CN106317325A - Triazole pesticide molecularly imprinted polymer microspheres, solid-phase extraction column and application of solid-phase extraction column - Google Patents

Triazole pesticide molecularly imprinted polymer microspheres, solid-phase extraction column and application of solid-phase extraction column Download PDF

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CN106317325A
CN106317325A CN201610825339.4A CN201610825339A CN106317325A CN 106317325 A CN106317325 A CN 106317325A CN 201610825339 A CN201610825339 A CN 201610825339A CN 106317325 A CN106317325 A CN 106317325A
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triazole
solid
phase extraction
triazole pesticide
extraction column
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CN106317325B (en
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佘永新
王静
赵风年
张超
王珊珊
金茂俊
金芬
邵华
郑露飞
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Beijing Purkinje General Instrument Co Ltd
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Institute of Agricultural Quality Standards and Testing Technology of CAAS
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08Selective adsorption, e.g. chromatography
    • B01D15/10Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/268Polymers created by use of a template, e.g. molecularly imprinted polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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    • C08J2201/00Foams characterised by the foaming process
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    • C08J2335/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/02Characterised by the use of homopolymers or copolymers of esters

Abstract

The invention relates to the field of compound extraction and separation purification, in particular to triazole pesticide molecularly imprinted polymer microspheres, a solid-phase extraction column filled with the riazole pesticide molecularly imprinted polymer microspheres and application of solid-phase extraction column. The triazole pesticide molecularly imprinted polymer microspheres are prepared by using triadimefon as the template molecule, methacrylic acid as the functional monomer, trimethylolpropane trimethyl acrylate as the crosslinking agent and azodiisobutyronitrile as initiator to perform reaction in an inert solvent and then removing the template molecule.

Description

Triazole pesticide molecular blotting polymer microsphere, solid-phase extraction column and application thereof
Technical field
The present invention relates to compound extraction and isolated and purified field, in particular to a kind of triazole pesticide molecule print Mark polymer microballoon, solid-phase extraction column and application thereof.
Background technology
Triazole pesticide has had shown that huge potentiality since 20 century 70s occur in terms of prevention and elimination of disease and pests. Triazole pesticide, based on antibacterial, the feature such as generally has efficiently, low toxicity, low-residual, lasting period length, interior absorption are strong.In addition Triazole type is at home and abroad widely used as plant growth regulator, particularly the application of paclobutrazol.
The triazole pesticide residence time in soil is the longest, and its metabolism relies primarily on photodissociation and microbial degradation. Although triazole pesticide low toxicity, low-residual, safer to people and animals, if but abusing in agricultural product and use, not only with excess Pest and disease damage Drug resistance can be made to be on the rise, its high residue problem in agricultural product and environment can be produced simultaneously, threaten food peace Complete and human life's health.
The method that predominantly detects of triazole pesticide residual is liquid chromatograph and multiple techniques thereof at present.But owing to its residual is dense Spending low, pre-treatment is loaded down with trivial details and matrix interference big, seriously limits conventional method for quick and instrument analytical method in sample Effective detection of this pesticide residue.It addition, the selective power of the pre-treating methods such as traditional QuEChERS is poor, in enrichment point While analysis thing, a large amount of matrixes and interfering material are also enriched with, and cause still containing in eluent matrix and impurity, disturb last Chromatography.Therefore, explore a kind of collect Sample Pretreatment Technique and highly sensitive be quickly detected as one new method, for Improve Residual Pesticides in Farm Produce detection sensitivity and accuracy is the most necessary.
