CN102121926B - Treatment method used before measurement of 2-cyanoacrylate residue-containing sample - Google Patents
Treatment method used before measurement of 2-cyanoacrylate residue-containing sample Download PDFInfo
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- CN102121926B CN102121926B CN201010596914A CN201010596914A CN102121926B CN 102121926 B CN102121926 B CN 102121926B CN 201010596914 A CN201010596914 A CN 201010596914A CN 201010596914 A CN201010596914 A CN 201010596914A CN 102121926 B CN102121926 B CN 102121926B
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Abstract
The invention discloses a treatment method used before measurement of a 2-cyanoacrylate residue-containing sample. The method comprises the following steps of: weighing 20.0g of wheat or soil sample; soaking the sample in 150ml of methanol for 24 hours; performing suction-filtration; transferring the filtrate to a separating funnel; washing the filtrate for two times with 100ml of n-hexane; removing the n-hexane phase; adding 100 to 200ml of aqueous solution of 2.5 percent sodium sulfate into the methanol layer; respectively performing extraction by using 40ml of dichloromethane; combining the dichloromethane phase; drying the mixture with anhydrous sodium sulfate; filtering the mixture to a triangular flask; concentrating the mixture under reduced pressure until the mixture is dry; and performing constant-volume test with acetone. Because purification with a solid-phase extraction column is eliminated, the method has the characteristics of simple operation, low cost, high recovery rate and the like.
Description
Technical field:
The invention belongs to the determination techniques field of persticide residue, relate to the assay method of 2-cyano-3-amino-3-phenylancryic acetate residual quantity in wheat and the soil.Particularly a kind of preceding disposal route of the residual sample determination of agricultural chemicals 2-cyano-3-amino-3-phenylancryic acetate that contains.
Background technology:
Residues of pesticides refer in agricultural production that a part of agricultural chemicals directly or indirectly remains in cereal, vegetables, fruit, livestock products, the aquatic products and the phenomenon in soil and the water body behind the applying pesticides.The residues of pesticides problem is produced along with agricultural chemicals is a large amount of and is widely used and produces.The agricultural chemicals that uses at present, can become innoxious substance some within a short period of time through biodegradation, and some organic chlorine agriculture chemicals are difficult to degraded, are the strong agricultural chemicals of residual.Vegetable pesticide residue exceeds standard, and can directly jeopardize the nervous system and the vitals such as liver, kidney of human body.Remains of pesticide is accumulated in human body simultaneously, after necessarily measuring, can cause some chronic diseases, like muscle numbness, cough etc., even can bring out vascular diseases, diabetes and cancer etc.Because residues of pesticides are very big to the mankind and biohazard, various countries all carry out strict management to using of agricultural chemicals, and residues of pesticides tolerance in the food has been made regulation.
The pesticide species that residues of pesticides are poisoned mainly is organophosphorus pesticide and carbamate chemicals for agriculture in China more causing to take place, like flolimat, Rogor, malathion, acephatemet, Azodrin, Entex, hectogram prestige, anti-bud prestige and sevin etc.These agricultural chemicals are to make it the dead insecticidal action of bringing into play through the cholinesterase that suppresses in the insect nervous centralis.But these agricultural chemicals also have inhibiting effect to the cholinesterase in the human body, and the transmission of its ability block nerves mediator causes that muscular paralysis causes poisoning.Though country expressly provides severe toxicity, high-toxic pesticide and must not be used for vegetables, melon and fruit, tealeaves and Chinese medicinal herbs that for example flolimat, parathion, thimet, acephatemet, isocarbophos, furan are fed pellet etc.But the vegetable grower of certain areas still uses hypertoxic high-toxic pesticides such as acephatemet, parathion-methyl in vegetables, occurs the consumer frequently because of the edible vegetables acute poisoning that contains methamidophos pesticide.
2-cyano-3-amino-3-phenylancryic acetate is a kind of new type bactericide, chemical name: 2-cyanic acid-3-aminoacrylic acid ethyl ester belongs to 2-cyanoacrylate germifuge.Pure article are white solid, 117 ℃～119 ℃ of fusing points (pure article).Be insoluble in non-polar solvents such as water, sherwood oil, toluene; Be soluble in chloroform, acetone, dimethyl sulfoxide, N, dinethylformamide isopolarity solvent.
2-cyano-3-amino-3-phenylancryic acetate belongs to novel agrochemical, the method that the pre-treating method that this patent adopted is researched and developed for my unit voluntarily.Pertinent literature " gas chromatography determination 2-cyano-3-amino-3-phenylancryic acetate in wheat residual " is arranged; The described method of the document is that sample extracts with acetonitrile, the solid phase extraction column purification; The described method of this patent has been omitted SPE column purification part, has practiced thrift detection cost and pre-treatment time.
Summary of the invention:
The described method of this patent is used methanol extraction, purifies with liquid-liquid extraction, and without the SPE column purification, has simple to operately, and cost is low, characteristics such as recovery height.In order to estimate the security after 2-cyano-3-amino-3-phenylancryic acetate uses in wheat, the present invention has set up the method for using 2-cyano-3-amino-3-phenylancryic acetate residual quantity in the gas chromatography determination wheat.Specifically be to use 2-cyano-3-amino-3-phenylancryic acetate in organic solvent extraction wheat or the soil, utilize the organic solvent after rotary evaporation will filter to be concentrated into the dry doubling constant volume fully, adopt gas chromatograph to detect at last.
The present invention adds recovery research through 2-cyano-3-amino-3-phenylancryic acetate, adopts vapor-phase chromatography, sets up 2-cyano-3-amino-3-phenylancryic acetate residue analysis method in the simple and direct feasible wheat.
