CN102023156A - Synthesis of shell-like molecularly imprinted polymer and application thereof for detecting persistent pesticides - Google Patents
Synthesis of shell-like molecularly imprinted polymer and application thereof for detecting persistent pesticides Download PDFInfo
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- CN102023156A CN102023156A CN2010105075792A CN201010507579A CN102023156A CN 102023156 A CN102023156 A CN 102023156A CN 2010105075792 A CN2010105075792 A CN 2010105075792A CN 201010507579 A CN201010507579 A CN 201010507579A CN 102023156 A CN102023156 A CN 102023156A
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Abstract
The invention discloses a novel approach to detecting pesticide residues and a method for detecting pesticide residues. The preparation of a molecularly imprinted polymer microsphere comprises the following steps of: preparing a mesoporous material; carrying out surface modification of the mesoporous material; synthesizing the surface molecularly imprinted polymer; and further making the molecularly imprinted polymer microsphere into a spherical shell structure. The method for detecting trace pesticide residues comprises the following steps of: putting the polymer in a prepared pillar for making a flowing cell; and then accessing the flowing cell in a flow path for detecting chemiluminescence signal strength. The molecularly imprinted polymer has strong specificity and high sensibility, can be put in the pillar and then is accessed in the flow path for detecting the chemiluminescence signal strength to achieve a mug level; the method only takes 3-5minutes to complete a basic detection process; and the cost is low. The method for detecting pesticide residues with the polymer is fast and simple to operate, and automatically completed and record reaction and results by using an instrument.
Description
Technical field
The present invention relates to residual pesticide detection technique field, a kind of preparation method who detects the spherical shell shape molecularly imprinted polymer of residual pesticide that more specifically says so the invention still further relates to and adopts the detection method of described molecularly imprinted polymer to residual pesticide.
Background technology
Pesticide is the medicine that is used to prevent and treat urban health insect and agricultural pests.Because a large amount of uses of various pesticides make ecologic environment be subjected to serious pollution, prevent and handle problems such as environment that pesticide causes, food pollution, efficient strategy is exactly in time, accurately to detect residual pesticide.
The pesticide residues analysis is field the most complicated in the analytical chemistry, and mainly by due to the following characteristics: the material that (1) pesticide residues analysis need separate and measure is at ng (10
-9G), pg (10
-12G) even fg (10
-15G) level, once successful analysis needs the correct understanding to many parameters.For example correct selection and the combination of retention analysis personnel to operating conditions depended in the success or not of extraction and purification method.(2) diversity of the not intellectual of sample use of insecticide history and sample type has caused the complicacy of analytic process.(3) being on the increase of insecticide variety proposed more and more higher technological adaptability and requirement to the pesticide multi-residue analysis.
At present, the chemical detection method that is used for pesticide residues in the world has spectrophotometric method, polarography, atomic absorption spectrography (AAS), thin layer chromatography, vapor-phase chromatography, liquid phase chromatography, isotope-labelling method, nuclear magnetic resonance spectroscopy, application of gas chromatorgraphy/mass method etc.Since nineteen nineties, the modern chemical analysis technology is maked rapid progress, and many new technologies enter the practical stage, as kapillary electricity arteries and veins instrument technology (CZE), application of gas chromatorgraphy/mass technology (GC-MS, HPLC-MS) supercritical fluid chromatography technology (SFC), direct sunshine spectral analysis technology etc.These The application of new technique improve the sensitivity that pesticide residues is analyzed greatly, simplify analytical procedure, have improved analysis efficiency.But the sensitivity that these analytical approachs have is not high, as spectrophotometric method, thin layer chromatography etc.The instrument of the needs costliness that has is as application of gas chromatorgraphy/mass method, nuclear magnetic resonance spectroscopy etc.The special equipment of needs that also has is as isotope-labelling method etc.Based on above-mentioned shortcoming, the present invention has set up a kind of detection method easily and efficiently.
Summary of the invention
The chemoluminescence method that the present invention sets up high sensitivity, high selectivity carries out the molecular engram-chemoluminescence method of fast measuring to multiple pesticide, make the insecticide residues detecting operation easy fast, realized high sensitivity, high selectivity chemoluminescence method fast measuring pesticide residual in the environment.
Mainly take following measure in order to solve the problems of the technologies described above the present invention:
(1) be the feedstock production mesoporous material with TEOS and octyl amine.
(2) utilize the easily character of functionalization of mesoporous material surface, further chemical modification is carried out on the surface of mesoporous material.
(3) in the water bath with thermostatic control oscillator, control reaction conditions synthetic surface molecularly imprinted polymer on request.
(4) by steps such as Soxhlet extractings molecular engram microsphere is made spherical shell structure.
(5) polymkeric substance is put in the homemade pillar, inserted stream then, carry out the detection of chemiluminescence signal intensity.
