CN102507820B - Method for detecting trichlorfon and monocrotophos - Google Patents
Method for detecting trichlorfon and monocrotophos Download PDFInfo
- Publication number
- CN102507820B CN102507820B CN201110316910.7A CN201110316910A CN102507820B CN 102507820 B CN102507820 B CN 102507820B CN 201110316910 A CN201110316910 A CN 201110316910A CN 102507820 B CN102507820 B CN 102507820B
- Authority
- CN
- China
- Prior art keywords
- azodrin
- metrifonate
- phase extraction
- molecularly imprinted
- solid phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Sampling And Sample Adjustment (AREA)
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 simultaneously metrifonate and Azodrin, belong to the food safety detection technical field.
Background technology
In the present agricultural chemicals using, most widely used (above 100 kinds) of organophosphorus insecticide, toxicity is maximum.Metrifonate and Azodrin are the broad spectrum pesticides in the organophosphorus pesticide, have efficient, low toxicity, low-residual, the characteristics such as good water solubility, be often used as insecticide spraying in fruit tree, on the vegetables, although it is more easily degraded than organo-chlorine pesticide, residual life, is shorter, but organophosphorus pesticide toxicity is also higher, if remain in fruit, agricultural chemicals on the vegetables or the agricultural chemicals in the entered environment enter organism, most of have inhibiting effect to cholinesterase in the biosome, suppressing cholinesterase makes it lose the ability of decomposing acetylcholine, cause the acetylcholine accumulation, cause nerve dysfunction, thereby cause the infringement of human body.As acetylcholine inhibitor, the environmental exposure of organophosphorus pesticide and skin contact can cause biotoxication.
It is the focus of International Food Safety Control area research and development that pesticide multi-residues detects, at present the main methods such as gas chromatography, liquid chromatography, immunoassay, gas chromatography-mass spectrum (GC-MS) and liquid chromatography-mass spectrography (LC-MS) that adopt.The chromatography mass spectrometry detection sensitivity is high but expensive.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 trace residues of pesticides and the export trade detect
-1), therefore before analyzing, usually need to carry out enrichment.The pre-treating method that adopts at present mainly contains Solid-Phase Extraction, liquid-liquid extraction, Dispersive solid phase extraction, solid-phase microextraction, supercritical fluid extraction and column chromatography etc.Wherein Solid-Phase Extraction and solid-phase microextraction have many advantages than liquid-liquid extraction, replace gradually liquid-liquid extraction.But often selectivity is relatively poor based on commercial Solid-Phase Extraction material, and the acting force between object and the adsorbent is nonspecific, and the efficient of extraction and cleaning is not high, sometimes also be difficult to thoroughly remove the interference of matrix, 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, to guaranteeing that effective examination and controlling supervision tool of organophosphorus pesticide is of great significance in China's food.
Summary of the invention
In order to overcome long, the defective such as instrument is expensive, poor accuracy, pre-treatment the are loaded down with trivial details detection time that exists in traditional metrifonate and the Azodrin detection method, the invention provides a kind of method that detects simultaneously metrifonate and Azodrin.
A kind of method that detects simultaneously metrifonate and Azodrin, finish 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 APTES, crosslinking chemical ethylene glycol dimethacrylate mix with the molar ratio of 1:4:10, then add the 100mg azoisobutyronitrile and carry out polyreaction as initiating agent; The polymkeric substance that obtains is ground rear usefulness 300 mL methyl alcohol/glacial acetic acid (9:1, v/v) continuous extractions 8 h, use again 300 mL methanol extractions, 4 h, get molecularly imprinted polymer after the drying.
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 Solid-Phase Extraction, and with the gas chromatography coupling, set up molecular engram solid phase extraction and gas chromatography coupling detection system.
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 finishes, with the mixed solution of 2 mL (methyl alcohol: water: glacial acetic acid=95:5:2, v/v/v) wash-out, eluent dries up with high pure nitrogen, is that the membrane filtration of 0.45 μ m obtains filtrate with the redissolution of 0.2 mL acetone and with the aperture then; Get the filtrate of 1 μ L and carry out gas chromatographic analysis.Methyl alcohol/glacial acetic acid (9:1, v/v) with 6 mL after enrichment finishes washes molecularly imprinted solid phase extraction column to be used for next time sample pretreatment.
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 rising to 150 ℃, stop 3.0 min, again with 1 ℃ of min
-1Speed rising to 170 ℃, stop 2.0 min, again with 30 ℃ of min
-1Speed rising to 250 ℃, stop 4.0 min, totally 35 min.Injector temperature: 200 ℃, the FPD detector temperature: 250 ℃, carrier gas is 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; Take metrifonate and Azodrin solution concentration as horizontal ordinate, take chromatographic peak area as ordinate, draw respectively metrifonate and Azodrin typical curve.
4. take by weighing testing sample, volume ratio (g/mL) 1:5 adds the ultrasonic extraction of distilled water 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 respectively metrifonate and Azodrin content in the analyte according to the gas chromatography peak area 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 the 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 pretreatment process of sample.
