CN102507820A - Method for detecting trichlorfon and monocrotophos - Google Patents
Method for detecting trichlorfon and monocrotophos Download PDFInfo
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- CN102507820A CN102507820A CN2011103169107A CN201110316910A CN102507820A CN 102507820 A CN102507820 A CN 102507820A CN 2011103169107 A CN2011103169107 A CN 2011103169107A CN 201110316910 A CN201110316910 A CN 201110316910A CN 102507820 A CN102507820 A CN 102507820A
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- azodrin
- metrifonate
- molecularly imprinted
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Abstract
The invention relates to a method for detecting trichlorfon and monocrotophos, comprises the steps of molecularly imprinted polymer preparation, molecularly imprinted solid-phase extraction and gas chromatography combination system establishment. The prepared molecularly imprinted polymers with high trichlorfon and monocrotophos selection and recognition performance are used as the adsorption materials, thus the defects of poor selectivity of the traditional adsorbent and the like are overcome. By using the molecularly imprinted solid-phase extraction and the solid-phase chromatography jointly, the rapid and sensitive method can be used for widely detecting a trace amount of trichlorfon and monocrotophos. The method for detecting the trichlorfon and the monocrotophos has low cost, simple experimental operation and high sensitivity and is suitable for rapidly detecting a trace amount of trichlorfon and monocrotophos in various products.
Description
Technical field
The present invention relates to a kind of method that detects metrifonate and Azodrin simultaneously, belong to the food safety detection technical field.
Background technology
In the agricultural chemicals that uses, the application of organophosphorus insecticide is (above 100 kinds) the most extensively at present, and toxicity is maximum.Metrifonate and Azodrin are the broad spectrum pesticides in the organophosphorus pesticide, have characteristics such as efficient, low toxicity, low-residual, good water solubility, often are used as insecticide spraying on fruit tree, vegetables; Though it is prone to degraded than organo-chlorine pesticide, residual life, is shorter, and organophosphorus pesticide toxicity is also higher; If the agricultural chemicals that remains in the agricultural chemicals on fruit, the vegetables or get in the environment gets into organism; Most of have inhibiting effect to cholinesterase in the biosome, suppresses cholinesterase and make it lose the ability of decomposing acetylcholine, causes the acetylcholine accumulation; Cause nerve dysfunction, thereby cause the infringement of human body.As acetylcholine inhibitor, the environmental exposure of organophosphorus pesticide contacts with skin can cause biotoxication.
It is the focus of domestic and international food security area research and development that pesticide multi-residues detects, main at present gas chromatography, liquid chromatography, immunoassay, gas chromatography-mass spectrum (GC-MS) and the liquid chromatography-mass spectrography methods such as (LC-MS) of adopting.The chromatography mass spectrometry detection sensitivity is high but cost an arm and a leg.Chromatography detects limit for height and (is generally 10-500 μ g kg
-1), (Japanese positive list is 10 μ g kg to the Pesticide Residue value can not to satisfy the actual needs that the trace residues of pesticides and the export trade detect
-1), therefore before analyzing, need carry out enrichment usually.The pre-treating method that adopts at present mainly contains SPE, liquid-liquid extraction, matrix dispersion SPE, SPME, supercritical fluid extraction and column chromatography etc.Wherein SPE and SPME have many advantages than liquid-liquid extraction, replace liquid-liquid extraction gradually.But often selectivity is relatively poor based on commercial SPE material, and the acting force between object and the adsorbent is nonspecific, and the efficient of extraction and cleaning is not high, also be difficult to thoroughly remove the interference of matrix sometimes, and cost is also higher.Therefore utilize the synthetic adsorption functional material that metrifonate and Azodrin are had the specific recognition ability of molecular imprinting; And with the gas chromatography coupling; Make testing process simple, fast and have high sensitivity, effective detection and the monitoring and supervising that guarantees organophosphorus pesticide in China's food had crucial meaning.
Summary of the invention
In order to overcome detection time of existing in traditional metrifonate and the Azodrin detection method of long, defective such as instrument costs an arm and a leg, poor accuracy, pre-treatment are loaded down with trivial details, the invention provides a kind of method that detects metrifonate and Azodrin simultaneously.