The concrete experimental procedure of the present invention is as follows:
(1) gets the TEOS of 0.05～0.2mol, get 0.01～0.2mol octyl amine again, both are mixed stir 3～5min, add molar ratio range then rapidly at 0.001～0.003 hydrochloric acid solution, continue to stir 5～8min, behind the vacuum filtration with the product of separating out at air drying.Speed with 1 ℃/min heats up at last, stops to heat up and temperature being controlled to this value when temperature rises to 400～600 ℃, and at this temperature lower calcination 5～8h, products therefrom is a mesoporous material.
(2) mesoporous material with 0.1～0.3g places its functional group of high temperature activation, and the mesoporous material after the activation is joined in the dry toluene, adds the APTS of 1～4ml then; the dry toluene that adds 50ml at last; be configured to solution, above-mentioned solution is fed nitrogen protection, 9～12h refluxes.Separate with hydro-extractor again, be dissolved into again in the fresh dry toluene after cleaning with toluene, add the propyl group acyl chlorides of 2～5ml, add anhydrous K
2CO
3As catalyzer, at room temperature use N
2Protection is stirred 9～12h fast with potpourri, and product separates the back and cleans the mesoporous material after so just obtaining modifying with toluene, water and ethanol.
(3) get that product is dissolved in the acetonitrile of 40～50ml in (2) of 15～20mg by sonic oscillation, order adds function monomer acrylamide 15～18mg, initiator A IBN 8～12mg, template molecule 25～30mg and crosslinking chemical EGDMA 170～190mg, sonic oscillation fully dissolves it, charge into argon gas 10min, ice-water bath cooling a period of time.
(4) on the water bath with thermostatic control oscillator, adopt intensification polymerization synthetic surface molecular imprinting microballoon.At first, carry out polymerization 20～25h at 50～60 ℃ again, then be warmed up to 80～90 ℃ of reaction 6～8h and obtain highly cross-linked polymkeric substance at 40～50 ℃ of prepolymerization 6～8h.
(5) molecularly imprinted polymer synthetic after the intensification polymerization is filtered, after cleaning respectively with acetonitrile and ethanol, in vacuum drying chamber, dry.Then with its taking-up, product is handled, being placed in the apparatus,Soxhlet's with ratio range is that 9: 1～12: 1 the methyl alcohol and the eluent of acetate carry out extracting with the molecular imprinting microballoon, template molecule inside and outside the nucleocapsid is washed away, to obtain the having molecularly imprinted polymer that " to remember " void structure of function.
(6) allow the template molecule flow of solution through the MIP post, the template molecule in the solution combines with the binding site of molecular engram microsphere shell, is adsorbed in the hole of MIP.Then use solvent washing MIP post instead, the template molecule of not absorption is rinsed well, the template molecule that prevents from simultaneously to be adsorbed onto on the molecular engram microsphere is eluted.The MIP separating column is protected.Make the luminescence reagent MIP separating column of flowing through,, produce luminous signal with the template molecule generation chemiluminescence reaction that is adsorbed on the MIP separating column.
Eluant, eluent of the present invention is acetonitrile, methyl alcohol-acetate or acetonitrile-acetate.
Function monomer of the present invention is acrylamide (MA), acrylic acid (AA), methacrylic acid (MAA), phenyltrimethoxysila,e (PTMOS) and methyltrimethoxy silane (MTMOS); Described crosslinking chemical is trimethylol-propane trimethacrylate (TRIM), N, N-methylene diacrylamine, 3,5-two (acrylamide) benzoic acid, ethylene glycol dimethacrylate (EGDMA), divinylbenzene (DVB) or pentaerythritol triacrylate (PETRA); Described initiating agent is an azoisobutyronitrile; Described pore-foaming agent adopts methylene chloride, chloroform, acetonitrile, methyl alcohol, isopropyl alcohol, phenixin, heterogeneous ring compound acid amides or sulfone class; The silicon source is an ethyl orthosilicate.
Beneficial effect of the present invention:
The present invention utilizes the surface molecule print technology to synthesize the molecular blotting polymer microsphere shell of pesticide, then this molecular engram microsphere is made the MIP separating column, uses this MIP post with chemoluminescence method pesticide to be detected.Having the following advantages of this method:
(1) template molecule that not only can flush away polymkeric substance outside in preparation process, template molecule that can also flush away inside, product no longer is a solid spherolite like this, has increased the combined surface area that is identified material like this.
(2) high selectivity of molecularly imprinted polymer and the highly sensitive advantage of chemoluminescence method are carried out combination by molecular imprinting, and utilized the fast detecting of IFFM-E type portable injection chemiluminescence analyser that measured object is detected.