2. the present invention has highly sensitive detection method with molecular engram solid phase extraction technology and gas chromatography coupling foundation to metrifonate and Azodrin, realized metrifonate and the Azodrin efficiently concentrating at aqueous phase, greatly shorten analysis time, 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 | Organophosphorous pesticides detects | |
| Adsorbent | Molecularly imprinted polymer | C 18 |
| Pre-treating method | The water efficiently concentrating | Organic solvent extracts, and nitrogen blows and redissolves with acetone afterwards. |
| Lowest detectable limit | 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 described; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The present invention has highly sensitive detection method with molecular engram solid phase extraction technology and gas chromatography coupling foundation 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.Then add crosslinking chemical 20 mmol EDGMA(ethylene glycol dimethacrylates) and initiating agent azoisobutyronitrile 100 mg, 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, use first 300 mL methyl alcohol/glacial acetic acid 9:1(9:1, v/v) continuous extraction 8 h, use again 300 mL100% methanol extractions, 4 h, 60 ℃ of vacuum drying 24 h get molecularly imprinted polymer.
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 Solid-Phase Extraction, and with the gas chromatography coupling, set up molecular engram solid phase extraction and gas chromatography coupling detection system.
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, with the mixed solution of 2 mL (methyl alcohol: water: glacial acetic acid=95:5:2, v/v/v) wash-out, eluent dries up with high pure nitrogen, then be the membrane filtration of 0.45 μ m with the redissolution of 0.2 mL acetone and with the aperture, get the filtrate of 1 μ L and carry out gas chromatographic analysis.Methyl alcohol/glacial acetic acid (9:1, v/v) with 6 mL after enrichment finishes washes molecularly imprinted solid phase extraction column to be used for next time sample pretreatment.
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 rising to 150 ℃, stop 3.0 min, again with 1 ℃ of min
-1Speed rising to 170 ℃, stop 2.0 min, again with 30 ℃ of min
-1Speed rising to 250 ℃, stop 4.0 min, totally 35 min.Injector temperature: 200 ℃, the FPD detector temperature: 250 ℃, carrier gas is 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.Take metrifonate and Azodrin solution concentration as horizontal ordinate, take chromatographic peak area as ordinate, draw respectively metrifonate and Azodrin typical curve.
4. take by weighing 2.0 g leek samples, add the ultrasonic extraction of double steaming solution 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. a molecular engram solid phase extraction and gas chromatography coupling detect metrifonate and Azodrin method simultaneously, it is characterized in that this detection method may further comprise the steps:
1) preparation of molecularly imprinted polymer: in chloroformic solution, potpourri, function monomer MAA, the crosslinking chemical ethylene glycol dimethacrylate of metrifonate and Azodrin mol ratio 1:1 are mixed with the molar ratio of 1:4:10, then add the 100mg azoisobutyronitrile and carry out polyreaction as initiating agent: ultrasonic 15min behind the abundant mixing, logical N
215min, water-bath 24h in 58 ℃ of constant temperature water baths ground behind 200 mesh sieves polymkeric substance that obtains with 300mL methyl alcohol/glacial acetic acid 9:1, v/v continuous extraction 8h uses 300mL methanol extraction 4h again, after the drying molecularly imprinted polymer;
2) foundation of molecular engram solid phase extraction and gas chromatography coupling system
With the molecularly imprinted polymer of preparation as the adsorbent of Solid-Phase Extraction, and with the gas chromatography coupling, set up molecular engram solid phase extraction and gas chromatography coupling detection system;
A. molecular engram solid phase extraction flow process:
The 100mg imprinted polymer that step 1 is obtained is filled in the empty solid-phase extraction column, the preparation molecularly imprinted solid phase extraction column, and respectively with 5mL methyl alcohol and the flushing of 5mL water; Then with 100mL0.05mg.L
-1The hybrid standard aqueous solution of metrifonate and Azodrin; Flow through molecularly imprinted solid phase extraction column, flow velocity is 2.0mL.min
-1After enrichment finishes, use 2mL methyl alcohol: water: glacial acetic acid=95:5:2, the mixed solution wash-out of v/v/v, eluent dries up with high pure nitrogen, is that the membrane filtration of 0.45 μ m obtains filtrate with the redissolution of 0.2mL acetone and with the aperture then; Get the filtrate of 1 μ L and carry out gas chromatographic analysis; Enrichment finishes rear methyl alcohol with 6mL/glacial acetic acid 9:1, and v/v flushing molecularly imprinted solid phase extraction column is to be used for next time sample pretreatment;
B. gas chromatographic detection:
The GC-2010FPD detecting device; The neutral capillary column of chromatographic column: RTX-1701:30.0m * 0.25mm * 0.25 μ m; Column temperature: 90 ℃, stop 1.0min, with 30 ℃ of .min
-1Speed rising to 150 ℃, stop 3.0min, again with 1 ℃ of .min
-1Speed rising to 170 ℃, stop 2.0min, again with 30 ℃ of .min
-1Speed rising to 250 ℃, stop 4.0min, altogether 35min; Injector temperature: 200 ℃, the FPD detector temperature: 250 ℃, carrier gas is high pure nitrogen, total flow: 14.0mL.min
-1, post flow: 1.0mL.min
-1, purge flow rate: 3.0mL.min
-1, tail wind drift amount: 30.0mL.min