A kind of method that detects metrifonate and Azodrin simultaneously, accomplish according to the following steps:
1. the preparation of molecularly imprinted polymer: in chloroformic solution; With metrifonate and Azodrin potpourri (1:1; Mol ratio), function monomer 3-aminopropyltriethoxywerene werene, crosslinking chemical ethylene glycol dimethacrylate mix with the molar ratio of 1:4:10, add the 100mg azoisobutyronitrile then and carry out polyreaction as initiating agent; The polymkeric substance that obtains is ground the back, and (9:1, v/v) continuous extraction 8 h use 300 mL methanol extractions, 4 h again, get molecularly imprinted polymer after the drying with 300 mL methyl alcohol/glacial acetic acids.
2. the foundation of molecular engram solid phase extraction and gas chromatography coupling system
With the molecularly imprinted polymer of preparation as the adsorbent of SPE, and with the gas chromatography coupling, set up molecular engram solid phase extraction and gas chromatography coupling detection architecture.
A. molecular engram solid phase extraction flow process:
The 100 mg imprinted polymers that step 1 is obtained are filled in the solid-phase extraction column, the preparation molecularly imprinted solid phase extraction column, and respectively with 5 mL methyl alcohol and the flushing of 5 mL water.Then with 100 mL0.05mg L
-1The hybrid standard water solution flow of metrifonate and Azodrin is crossed molecularly imprinted solid phase extraction column, and flow velocity is 2.0 mL min
-1After enrichment finished, (eluent dried up with high pure nitrogen for methyl alcohol: water: glacial acetic acid=95:5:2, v/v/v) wash-out, and using 0.2 mL acetone to redissolve then and using the aperture is that the membrane filtration of 0.45 μ m obtains filtrating with the mixed solution of 2 mL; Get the filtrating of 1 μ L and carry out gas chromatographic analysis.Enrichment finishes back methyl alcohol/glacial acetic acid with 6 mL, and (9:1, v/v) the flushing molecularly imprinted solid phase extraction column is to be used for sample pretreatment next time.
B. gas chromatographic detection:
GC-2010 FPD detecting device; Chromatographic column: RTX-1701 (the neutral capillary column of 30.0 m * 0.25 mm * 0.25 μ m); Column temperature: 90 ℃, stop 1.0 min, with 30 ℃ of min
-1Speed rise to 150 ℃, stop 3.0 min, again with 1 ℃ of min
-1Speed rise to 170 ℃, stop 2.0 min, again with 30 ℃ of min
-1Speed rise to 250 ℃, stop 4.0 min, totally 35 min.Injector temperature: 200 ℃, the FPD detector temperature: 250 ℃, carrier gas is a high pure nitrogen, total flow: 14.0 mL min
-1, post flow: 1.0 mL min
-1, purge flow rate: 3.0 mL min
-1, tail wind drift amount: 30.0 mL min
-1, pressure: 90.9 kPa, sample size: 1 μ L, split ratio: 10:1 obtains chromatographic peak area.
3. the drafting of typical curve
The metrifonate of preparation variable concentrations and Azodrin mixed standard solution and repeating step 2 operations; With metrifonate and Azodrin solution concentration is horizontal ordinate, is ordinate with the chromatographic peak area, draws metrifonate and Azodrin typical curve respectively.
4. take by weighing testing sample, volume ratio (g/mL) 1:5 adds the distilled water ultrasonic Extraction 3 times by weight, merges extract and constant volume and obtains sample extracting solution.
5. the sample extracting solution that obtains in the step 4 is replaced metrifonate and Azodrin standard solution, repeating step 2 operations calculate metrifonate and Azodrin content in the analyte according to the gas chromatography peak area respectively by typical curve.
Methanol concentration of the present invention is 95%; The ice concentration of alcohol is 36%; Acetone concentration is 100%.
Advantage of the present invention and good effect are:
1. the present invention as adsorbent, has avoided shortcomings such as traditional adsorbent poor selectivity with the molecular engram polymeric material that metrifonate and Azodrin are had high selectivity of preparation, has avoided the loaded down with trivial details pre-treatment process of sample.