Molecularly imprinted polymer (molecularly imprinted polymers, MIPs) is a kind of artificial design and rational The specific molecular identification material of preparation, the target molecule in complex sample substrate is had and well selects richness by its efficient identification Collection effect.In addition to precordainment, identity and the big feature of practicality three, also have that preparation is simple, low cost, template molecule can return Receive the features such as recycling, be therefore highly suitable as selected adsorbent.Simultaneously compared with biological antibody, show the steady of height Qualitative, there is the ability of anti-adverse environment.Therefore it is urged with biosensor, analogue enztme at chiral separation, Solid-Phase Extraction, chemistry The fields such as change, membrance separation are widely used.The preparation of molecularly imprinted polymer is frequently with precipitation polymerization method, and body gathers Conjunction is compared, and reduces grinding steps easy and simple to handle, and polymer form is more regular simultaneously, presents unifonn spherical.
The rarest, such as Peng about the molecularly imprinted polymer of triazole class compounds and the document report of MISPE method thereof Freely (2009) etc. use onitrophenol to be alternate template, and 4-vinylpridine is function monomer, has synthesized 7 kinds of triazole type Compound has the imprinted polymer of specific adsorption, and is applied in the analysis of pedotheque;Hu Yanyun (2014) etc. are with triazole Ketone is template molecule, and trifluoromethyl acrylate is function monomer, has synthesized and has had high selective MIP to 20 kinds of triazole pesticides Material, establishes 20 kinds of triazole pesticide molecular engram solid phase extraction technology in Rhizoma Nelumbinis, pears, Radix Dauci Sativae sample.
These methods all use traditional bulk polymerization, need grinding to sieve, and it is homogeneous that its polymer also exists absorption Property is poor, and the shortcomings such as class specific recognition capability is weak, simultaneously because the difference of function monomer, the polymer of above-mentioned synthesis is because of hydrophilic Can difference can not the many vegetables and fruits substrate of extraction water content, be not suitable in triazole pesticide using the widest paclobutrazol and uniconazole P yet Enrichment and extraction Deng medicine.
In view of this, the special proposition present invention.
Summary of the invention
It is an object of the invention to provide a kind of triazole pesticide molecular blotting polymer microsphere, described molecular engram gathers Specific recognition that compound microsphere can realize carrying out triazole pesticide, separate, be enriched with and purification;Utilize this triazole pesticide Molecular blotting polymer microsphere can be made into solid-phase extraction column as filler, present invention also offers described solid-phase extraction column in inspection Survey the application in triazole pesticide.
Present invention also offers the preparation method of a kind of described triazole pesticide molecular blotting polymer microsphere, the method system Standby MIP has good selectivity and evident characteristics to microsphere, and operating condition is simple, it is simple to universal.
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of triazole pesticide molecular blotting polymer microsphere, described molecular blotting polymer microsphere is with triazolone as template Molecule, methacrylic acid be function monomer, trimethylol-propane trimethacrylate be that cross-linking agent, azodiisobutyronitrile are for drawing Send out and remove template molecule after agent is reacted in atent solvent and obtain.
Optionally, described atent solvent is acetonitrile.
The present invention is template molecule by selecting triazolone, has synthesized and has had height " class " specificity, selective molecule Imprinted polymer microsphere (MIP), can be achieved in the detection to triazole pesticide simultaneously.
The selection of function monomer has a significant impact for the absorption property of molecularly imprinted polymer, needs according to template molecule Structure and fundamental property select.The present invention has selected methacrylic acid (MAA) as function monomer, can extraordinary carry The high compound recognition reaction to template molecule.
In order to make the imprinted polymer of generation have certain spacial framework and stable binding site, molecular engram The degree of cross linking that polymer requires is the highest.Trimethylol-propane trimethacrylate (TRIM) preferred for this invention has higher The degree of cross linking (70~90%), and there is in pre-polymer solution good dissolubility.
In molecular engram polyreaction, it mostly is radical initiation reaction, therefore need to add initiator when reaction and cause poly- Closing reaction, the preferred azodiisobutyronitrile of the present invention (AIBN) is as initiator.Azodiisobutyronitrile is that oil-soluble azo causes Agent, azo-initiator stable reaction, is first order reaction, does not has side reaction, relatively good control.