(3) this method has selectivity height, highly sensitive, advantage that detection speed is fast, measures the accuracy height of pesticide content residual in food with this method, and real result is reliable.
Embodiment
(1) be the feedstock production mesoporous material with TEOS and octyl amine.
(2) utilize the easily character of functionalization of mesoporous material surface, further chemical modification is carried out on the surface of mesoporous material.
(3) in the water bath with thermostatic control oscillator, control reaction conditions synthetic surface molecularly imprinted polymer on request.
(4) by steps such as Soxhlet extractings molecular engram microsphere is made spherical shell structure.
(5) polymkeric substance is placed pillar, insert stream then, carry out the detection of chemiluminescence signal intensity.
The concrete experimental procedure of the present invention is as follows:
(1) gets the TEOS of 0.05～0.2mol, get 0.01～0.2mol octyl amine again, both are mixed stir 3～5min, add molar ratio range then rapidly at 0.001～0.003 hydrochloric acid solution, continue to stir 5～8min, behind the vacuum filtration with the product of separating out at air drying.Speed with 1 ℃/min heats up at last, stops to heat up and temperature being controlled to this value when temperature rises to 400～600 ℃, and at this temperature lower calcination 5～8h, products therefrom is a mesoporous material.
(2) mesoporous material with 0.1～0.3g places its functional group of high temperature activation, and the mesoporous material after the activation is joined in the dry toluene, adds the APTS of 1～4ml then; the dry toluene that adds 50ml at last; be configured to solution, above-mentioned solution is fed nitrogen protection, 9～12h refluxes.Separate with hydro-extractor again, be dissolved into again in the fresh dry toluene after cleaning with toluene, add the propyl group acyl chlorides of 2～5ml, add anhydrous K
2CO
3As catalyzer, at room temperature use N
2Protection is stirred 9～12h fast with potpourri, and product separates the back and cleans the mesoporous material after so just obtaining modifying with toluene, water and ethanol.
(3) get that product is dissolved in the acetonitrile of 40～50ml in (2) of 15～20mg by sonic oscillation, order adds function monomer acrylamide 15～18mg, initiator A IBN 8～12mg, template molecule 25～30mg and crosslinking chemical EGDMA 170～190mg, sonic oscillation fully dissolves it, charge into argon gas 10min, ice-water bath cooling a period of time.
(4) on the water bath with thermostatic control oscillator, adopt intensification polymerization synthetic surface molecular imprinting microballoon.At first, carry out polymerization 20～25h at 50～60 ℃ again, then be warmed up to 80～90 ℃ of reaction 6～8h and obtain highly cross-linked polymkeric substance at 40～50 ℃ of prepolymerization 6～8h.
(5) molecularly imprinted polymer synthetic after the intensification polymerization is filtered, after cleaning respectively with acetonitrile and ethanol, in vacuum drying chamber, dry.Then with its taking-up, product is handled, being placed in the apparatus,Soxhlet's with ratio range is that 9: 1～12: 1 the methyl alcohol and the eluent of acetate carry out extracting with the molecular imprinting microballoon, template molecule inside and outside the nucleocapsid is washed away, to obtain the having molecularly imprinted polymer that " to remember " void structure of function.
(6) allow the template molecule flow of solution through the MIP post, the template molecule in the solution combines with the binding site of molecular engram microsphere shell, is adsorbed in the hole of MIP.Then use solvent washing MIP post instead, the template molecule of not absorption is rinsed well, the template molecule that prevents from simultaneously to be adsorbed onto on the molecular engram microsphere is eluted.The MIP separating column is protected.Make the luminescence reagent MIP separating column of flowing through,, produce luminous signal with the template molecule generation chemiluminescence reaction that is adsorbed on the MIP separating column.
Eluant, eluent of the present invention is acetonitrile, methyl alcohol-acetate or acetonitrile-acetate.
Function monomer of the present invention is acrylamide (MA), acrylic acid (AA), methacrylic acid (MAA), phenyltrimethoxysila,e (PTMOS) and methyltrimethoxy silane (MTMOS); Described crosslinking chemical is trimethylol-propane trimethacrylate (TRIM), N, N-methylene diacrylamine, 3,5-two (acrylamide) benzoic acid, ethylene glycol dimethacrylate (EGDMA), divinylbenzene (DVB) or pentaerythritol triacrylate (PETRA); Described initiating agent is an azoisobutyronitrile; Described pore-foaming agent adopts methylene chloride, chloroform, acetonitrile, methyl alcohol, isopropyl alcohol, phenixin, heterogeneous ring compound acid amides or sulfone class; The silicon source is an ethyl orthosilicate.