2. the present invention sets up the molecular engram solid phase extraction technology metrifonate and Azodrin is had highly sensitive detection method with the gas chromatography coupling; Realized metrifonate and Azodrin efficiently concentrating at aqueous phase; Shorten analysis time greatly, be applicable to the fast detecting of pesticide multi-residues.
3. the present invention is with low cost, and is highly sensitive, and experimental implementation is simple, is applicable to the fast detecting of metrifonate and Azodrin in the various agricultural product.
The present invention and the comparison that has other detection methods now:
| ? | Detection method of the present invention | SPE-gas chromatographic detection |
| Adsorbent | Molecularly imprinted polymer | C 18 |
| Pre-treating method | The water efficiently concentrating | Organic solvent extraction, nitrogen blow the back and redissolve with acetone. |
| LDL | 0.52-1.54 μ g L -1 | 10 μ g L -1 |
Description of drawings
Fig. 1 is 0.05 mg L
-1The gas chromatogram of four kinds of organophosphorus pesticide standard solution.Flow velocity is 2.0 mL min
-1, enrichment 100 mL; Sorbing material is respectively (a) MIP, (b) NMIP, (c) C
18
Embodiment
Below in conjunction with embodiment, the present invention is further specified; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The present invention sets up the molecular engram solid phase extraction technology has highly sensitive detection method with the gas chromatography coupling to metrifonate and Azodrin.Its specific embodiment is:
1. the preparation of molecularly imprinted polymer: template molecule metrifonate 1 mmol and Azodrin 1 mmol are dissolved in the 3 mL chloroforms, add 8 mmol MAA, vibration 30 min in oscillator.Add crosslinking chemical 20 mmol EDGMA (ethylene glycol dimethacrylate) and initiating agent azoisobutyronitrile 100 mg then, fully ultrasonic 15 min behind the mixing lead to N
215 min.The three-necked bottle of good seal is put into 58 ℃ of constant temperature water bath water-bath 24 h.After the polymkeric substance that obtains ground 200 mesh sieves with mortar, (9:1, v/v) continuous extraction 8 h used 300 mL100% methanol extractions, 4 h again, and 60 ℃ of vacuum drying 24 h must molecularly imprinted polymer with 300 mL methyl alcohol/glacial acetic acid 9:1 earlier.
2. the foundation of molecular engram solid phase extraction and gas chromatography coupling system
With the molecularly imprinted polymer of preparation as the adsorbent of SPE, and with the gas chromatography coupling, set up molecular engram solid phase extraction and gas chromatography coupling detection architecture.
A. molecular engram solid phase extraction flow process:
100 mg imprinted polymers are filled in the empty solid-phase extraction column, the preparation molecularly imprinted solid phase extraction column, and wash with the first alcohol and water of 5 mL respectively.Then with 100 mL0.05mg L
-1The hybrid standard water solution flow of metrifonate and Azodrin is crossed molecularly imprinted solid phase extraction column, and flow velocity is 2.0 mL min
-1After enrichment finishes; (eluent dries up with high pure nitrogen for methyl alcohol: water: glacial acetic acid=95:5:2, v/v/v) wash-out with the mixed solution of 2 mL; Using 0.2 mL acetone to redissolve and use the aperture then is the membrane filtration of 0.45 μ m, gets the filtrating of 1 μ L and carries out gas chromatographic analysis.Enrichment finishes back methyl alcohol/glacial acetic acid with 6 mL, and (9:1, v/v) the flushing molecularly imprinted solid phase extraction column is to be used for sample pretreatment next time.
B. gas chromatographic detection:
GC-2010 FPD detecting device; Chromatographic column: RTX-1701 (the neutral capillary column of 30.0 m * 0.25 mm * 0.25 μ m); Column temperature: 90 ℃, stop 1.0 min, with 30 ℃ of min
-1Speed rise to 150 ℃, stop 3.0 min, again with 1 ℃ of min
-1Speed rise to 170 ℃, stop 2.0 min, again with 30 ℃ of min
-1Speed rise to 250 ℃, stop 4.0 min, totally 35 min.Injector temperature: 200 ℃, the FPD detector temperature: 250 ℃, carrier gas is a high pure nitrogen, total flow: 14.0 mL min
-1, post flow: 1.0 mL min
-1, purge flow rate: 3.0 mL min
-1, tail wind drift amount: 30.0 mL min
-1, pressure: 90.9 kPa, sample size: 1 μ L, split ratio: 10:1.Obtain chromatographic peak area.