The effect of the actual also act as solvents of porogen.The selection of solvent plays an important role in prepared by molecular engram, Very big to the morphology influence of intermolecular active force and MD, and play a part porogen.The solvent being generally selected to possess with Lower 3 conditions: 1), template molecule and function monomer can be dissolved;2), big opening can be formed;3), to template molecule and function Interaction interference between monomer is little.It is typically based on active force type selecting possible between microsphere and function monomer suitable The solvent of polarity, the polarity of solvent is the biggest, and the interference to molecular recognition is the biggest, and adsorption rate is the lowest.The present invention is used Acetonitrile polarity little, dielectric constant is low, simultaneously also very good to the dissolubility of several reactants.
Optionally, triazole pesticide molecular blotting polymer microsphere as above, described triazolone and described methyl-prop The mol ratio of olefin(e) acid is 1:(5~7).
Optionally, triazole pesticide molecular blotting polymer microsphere as above, particle diameter≤2 μm of described microsphere.
The preparation method of triazole pesticide molecular blotting polymer microsphere as above, including:
Described template molecule, function monomer, cross-linking agent and initiator are dissolved in atent solvent, lead to noble gas subsequently Deoxygenation, thermal-initiated polymerization reacts, then through eluting and dried and get final product.
The polymerization of the present invention is precipitation polymerization method, and feature is that the particle size ratio obtained is more uniform, and specific surface area is big, There is more recognition site, thus there is more excellent absorption property.
Optionally, the preparation method of triazole pesticide molecular blotting polymer microsphere as above, described template is divided When son, function monomer, cross-linking agent and initiator are dissolved in atent solvent, first described template molecule and function monomer are dissolved In atent solvent and after prepolymerization 25~35min, add described cross-linking agent and initiator.
Optionally, the preparation method of triazole pesticide molecular blotting polymer microsphere as above, described thermal initiation gathers The reaction condition closing reaction is 55~65 DEG C of polyreactions 22~26h.
A kind of solid-phase extraction column, described solid-phase extraction column is with triazole pesticide molecular blotting polymer microsphere as above For filler.
As above the application in detection triazole pesticide of the solid-phase extraction column.
Optionally, applying as above, the kind of described triazole pesticide includes antibacterial and plant growth regulator;
Optionally, described antibacterial includes paclobutrazol and/or uniconazole P;
Optionally, described plant growth regulator include metconazole, triazolone, bitertanol, olefin conversion, Triadimenol, Hexaconazole, SAN-619F, Tebuconazole, bromuconazole, Difenoconazole, epoxiconazole, RH-7592, nitrile bacterium azoles, Wu Junzuo, propiconazole, One or more in tetraconazole, fluorine bacterium azoles and diclobutrazol.
Convenient for statement, below solid-phase extraction column is referred to as SPE, will be filled with triazole pesticide molecularly imprinted polymer The solid-phase extraction column of microsphere is referred to as MISPE post.
Compared with prior art, the invention have the benefit that
1), first by methacrylic acid (MAA) triazole pesticide molecule is prepared as function monomer, employing precipitation polymerization method Imprinted polymer, the MISPE post made for filler with this polymer, solve the absorption universality of conventional solid extraction column, wash De-complexity, cannot reusable shortcoming, it is achieved that molecularly imprinted polymer and the Integration ofTechnology of solid-phase extraction column.
2), adsorbing class specificity, the adsorbent substantial selectivity conventional due to SPE is poor, while enrichment of analyte, A large amount of matrixes and interfering material are also enriched with, and cause still containing in eluent matrix and impurity, disturb last chromatography.With Time, the MISPE post on market can only specific adsorption one material, and the solid phase extraction column currently developed, having can height Selectivity and adsorptivity and class specificity, it is achieved that adsorb with molecularly imprinted polymer simultaneously and be enriched with multiple similar drugs The application of solid phase extraction techniques.
