing materials |
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