Embodiment 1 (carbamates is as carbofuran)
A kind of preparation method who detects the molecularly imprinted polymer of carbofuran may further comprise the steps:
(1) optium concentration that adopts quantity method one by one that luminous experiment condition is selected to draw NaOH is 0.3mo1L
-1, luminol optium concentration be 5.0 * 10
-5MolL
-1, hydrogen peroxide optium concentration be 3%, best main pump speed is 1.8mLmin
-1, best auxiliary pump speed is 2.4mLmin
-1
(2) get the TEOS of 0.1mol, get the 0.06mol octyl amine again, both are mixed stir 3min, add mol ratio then rapidly and be 0.0013 hydrochloric acid solution, continue to stir 5min, behind the vacuum filtration with the product of separating out at air drying.Speed with 1 ℃/min heats up at last, stops to heat up and temperature being controlled to this value when temperature rises to 550 ℃, and at this temperature lower calcination 6h, products therefrom is a mesoporous material.
(3) mesoporous material with 0.1g places its functional group of high temperature activation, and the mesoporous material after the activation is joined in the dry toluene, adds the APTS of 2ml then; the dry toluene that adds 50ml at last; be configured to solution, above-mentioned solution is fed nitrogen protection, backflow 12h.Separate with hydro-extractor again, be dissolved into again in the fresh dry toluene after cleaning with toluene, add the propyl group acyl chlorides of 2ml, with an amount of anhydrous K
2CO
3As catalyzer, at room temperature use N
2Protection is stirred 12h fast with potpourri, and product separates the back and cleans the mesoporous material after so just obtaining modifying with toluene, water and ethanol.
(4) get that product is dissolved in the acetonitrile of 50ml in (2) of 20mg by sonic oscillation, order adds function monomer acrylamide 17mg, initiator A IBN 10mg, template molecule 30mg and crosslinking chemical EGDMA 183mg, sonic oscillation fully dissolves it, charge into argon gas 10min, ice-water bath cooling a period of time.
(5) on the water bath with thermostatic control oscillator, adopt intensification polymerization synthetic surface molecular imprinting microballoon.At first, carry out polymerization 24h at 60 ℃ again, then be warmed up to 85 ℃ of reaction 6h and obtain highly cross-linked polymkeric substance at 50 ℃ of prepolymerization 6h.
(6) molecular imprinting microballoon synthetic after the intensification polymerization is filtered, after cleaning respectively with acetonitrile and ethanol, in vacuum drying chamber, dry.Then with its taking-up, after product handled, place apparatus,Soxhlet's, eluent with 9: 1 methyl alcohol and acetate carries out extracting with the molecular imprinting microballoon, the template molecule that nucleocapsid is inside and outside washes away, to obtain the having molecularly imprinted polymer that can " remember " void structure of function.
(7) allow the carbofuran molecular solution MIP post of flowing through under the optimal luminescent experiment condition, the carbofuran molecule in the solution combines with the binding site of molecular engram microsphere shell, is adsorbed in the hole of MIP.Then use secondary deionized water flushing MIP post instead, the carbofuran molecule of not absorption is rinsed well, the carbofuran molecule that prevents from simultaneously to be adsorbed onto on the molecular engram microsphere is eluted.The MIP separating column is protected.Make NaOH (0.3molL
-1), luminol (5.0 * 10
-5MolL
-1), hydrogen peroxide (0.3molL
-1) luminescence reagent formed, the MIP separating column of flowing through with the carbofuran molecule generation chemiluminescence reaction that is adsorbed on the MIP separating column, produces luminous signal.
Table 1 the present invention is to the detection effect of carbofuran
Molecularly imprinted polymer is compared with other method for the chemoluminescence method on basis, has better choice, higher sensitivity, and detection speed improves greatly.By form as can be seen molecular engram microsphere than molecular engram microsphere shell the wideer range of linearity is arranged, lower detection limit is arranged.
Embodiment 2 (chrysanthemum ester class is as Fenpropathrin)
A kind of preparation method who detects the molecularly imprinted polymer of Fenpropathrin may further comprise the steps:
(1) adopting one by one quantity method that luminous experiment condition is selected to draw Fenpropathrin concentration is 2.0 μ gmL
-1, luminol optium concentration be 7.0 * 10
-5The optium concentration of molL-1, hydrogen peroxide is 2.5%, best main pump speed is 1.6mLmin
-1, best auxiliary pump speed is 2.4mLmin
-1
(2) get the TEOS of 0.1mol, get the 0.06mol octyl amine again, both are mixed stir 3min, add mol ratio then rapidly and be 0.0013 hydrochloric acid solution, continue to stir 5min, behind the vacuum filtration with the product of separating out at air drying.Speed with 1 ℃/min heats up at last, stops to heat up and temperature being controlled to this value when temperature rises to 550 ℃, and at this temperature lower calcination 6h, products therefrom is a mesoporous material.