3), convenient and swift, use MISPE post to carry out sample pre-treatments, step is simple, and separate, enrichment, clean-up effect Good.
4), environmental protection, MISPE post pretreatment technology organic solvent usage amount is few, meets the requirement of current environmental protection.
5), recycling, the template molecule used in the preparation of MIP can recycle, and reduces cost.
6), the present invention by solvent, function monomer, cross-linking agent, the kind of initiator and consumption are selected, optimize poly- Conjunction condition, prepares and has the distribution of more preferable particle diameter, physical stability, the molecularly imprinted polymer of excellent absorption property, it is possible to 20 kinds of triazole pesticides that Selective recognition is similar with template molecule structure, have good " class " specificity.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art will Understanding, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.In embodiment unreceipted specifically Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, be Can be by the commercially available conventional products bought and obtain.
A kind of triazole pesticide molecular blotting polymer microsphere, described molecular blotting polymer microsphere is with triazolone as template Molecule, methacrylic acid be function monomer, trimethylol-propane trimethacrylate be that cross-linking agent, azodiisobutyronitrile are for drawing Send out and remove template molecule after agent is reacted in atent solvent and obtain.
Based on being actually needed that more than MIPs feature and triazole pesticide detect, use precipitation polymerization method, synthesized and had Highly " class " specificity, molecularly imprinted polymers selective microsphere, and develop as filler and be applicable to specific adsorption The general pillar of MISPE of triazole pesticide, it is achieved that many residuals efficiently concentrating and the detection to 20 kinds of triazole pesticides.
So far, there is not yet with triazolone as template molecule, methacrylic acid is function monomer, and acetonitrile is solvent, AIBN is initiator, and TRIM is the report that triazole pesticide MISPE post prepared by cross-linking agent.
Therefore, triazolone of the present invention is template, and MAA is function monomer, and acetonitrile is solvent, and AIBN is initiator and TRIM For cross-linking agent, precipitation polymerization method synthesis is used to have the MIP of relatively high absorption property to multiple triazole pesticide, using this MIP as filling out The MISPE post that material is made is to can be used for the detection of trace triazole pesticide in sample, and its method is simple and efficient, and the response rate is high.This Method is that the convenience of solid-phase extraction column and the specific binding of molecularly imprinted polymer are reached sample pre-treatments is quick, simple Just purpose.
Preferably, one or more during described atent solvent includes toluene, dichloromethane, acetonitrile, chloroform;More preferably , described atent solvent is acetonitrile.
Preferably, triazole pesticide molecular blotting polymer microsphere as above, described triazolone and described methyl-prop The mol ratio of olefin(e) acid is 1:(5~7);It is furthermore preferred that the mol ratio of described triazolone and described methacrylic acid is 1:6;
It is further preferred that in described template molecule triazolone concentration in described atent solvent be 0.05mmol~ 0.15mmol, more preferably 0.1mmol;Described methacrylic acid concentration in described atent solvent be 0.3mmol~ 0.9mmol, more preferably 0.6mmol.
Preferably, described trimethylol-propane trimethacrylate concentration in described atent solvent is 0.6mmol ~1.4mmol, more preferably 1.0mmol.
Preferably, particle diameter≤2 μm of described microsphere;Preferred particle diameter≤1 μm;Preferred particle diameter≤0.5 μm.
Those skilled in the art can be according to the molecularly imprinted polymer of present invention offer, template molecule, function monomer, crosslinking Agent kind selects mass polymerization, precipitation polymerization method, suspension polymerization, electropolymerization;Most preferably, use precipitation polymerization method, The method includes:
Described template molecule, function monomer, cross-linking agent and initiator are dissolved in atent solvent, lead to noble gas subsequently Deoxygenation, thermal-initiated polymerization reacts, then through eluting and dried and get final product;
Preferably, described noble gas is nitrogen.