3. the drafting of typical curve
Again respectively with 0.1,0.25,0.5,1.5,2.5,5.0 and 10.0mg L
-1Metrifonate and 2 operations of Azodrin mixed standard solution repeating step.With metrifonate and Azodrin solution concentration is horizontal ordinate, is ordinate with the chromatographic peak area, draws metrifonate and Azodrin typical curve respectively.
4. take by weighing 2.0 g leek samples, add the double steaming solution ultrasonic Extraction 3 times of 10 mL, merge extract and be settled to 100 mL and obtain sample extracting solution.
5. the sample extracting solution that obtains in the step 4 is replaced metrifonate and Azodrin standard solution, repeating step 2 operations are respectively 6.0 μ g L according to resulting gas chromatography peak area by the content that typical curve calculates metrifonate and Azodrin
-1With 4.6 μ g L
-1Therefore, survey that the residual quantity of metrifonate and Azodrin is 0.30 μ g g in the leek
-1With 0.23 μ g g
-1
Claims (1)
1. method that detects metrifonate and Azodrin simultaneously is characterized in that may further comprise the steps:
1) preparation of molecularly imprinted polymer: in chloroformic solution; Metrifonate and Azodrin potpourri (1:1, mol ratio), function monomer 3-aminopropyltriethoxywerene werene, crosslinking chemical ethylene glycol dimethacrylate are mixed with the molar ratio of 1:4:10, add the 100mg azoisobutyronitrile then and carry out polyreaction: ultrasonic 15 min behind the abundant mixing as initiating agent; Logical N2 15 min; Water-bath 24 h in 58 ℃ of constant temperature water baths ground behind 200 mesh sieves polymkeric substance that obtains with 300 mL methyl alcohol/glacial acetic acids (9:1, v/v) continuous extraction 8 h; Use 300 mL methanol extractions, 4 h again, get molecularly imprinted polymer after the drying;
2) foundation of molecular engram solid phase extraction and gas chromatography coupling system
With the molecularly imprinted polymer of preparation as the adsorbent of SPE, and with the gas chromatography coupling, set up molecular engram solid phase extraction and gas chromatography coupling detection architecture;
A. molecular engram solid phase extraction flow process:
The 100 mg imprinted polymers that step 1 is obtained are filled in the empty solid-phase extraction column, the preparation molecularly imprinted solid phase extraction column, and respectively with 5 mL methyl alcohol and the flushing of 5 mL water; Then the hybrid standard water solution flow of 100 mL metrifonate and Azodrin is crossed molecularly imprinted solid phase extraction column, flow velocity is 2.0 mL min
-1After enrichment finished, (eluent dried up with high pure nitrogen for methyl alcohol: water: glacial acetic acid=95:5:2, v/v/v) wash-out, and using 0.2 mL acetone to redissolve then and using the aperture is that the membrane filtration of 0.45 μ m obtains filtrating with the mixed solution of 2 mL; Get the filtrating of 1 μ L and carry out gas chromatographic detection; Back methyl alcohol/the glacial acetic acid with 6 mL of enrichment end (9:1, v/v) the flushing molecularly imprinted solid phase extraction column is to be used for sample pretreatment next time;
B. gas chromatographic detection:
GC-2010 FPD detecting device; Chromatographic column: RTX-1701 (the neutral capillary column of 30.0 m * 0.25 mm * 0.25 μ m); Column temperature: 90 ℃, stop 1.0 min, with 30 ℃ of min
-1Speed rise to 150 ℃, stop 3.0 min, again with 1 ℃ of min
-1Speed rise to 170 ℃, stop 2.0 min, again with 30 ℃ of min
-1Speed rise to 250 ℃, stop 4.0 min, totally 35 min; Injector temperature: 200 ℃, the FPD detector temperature: 250 ℃, carrier gas is a high pure nitrogen, total flow: 14.0 mL min
-1, post flow: 1.0 mL min
-1, purge flow rate: 3.0 mL min
-1, tail wind drift amount: 30.0 mL min
-1, pressure: 90.9 kPa, sample size: 1 μ L, split ratio: 10:1; Obtain chromatographic peak area;
3) drafting of typical curve
The metrifonate of preparation variable concentrations and Azodrin mixed standard solution and repeating step 2 operations; With metrifonate and Azodrin solution concentration is horizontal ordinate, is ordinate with the chromatographic peak area, draws metrifonate and Azodrin typical curve respectively;
4) take by weighing testing sample, volume ratio (g/mL) 1:5 adds the distilled water ultrasonic Extraction 3 times by weight, and merging extract and constant volume is sample extracting solution;
5) sample extracting solution that obtains in the step 4 is replaced metrifonate and Azodrin standard solution, repeating step 2 is operated, and calculates metrifonate and Azodrin content in the analyte according to the peak area of gas chromatography respectively by typical curve;
Described methanol concentration is 95%; Glacial acetic acid concentration is 36%; Acetone concentration is 100%.