-1, pressure: 90.9kPa, sample size: 1 μ L, split ratio: 10:1;
3) drafting of typical curve
The metrifonate of preparation variable concentrations and Azodrin mixed standard solution and repeating step 2 operations; Take metrifonate and Azodrin solution concentration as horizontal ordinate, take chromatographic peak area as ordinate, draw respectively metrifonate and Azodrin typical curve;
4) take by weighing testing sample, volume ratio g/mL1:5 adds the ultrasonic extraction of distilled water 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 operations calculate respectively metrifonate and Azodrin content in the analyte according to the peak area of gas chromatography by typical curve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110316910.7A CN102507820B (en) | 2011-10-18 | 2011-10-18 | Method for detecting trichlorfon and monocrotophos |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110316910.7A CN102507820B (en) | 2011-10-18 | 2011-10-18 | Method for detecting trichlorfon and monocrotophos |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102507820A CN102507820A (en) | 2012-06-20 |
| CN102507820B true CN102507820B (en) | 2013-10-16 |
Family
ID=46219926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110316910.7A Expired - Fee Related CN102507820B (en) | 2011-10-18 | 2011-10-18 | Method for detecting trichlorfon and monocrotophos |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102507820B (en) |
Families Citing this family (4)
| 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 |
| CN106483218B (en) * | 2016-09-30 | 2019-03-29 | 山东农业大学 | A kind of molecular engram solid phase extraction-liquid chromatogram detects metrifonate and Azodrin method simultaneously |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263777C (en) * | 2004-12-28 | 2006-07-12 | 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 |
| CN101644680B (en) * | 2009-09-01 | 2012-03-14 | 济南大学 | Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof |
-
2011
- 2011-10-18 CN CN201110316910.7A patent/CN102507820B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102507820A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103399099B (en) | Method for detecting nine organophosphorus pesticides simultaneously | |
| Zhou et al. | Preparation, evaluation and application of molecularly imprinted solid-phase microextraction monolith for selective extraction of pirimicarb in tomato and pear | |
| Du et al. | An in situ immobilized pipette tip solid phase microextraction method based on molecularly imprinted polymer monolith for the selective determination of difenoconazole in tap water and grape juice | |
| CN102371084A (en) | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) solid phase extraction column and preparation method and application thereof | |
| CN101768238B (en) | Citrinin molecular engram material and preparation method as well as application thereof | |
| CN102532390A (en) | Triazine weedicide, and metabolite molecular engram polymer microspheres, preparation method and application thereof | |
| CN102372821A (en) | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) and preparation method thereof | |
| CN103901129A (en) | Method for detecting ten types of organophosphorus pesticides by using magnetic separation-gas chromatography | |
| Hu et al. | An amobarbital molecularly imprinted microsphere for selective solid-phase extraction of phenobarbital from human urine and medicines and their determination by high-performance liquid chromatography | |
| CN102507820B (en) | Method for detecting trichlorfon and monocrotophos | |
| CN102174148A (en) | Preparation of triazine phytocide molecular imprinting solid phase extracting material | |
| CN102924645A (en) | Preparation method and application of molecularly imprinted polymer of penicillin antibiotics and intermediate of penicillin antibiotics | |
| Du et al. | Pipette tip-based molecularly imprinted monolith for selective micro-solid-phase extraction of methomyl in environmental water | |
| CN104083904B (en) | Functionalization porous zinc sulfide nano microballoon solid-phase extraction column and preparation method thereof | |
| CN104558361A (en) | Preparation method and application of hydrophilic polyaromatic hydrocarbon molecularly imprinted solid phase extraction filler | |
| CN104568562A (en) | Water sample and pretreatment method of nitrosoamine compound in suspended matter of water sample | |
| CN102731706B (en) | Carbofuran molecularly imprinted microspheres, preparation and application thereof | |
| CN105974018A (en) | Method for detecting toxoflavin in foodstuff based on multifunctional purifying column-high performance liquid chromatography | |
| CN103396512B (en) | The preparation method and application of hybrid template molecularly imprinted polymer and solid-phase extraction column thereof | |
| CN103551125A (en) | Preparation method of Sudan red II molecular imprinting solid-phase extraction column filling material | |
| CN101497035B (en) | Preparation method of solid-phase extraction small column for molecular imprinting of substituted carbamide pesticide | |
| CN104101661B (en) | A kind of method for quick of Detection of Magdala in Food Through | |
| CN103342774A (en) | Preparation method and application of bitertanol based molecularly-imprinted solid-phase extraction column | |
| CN101914066B (en) | Method for purifying and detecting pirimicarb by utilizing molecularly imprinted polymer (MIP) | |
| CN104001347A (en) | Preparation method of hydrophilic broad-spectrum solid-phase extraction column |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131016 Termination date: 20211018 |