Preferably, the preparation method of triazole pesticide molecular blotting polymer microsphere as above, described template is divided When son, function monomer, cross-linking agent and initiator are dissolved in atent solvent, first described template molecule and function monomer are dissolved In atent solvent and after prepolymerization 25~35min, add described cross-linking agent and initiator;It is further preferred that it is described pre- During polymerization, the condition of reaction is under room temperature, shakes 25~35min in earthquake device, and the frequency of oscillation of described oscillator is 200 Rev/min.
Preferably, the reaction condition of described thermal-initiated polymerization reaction is 55~65 DEG C of polyreactions 22~26h.
A kind of solid-phase extraction column, described solid-phase extraction column is with triazole pesticide molecular blotting polymer microsphere as above For filler.
Preferably, time in described triazole pesticide molecular blotting polymer microsphere is filled in solid-phase extraction column, loading is 5mg~50mg, more preferably 20mg~40mg.
The solid-phase extraction column as above application in detection triazole pesticide.
Preferably, applying as above, the kind of described triazole pesticide includes antibacterial and plant growth regulator;
It is furthermore preferred that described antibacterial includes paclobutrazol and/or uniconazole P;
It is furthermore preferred that described plant growth regulator includes metconazole, triazolone, bitertanol, olefin conversion, triazole Alcohol, hexaconazole, SAN-619F, Tebuconazole, bromuconazole, Difenoconazole, epoxiconazole, RH-7592, nitrile bacterium azoles, Wu Junzuo, the third ring One or more in azoles, tetraconazole, fluorine bacterium azoles and diclobutrazol.
Preferably, applying as above, concrete operations during its detection triazole pesticide include:
After using acetonitrile and water activation MISPE post, by crossing solid-phase extraction column after determinand pretreatment, use volume basis subsequently Number is the aqueous solution drip washing of the acetonitrile of 15%~25%, then uses acetonitrile eluting, collects eluent, and nitrogen dries up for detection;Preferably , the method for described detection is LC-MS/MS.
Embodiment 1
A), 0.0145g triazolone template molecule (0.05mmol) and 0.07mL methacrylic acid (0.35mmol) are dissolved in In 20mL acetonitrile, earthquake device shakes preact 25min;
B), after template molecule and methacrylic acid prepolymerization, to A) in mixed liquor in add 0.1824mL TRIM (eventually Concentration 0.6mmol) and 30.0mg AIBN fully mix.Seal after inflated with nitrogen deoxygenation;
C), 55 DEG C of waters bath with thermostatic control heating 26h, cool down, be centrifuged, sieve, abandoning supernatant, be precipitated thing, then will precipitation Thing natural drying;
D), the materials such as remaining monomer and cross-linking agent are removed with acetic acid and the mixed solution eluting that methanol volume ratio is 1:9, Again with methanol washing 5h removes acetic acid, until can't detect triazolone by high performance liquid chromatography;
The powder that eluting is removed template molecule is placed in drying baker drying, obtains triazole pesticide molecularly imprinted polymer Microsphere, it is white, particle diameter≤2 μm;
E), weigh 30mg polymer uniform to fill in solid-phase extraction column obtains MISPE post.
Embodiment 2
A), 0.0435g triazolone template molecule (0.15mmol) and 0.15mL methacrylic acid (0.75mmol) are dissolved in In 20mL acetonitrile, earthquake device shakes preact 35min;
B), after template molecule and methacrylic acid prepolymerization, to A) in mixed liquor in add 0.4256mL TRIM (eventually Concentration 1.4mmol) and 30.0mg AIBN fully mix.Seal after inflated with nitrogen deoxygenation;
C), 65 DEG C of waters bath with thermostatic control heating 22h, cool down, be centrifuged, sieve, abandoning supernatant, be precipitated thing, then will precipitation Thing natural drying;
D), the materials such as remaining monomer and cross-linking agent are removed with acetic acid and the mixed solution eluting that methanol volume ratio is 1:9, Again with methanol washing 5h removes acetic acid, until can't detect triazolone by high performance liquid chromatography;
The powder that eluting is removed template molecule is placed in drying baker drying, obtains triazole pesticide molecularly imprinted polymer Microsphere, it is white, particle diameter≤2 μm;
E), weigh 30mg polymer uniform to fill in solid-phase extraction column obtains MISPE post.