(3) mesoporous material with 0.1g places its functional group of high temperature activation, and the mesoporous material after the activation is joined in the dry toluene, adds the APTS of 2ml then; the dry toluene that adds 50ml at last; be configured to solution, above-mentioned solution is fed nitrogen protection, backflow 12h.Separate with hydro-extractor again, be dissolved into again in the fresh dry toluene after cleaning with toluene, add the propyl group acyl chlorides of 2ml, with an amount of anhydrous K
2CO
3As catalyzer, at room temperature use N
2Protection is stirred 12h fast with potpourri, and product separates the back and cleans the mesoporous material after so just obtaining modifying with toluene, water and ethanol.
(4) get that product is dissolved in the acetonitrile of 50ml in (2) of 20mg by sonic oscillation, order adds function monomer methacrylic acid (MAA) 10mg, initiator A IBN 8mg, Fenpropathrin 12mg and crosslinking chemical EGDMA 150mg, sonic oscillation fully dissolves it, charge into argon gas 10min, ice-water bath cooling a period of time.
(5) on the water bath with thermostatic control oscillator, adopt intensification polymerization synthetic surface molecular imprinting microballoon.At first, carry out polymerization 24h at 60 ℃ again, then be warmed up to 85 ℃ of reaction 6h and obtain highly cross-linked polymkeric substance at 50 ℃ of prepolymerization 6h.
(6) Fenpropathrin marking microballoon synthetic after the intensification polymerization is filtered, after cleaning respectively with acetonitrile and ethanol, in vacuum drying chamber, dry.Then with its taking-up, after product handled, place apparatus,Soxhlet's the molecular imprinting microballoon to be carried out extracting, the template molecule inside and outside the nucleocapsid is washed away, to obtain the having molecularly imprinted polymer that " to remember " void structure of function with 9: 1 the methyl alcohol and the eluent of acetate.
(7) allow the Fenpropathrin molecular solution MIP post of flowing through under the optimal luminescent experiment condition, the Fenpropathrin in the solution combines with the binding site of molecular engram microsphere shell, is adsorbed in the hole of MIP.Then use secondary deionized water flushing MIP post instead, the Fenpropathrin molecule of not absorption is rinsed well, the Fenpropathrin molecule that prevents from simultaneously to be adsorbed onto on the molecular engram microsphere is eluted.The MIP separating column is protected.Make luminol (7.0 * 10
-5MolL
-1), the luminescence reagent formed of hydrogen peroxide (2.5%), the MIP separating column of flowing through with the Fenpropathrin molecule generation chemiluminescence reaction that is adsorbed on the MIP separating column, produces luminous signal.
Table 2 the present invention is to the detection effect of Fenpropathrin
Molecularly imprinted polymer is compared with other method for the chemoluminescence method on basis, has better choice, higher sensitivity, and detection speed improves greatly.By form as can be seen molecular engram microsphere than molecular engram microsphere shell the wideer range of linearity is arranged, lower detection limit is arranged.
Embodiment 3 (organochlorine class, tetradiphon)
A kind of preparation method who detects the molecularly imprinted polymer of tetradiphon may further comprise the steps:
(1) adopting one by one quantity method that luminous experiment condition is selected to draw tetradiphon concentration is 4.0 * 10
-5MolL
-1, the NaOH optium concentration is 0.1molL
-1, luminol optium concentration be 4.0 * 10
-5MolL
-1, hydrogen peroxide optium concentration be 6%, best main pump speed is 1.7mLmin
-1, best auxiliary pump speed is 3.0mLmin
-1
(2) get the TEOS of 0.1mol, get the 0.06mol octyl amine again, both are mixed stir 3min, add mol ratio then rapidly and be 0.0013 hydrochloric acid solution, continue to stir 5min, behind the vacuum filtration with the product of separating out at air drying.Speed with 1 ℃/min heats up at last, stops to heat up and temperature being controlled to this value when temperature rises to 550 ℃, and at this temperature lower calcination 6h, products therefrom is a mesoporous material.
(3) mesoporous material with 0.1g places its function group of high temperature activation, and the mesoporous material after the activation is joined in the dry toluene, adds the APTS of 2ml then; at last with dry toluene with its constant volume to 50ml; be configured to solution, above-mentioned solution is fed nitrogen protection, backflow 12h.Separate with hydro-extractor again, be dispersed into again in the fresh dry toluene after cleaning with toluene, add the propyl group acyl chlorides of 2ml, add anhydrous K
2CO
3As catalyzer, at room temperature use N
2Protection is stirred 12h fast with potpourri, and product separates the back and cleans the mesoporous material after so just obtaining modifying with toluene, water and ethanol.