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| CN201110316910.7A CN102507820B (en) | 2011-10-18 | 2011-10-18 | Method for detecting trichlorfon and monocrotophos |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104360000A (en) * | 2014-11-20 | 2015-02-18 | 山东农业大学 | Method for simultaneously detecting three organophosphorus pesticides |
| CN105319293A (en) * | 2014-08-04 | 2016-02-10 | 浙江海洋学院 | Method for detecting trichlorfon chiral enantiomers in seawater |
| CN106483218A (en) * | 2016-09-30 | 2017-03-08 | 山东农业大学 | A kind of molecular engram solid phase extraction liquid chromatograph detects metrifonate and Azodrin method simultaneously |
| CN109856091A (en) * | 2018-03-16 | 2019-06-07 | 北方工业大学 | Time-resolved fluorescence test strip for detecting monocrotophos and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635000A (en) * | 2004-12-28 | 2005-07-06 | 中国农业大学 | Molecular engram polyaromatics of organophosphorus parasiticide, method for preparation and application |
| CN1699981A (en) * | 2005-05-13 | 2005-11-23 | 中国人民解放军军事医学科学院卫生学环境医学研究所 | Process for preparation of nano print polymer microballoon for detecting long-lasting phosphorus |
| CN101374411A (en) * | 2006-01-12 | 2009-02-25 | 巴斯夫欧洲公司 | Agrochemical formulations based on molecularly imprinted acrylates |
| CN101644680A (en) * | 2009-09-01 | 2010-02-10 | 济南大学 | Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof |
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2011
- 2011-10-18 CN CN201110316910.7A patent/CN102507820B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635000A (en) * | 2004-12-28 | 2005-07-06 | 中国农业大学 | Molecular engram polyaromatics of organophosphorus parasiticide, method for preparation and application |
| CN1699981A (en) * | 2005-05-13 | 2005-11-23 | 中国人民解放军军事医学科学院卫生学环境医学研究所 | Process for preparation of nano print polymer microballoon for detecting long-lasting phosphorus |
| CN101374411A (en) * | 2006-01-12 | 2009-02-25 | 巴斯夫欧洲公司 | Agrochemical formulations based on molecularly imprinted acrylates |
| CN101644680A (en) * | 2009-09-01 | 2010-02-10 | 济南大学 | Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof |
Non-Patent Citations (14)
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105319293A (en) * | 2014-08-04 | 2016-02-10 | 浙江海洋学院 | Method for detecting trichlorfon chiral enantiomers in seawater |
| CN104360000A (en) * | 2014-11-20 | 2015-02-18 | 山东农业大学 | Method for simultaneously detecting three organophosphorus pesticides |
| CN106483218A (en) * | 2016-09-30 | 2017-03-08 | 山东农业大学 | A kind of molecular engram solid phase extraction liquid chromatograph detects metrifonate and Azodrin method simultaneously |
| CN109856091A (en) * | 2018-03-16 | 2019-06-07 | 北方工业大学 | Time-resolved fluorescence test strip for detecting monocrotophos and application thereof |
| CN109856091B (en) * | 2018-03-16 | 2021-08-03 | 北方工业大学 | Time-resolved fluorescence test strip for detecting monocrotophos and application thereof |
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