Embodiment 3
A), 0.029g triazolone template molecule (0.1mmol) and 0.12mL methacrylic acid (0.6mmol) are dissolved in 20mL In acetonitrile, earthquake device shakes preact 30min;
B), after template molecule and methacrylic acid prepolymerization, to A) in mixed liquor in add 0.304mL TRIM (the denseest Degree 1.0mmol) and 30.0mg AIBN fully mix.Seal after inflated with nitrogen deoxygenation;
C), 60 DEG C of waters bath with thermostatic control heating 24h, cool down, be centrifuged, sieve, abandoning supernatant, be precipitated thing, then will precipitation Thing natural drying;
D), the materials such as remaining monomer and cross-linking agent are removed with acetic acid and the mixed solution eluting that methanol volume ratio is 1:9, Again with methanol washing 5h removes acetic acid, until can't detect triazolone by high performance liquid chromatography;
The powder that eluting is removed template molecule is placed in drying baker drying, obtains triazole pesticide molecularly imprinted polymer Microsphere, it is white, particle diameter≤2 μm;
E), weigh 30mg polymer uniform to fill in solid-phase extraction column obtains MISPE post.
Experimental example
The MISPE post that Example 3 prepares activates with 3mL acetonitrile, 1mL water in advance, and the most each MISPE post measures Interpolation concentration is 1 μ g/kg, 20 kinds of triazole pesticide Fructus Vitis viniferaes of 2 μ g/kg and 10 μ g/kg extract samples;
Each MISPE post 1mL percentage by volume is that the removal of impurity is gone in the aqueous solution drip washing of the acetonitrile of 20%, then uses 3mL second Nitrile eluting, collects eluent, and nitrogen dries up to 1mL, uses LC-MS/MS detection.
Wherein, the adsorptivity of 20 kinds of triazole pesticide molecularly imprinted solid phase extraction columns is as shown in table 1:
The response rate of 1 20 kinds of triazole pesticide molecularly imprinted solid phase extraction columns of table and precision values
For the effect of the application is better described, applicant is according to (molecular engram solid phase extraction liquid phase colors such as Hu Yanyun 20 kinds of triazole pesticide residuals in spectrum-mass spectrometric determination fruit and vegerable, in February, 2014, analytical chemistry research report the 2nd phase of volume 42, 227~232) method described in article has synthesized corresponding MIP and has been prepared as MISPE pillar as a comparison case, each pillar In weigh 30mg polymer equally, experiment condition is all identical with described in comparative example article with operation.Experimental result such as table 2 institute Show:
The response rate of table 2 20 kinds of triazole pesticide molecularly imprinted solid phase extraction columns of comparative example and precision values
The present invention uses precipitation polymerization technology, and with triazolone as template molecule, methacrylic acid is function monomer, three hydroxyl first Base propane trimethyl acrylic ester is to obtain 20 kinds of conventional triazoles such as paclobutrazols in the new polymerization systems that cross-linking agent is constituted Class pesticide has the molecular blotting polymer microsphere of class specific adsorption ability, it is achieved that be applicable to the multiple vegetables and fruits samples such as Fructus Vitis viniferae In 20 kinds of triazole pesticides efficiently concentrating, extract and separate, solving molecularly imprinted polymer technology can not specific recognition The technical barrier of the triazole pesticides such as paclobutrazol.