(4) get that product is dissolved in the acetonitrile of 50ml in (2) of 20mg by sonic oscillation, order adds function monomer methacrylic acid (MAA) 16mg, initiator A IBN 9mg, Fenpropathrin 14mg and crosslinking chemical EGDMA 140mg, sonic oscillation fully dissolves it, charge into argon gas 10min, ice-water bath cooling a period of time.
(5) on the water bath with thermostatic control oscillator, adopt intensification polymerization synthetic surface molecular imprinting microballoon.At first, carry out polymerization 24h at 60 ℃ again, then be warmed up to 85 ℃ of reaction 6h and obtain highly cross-linked polymkeric substance at 50 ℃ of prepolymerization 6h.
(6) Fenpropathrin marking microballoon synthetic after the intensification polymerization is filtered, after cleaning respectively with acetonitrile and ethanol, in vacuum drying chamber, dry.Then with its taking-up, after product handled, place apparatus,Soxhlet's the molecular imprinting microballoon to be carried out extracting, the template molecule inside and outside the nucleocapsid is washed away, to obtain the having molecularly imprinted polymer that " to remember " void structure of function with 9: 1 the methyl alcohol and the eluent of acetate.
(7) allow the full sulfone molecular solution of the three chlorbensides MIP post of flowing through under the optimal luminescent experiment condition, the full sulfone of three chlorbensides in the solution combines with the binding site of molecular engram microsphere shell, is adsorbed in the hole of MIP.Then use secondary deionized water flushing MIP post instead, the full sulfone molecule of three chlorbensides of not absorption is rinsed well, the full sulfone molecule of three chlorbensides that prevents from simultaneously to be adsorbed onto on the molecular engram microsphere is eluted.The MIP separating column is protected.Make luminol (4.0 * 10
-5MolL
-1), hydrogen peroxide (6%), NaOH (0.1molL
-1) luminescence reagent formed, the MIP separating column of flowing through, the full sulfone molecule generation chemiluminescence reaction of three chlorbensides with being adsorbed on the MIP separating column produces luminous signal.
Table 3 the present invention is to the detection effect of tetradiphon
Molecularly imprinted polymer is compared with other method for the chemoluminescence method on basis, has better choice, higher sensitivity, and detection speed improves greatly.By form as can be seen molecular engram microsphere than molecular engram microsphere shell the wideer range of linearity is arranged, lower detection limit is arranged.
Embodiment 4 (pyrethroid, decis)
A kind of preparation method who detects the molecularly imprinted polymer of decis may further comprise the steps:
(1) adopting one by one quantity method that luminous experiment condition is selected to draw decis concentration is 5.0 * 10
-5MolL
-1, the NaOH optium concentration is 0.3molL
-1, luminol optium concentration be 3.0 * 10
-5MolL
-1, hydrogen peroxide optium concentration be 4%, best main pump speed is 2.1mLmin
-1, best auxiliary pump speed is 3.0mLmin
-1
(2) get the TEOS of 0.1mol, get the 0.06mol octyl amine again, both are mixed stir 3min, add mol ratio then rapidly and be 0.0013 hydrochloric acid solution, continue to stir 5min, behind the vacuum filtration with the product of separating out at air drying.Speed with 1 ℃/min heats up at last, stops to heat up and temperature being controlled to this value when temperature rises to 550 ℃, and at this temperature lower calcination 6h, products therefrom is a mesoporous material.
(3) mesoporous material with 0.1g places its functional group of high temperature activation, and the mesoporous material after the activation is joined in the dry toluene, adds the APTS of 2ml then; at last with dry toluene with its constant volume to 50ml; be configured to solution, above-mentioned solution is fed nitrogen protection, backflow 12h.Separate with hydro-extractor again, be dispersed into again in the fresh dry toluene after cleaning with toluene, add the propyl group acyl chlorides of 2ml, add anhydrous K
2CO
3As catalyzer, at room temperature use N
2Protection is stirred 12h fast with potpourri, and product separates the back and cleans the mesoporous material after so just obtaining modifying with toluene, water and ethanol.
(4) get that product is dissolved in the acetonitrile of 50ml in (2) of 20mg by sonic oscillation, order adds function monomer methacrylic acid (MAA) 16mg, initiator A IBN 9mg, decis 14mg and crosslinking chemical EGDMA 140mg, sonic oscillation fully dissolves it, charge into argon gas 10min, ice-water bath cooling a period of time.
(5) on the water bath with thermostatic control oscillator, adopt intensification polymerization synthetic surface molecular imprinting microballoon.At first, carry out polymerization 24h at 60 ℃ again, then be warmed up to 85 ℃ of reaction 6h and obtain highly cross-linked polymkeric substance at 50 ℃ of prepolymerization 6h.
(6) decis marking microballoon synthetic after the intensification polymerization is filtered, after cleaning respectively with acetonitrile and ethanol, in vacuum drying chamber, dry.Then with its taking-up, after product handled, place apparatus,Soxhlet's the molecular imprinting microballoon to be carried out extracting, the template molecule inside and outside the nucleocapsid is washed away, to obtain the having molecularly imprinted polymer that " to remember " void structure of function with 9: 1 the methyl alcohol and the eluent of acetate.
(7) allow the decis molecular solution MIP post of flowing through under the optimal luminescent experiment condition, the decis in the solution combines with the binding site of molecular engram microsphere shell, is adsorbed in the hole of MIP.Then use secondary deionized water flushing MIP post instead, the decis molecule of not absorption is rinsed well, the decis molecule that prevents from simultaneously to be adsorbed onto on the molecular engram microsphere is eluted.The MIP separating column is protected.Make luminol (3.0 * 10
-5MolL
-1), hydrogen peroxide (4%), NaOH (0.3molL
-1) luminescence reagent formed, the MIP separating column of flowing through with the decis molecule generation chemiluminescence reaction that is adsorbed on the MIP separating column, produces luminous signal.
Table 4 the present invention is to the detection effect of decis
Molecularly imprinted polymer is compared with other method for the chemoluminescence method on basis, has better choice, higher sensitivity, and detection speed improves greatly.By form as can be seen molecular engram microsphere than molecular engram microsphere shell the wideer range of linearity is arranged, lower detection limit is arranged.
Embodiment 5 (organic nitrogen is as Spanon)
A kind of preparation method who detects the molecularly imprinted polymer of Spanon may further comprise the steps:
(1) optium concentration that adopts quantity method one by one that luminous experiment condition is selected to draw NaOH is 0.4molL
-1, luminol optium concentration be 3.0 * 10
-5MolL
-1, hydrogen peroxide optium concentration be 4%, best main pump speed is 2.3mLmin
-1, best auxiliary pump speed is 2.7mLmin
-1
(2) get the TEOS of 0.1mol, get the 0.06mol octyl amine again, both are mixed stir 3min, add mol ratio then rapidly and be 0.0013 hydrochloric acid solution, continue to stir 5min, behind the vacuum filtration with the product of separating out at air drying.Speed with 1 ℃/min heats up at last, stops to heat up and temperature being controlled to this value when temperature rises to 550 ℃, and at this temperature lower calcination 6h, products therefrom is a mesoporous material.
(3) mesoporous material with 0.1g places its functional group of high temperature activation, and the mesoporous material after the activation is joined in the dry toluene, adds the APTS of 2ml then; the dry toluene that adds 50ml at last; be configured to solution, above-mentioned solution is fed nitrogen protection, backflow 12h.Separate with hydro-extractor again, be dissolved into again in the fresh dry toluene after cleaning with toluene, add the propyl group acyl chlorides of 2ml, with an amount of anhydrous K
2CO
3As catalyzer, at room temperature use N
2Protection is stirred 12h fast with potpourri, and product separates the back and cleans the mesoporous material after so just obtaining modifying with toluene, water and ethanol.
(4) get that product is dissolved in the acetonitrile of 50ml in (2) of 20mg by sonic oscillation, order adds function monomer acrylamide 12mg, initiator A IBN 8mg, template molecule 18mg and crosslinking chemical EGDMA 126mg, sonic oscillation fully dissolves it, charge into argon gas 10min, ice-water bath cooling a period of time.
(5) on the water bath with thermostatic control oscillator, adopt intensification polymerization synthetic surface molecular imprinting microballoon.At first, carry out polymerization 24h at 60 ℃ again, then be warmed up to 85 ℃ of reaction 6h and obtain highly cross-linked polymkeric substance at 50 ℃ of prepolymerization 6h.
(6) molecular imprinting microballoon synthetic after the intensification polymerization is filtered, after cleaning respectively with acetonitrile and ethanol, in vacuum drying chamber, dry.Then with its taking-up, after product handled, place apparatus,Soxhlet's, eluent with 9: 1 methyl alcohol and acetate carries out extracting with the molecular imprinting microballoon, the template molecule that nucleocapsid is inside and outside washes away, to obtain the having molecularly imprinted polymer that can " remember " void structure of function.
(7) allow the Spanon molecular solution MIP post of flowing through under the optimal luminescent experiment condition, the Spanon molecule in the solution combines with the binding site of molecular engram microsphere shell, is adsorbed in the hole of MIP.Then use secondary deionized water flushing MIP post instead, the Spanon molecule of not absorption is rinsed well, the Spanon molecule that prevents from simultaneously to be adsorbed onto on the molecular engram microsphere is eluted.The MIP separating column is protected.Make NaOH (0.4molL
-1), luminol (3.0 * 10
-5MolL
-1), the luminescence reagent formed of hydrogen peroxide (4%), the MIP separating column of flowing through with the Spanon molecule generation chemiluminescence reaction that is adsorbed on the MIP separating column, produces luminous signal.