Knowable to result above, most of MIP prepared by comparative example method triazole pesticide residual in carrying out Fructus Vitis viniferae During detection, with the application effect without being clearly distinguished from the response rate with RSD, but at paclobutrazol, uniconazole P and diclobutrazol Significant difference is there is in detection.And paclobutrazol, uniconazole P are the most conventional triazole pesticide molecule.This species diversity On the one hand produce and be likely due to the hydrophilicity of MIP prepared by the preparation method of different polymer and differ greatly, thus result in More in moisture it is that (in this example, i.e. Fructus Vitis viniferae) using effect there occurs larger difference in fruit;On the other hand, by MAA is used to be function monomer in the application so that the MIP of preparation still has outstanding adsorptivity in the environment of slant acidity Energy.
In sum, MIP and MISPE pillar provided by the present invention, except can detecting the fruit and vegerable that water content is relatively low Outward, the fruit and vegerable (such as Fructus Vitis viniferae, Fructus Lycopersici esculenti, Fructus Cucumidis sativi, Fructus Persicae etc.) that can also be for high-moisture detect, and more to detection environment (as PH value) there is higher tolerance, thus have and be more widely applied.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit;For Narration is convenient, and the present invention only gives the effect of most preferred embodiment 3 in experimental example, but actually in the application claim In the range of record, this effect all can realize, wherein the experimental data (response rate and RSD) of embodiment 1~2 and the experiment of embodiment 3 Data compare floating less than 8%.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's May be made that in the case of spirit and scope many other change and amendment.It is, therefore, intended that in the following claims Including all such changes and modifications belonged in the scope of the invention.

Claims (10)

1. a triazole pesticide molecular blotting polymer microsphere, it is characterised in that described molecular blotting polymer microsphere is with three Oxazolone be template molecule, methacrylic acid be function monomer, trimethylol-propane trimethacrylate be cross-linking agent, azo two Isopropyl cyanide is to remove template molecule after initiator reacts in atent solvent to obtain.
Triazole pesticide molecular blotting polymer microsphere the most according to claim 1, it is characterised in that described atent solvent For acetonitrile.
Triazole pesticide molecular blotting polymer microsphere the most according to claim 1, it is characterised in that described triazolone with The mol ratio of described methacrylic acid is 1:(5~7).
Triazole pesticide molecular blotting polymer microsphere the most according to claim 1, it is characterised in that the grain of described microsphere Footpath≤2 μm.
5. the preparation method of the triazole pesticide molecular blotting polymer microsphere described in any one of Claims 1 to 4, its feature exists In, including:
Described template molecule, function monomer, cross-linking agent and initiator are dissolved in atent solvent, lead to noble gas subsequently and remove Oxygen, thermal-initiated polymerization reacts, then through eluting and dried and get final product.
The preparation method of triazole pesticide imprinted polymer microsphere the most according to claim 5, it is characterised in that by described When template molecule, function monomer, cross-linking agent and initiator are dissolved in atent solvent, first by described template molecule and function list Body is dissolved in atent solvent and after prepolymerization 25~35min, adds described cross-linking agent and initiator.
The preparation method of triazole pesticide imprinted polymer microsphere the most according to claim 5, it is characterised in that described heat The reaction condition of initiated polymerization is 55~65 DEG C of polyreactions 22~26h.
8. a solid-phase extraction column, it is characterised in that described solid-phase extraction column is with the triazole described in any one of Claims 1 to 4 Class pesticide molecule imprinted polymer microsphere is filler.
9. the application in detection triazole pesticide of the solid-phase extraction column described in claim 8.
Application the most according to claim 9, it is characterised in that the kind of described triazole pesticide includes antibacterial and plants Thing growth regulator;
Preferably, described antibacterial includes paclobutrazol and/or uniconazole P;
Preferably, described plant growth regulator includes metconazole, triazolone, bitertanol, olefin conversion, Triadimenol, own azoles Alcohol, SAN-619F, Tebuconazole, bromuconazole, Difenoconazole, epoxiconazole, RH-7592, nitrile bacterium azoles, Wu Junzuo, propiconazole, tetrafluoro One or more in ether azoles, fluorine bacterium azoles and diclobutrazol.
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