Table 5 the present invention is to the detection effect of Spanon
Molecularly imprinted polymer is compared with other method for the chemoluminescence method on basis, has better choice, higher sensitivity, and detection speed improves greatly.By form as can be seen molecular engram microsphere than molecular engram microsphere shell the wideer range of linearity is arranged, lower detection limit is arranged.
Claims (6)
1. preparation method who detects the portable injection chemiluminescence sensor of residual pesticide is characterized in that may further comprise the steps:
1.1 select to discern the identification body of pesticide residue;
1.2 utilize homemade mesoporous material to be substrate, control the synthetic hollow ball shelly molecularly imprinted polymer of reaction conditions on request;
1.3 with the synthetic molecularly imprinted polymer homemade flow cell of packing into, then flow cell is inserted stream, makes up molecular imprinting chemiluminescence sensor with " Y " type pillar.
2. according to the preparation method of the described molecular imprinting chemiluminescence sensor of claim 1, it is characterized in that the molecularly imprinted polymer that is synthesized is packed in the self-control flow cell, flow cell is inserted the detection that stream carries out chemiluminescence signal intensity may further comprise the steps:
2.1 on the polymethylmethacrylate module of column type, bore the passage of " Y " type, be made into flow cell;
2.2 then made hollow ball shelly molecularly imprinted polymer is encased on the branch road of " Y " type pipe, and with glass wool jam-pack branch road two ends;
2.3 replace traditional detection cell to be connected in the portable injection chemiluminescence instrument homemade flow cell.
3. according to the described transducer production method of claim 1, it is characterized in that described polymeric material is a hollow ball shelly molecular engram microsphere.
4. according to the preparation method of the described sensor of claim 3, it is characterized in that: used hollow ball shelly molecularly imprinted polymer is made by following steps: synthetic mesoporous material was carried out for two steps modify, grafting is carried out on the mesoporous material surface, under vacuum condition, with mesoporous material and the EGDMA after modifying, MAA, the agricultural chemicals template molecule polymerization that heats up, synthetic hollow ball shelly molecularly imprinted polymer.
5. according to the preparation method of the described micro polymer spherical shell of claim 3, it is characterized in that: function monomer of the present invention is for being acrylamide (MA), acrylic acid (AA), methacrylic acid (MAA), phenyltrimethoxysila,e (PTMOS) and methyltrimethoxy silane (MTMOS); Described crosslinking chemical is trimethylol-propane trimethacrylate (TRIM), N, N-methylene diacrylamine, 3,5-two (acrylamide) benzoic acid, ethylene glycol dimethacrylate (EGDMA), divinylbenzene (DVB) or pentaerythritol triacrylate (PETRA); Described initiating agent is an azoisobutyronitrile; Described pore-foaming agent adopts methylene chloride, chloroform, acetonitrile, methyl alcohol, isopropyl alcohol, phenixin, heterogeneous ring compound acid amides or sulfone class; The silicon source is an ethyl orthosilicate.
6. method that detects trace amount pesticide residue is characterized in that comprising the steps: with the described hollow ball shelly of claim 1 molecularly imprinted polymer being used for the detection to the pesticide residue of environment, food samples in conjunction with the portable injection chemiluminescence instrument.
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| CN2010105075792A CN102023156A (en) | 2010-10-15 | 2010-10-15 | Synthesis of shell-like molecularly imprinted polymer and application thereof for detecting persistent pesticides |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102288749A (en) * | 2011-07-28 | 2011-12-21 | 山东农业大学 | Dipterex bionic enzyme linked immunosorbent detection method |
| CN102731706A (en) * | 2012-06-20 | 2012-10-17 | 浙江省农业科学院 | Carbofuran molecularly imprinted microspheres, preparation and application thereof |
| CN107894453A (en) * | 2017-10-25 | 2018-04-10 | 中国农业大学 | A kind of preparation method of molecular engram sensor |
-
2010
- 2010-10-15 CN CN2010105075792A patent/CN102023156A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102288749A (en) * | 2011-07-28 | 2011-12-21 | 山东农业大学 | Dipterex bionic enzyme linked immunosorbent detection method |
| CN102288749B (en) * | 2011-07-28 | 2013-07-31 | 山东农业大学 | Dipterex bionic enzyme linked immunosorbent detection method |
| CN102731706A (en) * | 2012-06-20 | 2012-10-17 | 浙江省农业科学院 | Carbofuran molecularly imprinted microspheres, preparation and application thereof |
| CN107894453A (en) * | 2017-10-25 | 2018-04-10 | 中国农业大学 | A kind of preparation method of molecular engram sensor |
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Application publication date: 20110420 |