The more detailed assay method of the present invention is following:
Sample pre-treatments
1.1 test material
Agilent 6890 gas chromatographs (ECD), sample comminutor, BUCHI rotary evaporator etc.; Methyl alcohol (chromatographically pure); Acetone (chromatographically pure); Normal hexane (chromatographically pure); Methylene chloride (analyzing pure); Anhydrous sodium sulfate (analyzing pure); 2-cyano-3-amino-3-phenylancryic acetate standard items (content 99%)
1.2 pre-treatment step
Take by weighing sample 20.0g in triangular flask, add 150ml methyl alcohol soaked overnight, then suction filtration; Filtrating is transferred to separating funnel,, discards the normal hexane phase with 50ml normal hexane washing 2 times; In methanol layer, add 2.5% aqueous sodium persulfate solution 100ml, use the 40ml dichloromethane extraction respectively 3 times, the combined dichloromethane phase; Through anhydrous sodium sulfate drying and be filtered in the triangular flask, be evaporated to dried, to be measured with the acetone constant volume.
2, analytical test
2.1 instrument condition
Agilent 6890N (ECD), chromatographic column: DB-1701,30m * 0.25mm * 0.25 μ m, column temperature: 100 ℃ of initial temperatures, 15 ℃/min is warming up to 250 ℃, keeps 15min.Vapourizing temperature: 250 ℃ of detected temperatures: 250 ℃.Carrier gas: N
2(>=99.999%).Column flow rate: 1.0mL/min.Replenish gas: 30mL/min.Sample size: 2 μ L
2.2 typical curve
This test adopts external standard method (peak area) to measure content.Under these conditions, measure 2-cyano-3-amino-3-phenylancryic acetate sample size (ng) and peak area (μ vs) correlativity.The result is following:
Y＝17555X-105；r＝0.9997
2.3 residual quantity computing formula
R=Q * V
Eventually/ (V
Appearance* W)
Persticide residue in the R-sample (mg/kg)
The corresponding pesticide volume (ng) that Q-calculates through typical curve
V
EventuallyThe final constant volume of-sample solution (ml)
V
Appearance-sample solution sampling volume (μ l)
W-claims a kind weight (g)
3, sensitivity, degree of accuracy and accuracy test result
Minimum detectable activity: measuring the 2-cyano-3-amino-3-phenylancryic acetate minimum detectable activity is 4.8 * 10
-11g
Concentration limit: wheat seed and soil are 0.003mg/kg.
This method adopts external standard method (peak area) to measure content.Under above-mentioned instrument condition, measure 2-cyano-3-amino-3-phenylancryic acetate sample size (ng) and peak area (μ vs) correlativity.The result is following:
Y＝17555X-105；r＝0.9997
Table 1 2-cyano-3-amino-3-phenylancryic acetate standard items sample size and peak area correlativity
| Sample size (ng) | 0.2 | 1.0 | 2.0 | 4.0 | 8.0 |
| Peak area (μ vs) | 5136 | 16101 | 35103 | 68957 | 141017 |
Table 2 adds recovery test table as a result
Advantage and the characteristics that contain the processing before the residual appearance of 2-cyano-3-amino-3-phenylancryic acetate agricultural product is measured disclosed by the invention are:
(1) disposal route of the present invention can effectively be avoided the interference of residual sample mesostroma, obtains good effect.
(2) disposal route of the present invention has higher accuracy, and precision and sensitivity are simple and quick, and the recovery is high, and finding speed is fast, and equipment is simple, cost of determination is low, stability and reliability high (methodology developments description of drawings).
Description of drawings:
Fig. 1 is 2-cyano-3-amino-3-phenylancryic acetate standard items spectrograms;
Fig. 2 adds the 2-cyano-3-amino-3-phenylancryic acetate spectrogram for soil;
Fig. 3 does not add the 2-cyano-3-amino-3-phenylancryic acetate spectrogram for soil;
Fig. 4 adds the 2-cyano-3-amino-3-phenylancryic acetate spectrogram for wheat;
Fig. 5 does not add the 2-cyano-3-amino-3-phenylancryic acetate spectrogram for wheat.
Embodiment
Below in conjunction with embodiment the present invention is done further explanation, it is indicative that embodiment is merely, and means that never it limits scope of the present invention by any way.Wherein used raw material or reagent all have commercially available.
Embodiment 1
Take by weighing wheat samples 20.0g in triangular flask, add 200ml methyl alcohol and soaked 308 hours, then suction filtration; Filtrating is transferred to separating funnel,, discards the normal hexane phase with 50ml normal hexane washing 2 times; In methanol layer, add 2.5% aqueous sodium persulfate solution 150ml, use the 40ml dichloromethane extraction respectively 2 times, the combined dichloromethane phase; Through anhydrous sodium sulfate drying and be filtered in the triangular flask, be evaporated to dried, to be measured with the acetone constant volume.Adopt ultra high efficiency liquid phase-mass spectrum/GC-MS to measure.
The result who measures by above-mentioned condition is and does not detect.
Embodiment 2
The soil 20.0g that takes by weighing the plantation wheat adds 150ml methyl alcohol soaked overnight, then suction filtration in triangular flask; Filtrating is transferred to separating funnel,, discards the normal hexane phase with 50ml normal hexane washing 2 times; In methanol layer, add 2.5% aqueous sodium persulfate solution 100ml, use the 40ml dichloromethane extraction respectively 3 times, the combined dichloromethane phase; Through anhydrous sodium sulfate drying and be filtered in the triangular flask, be evaporated to dried, to be measured with the acetone constant volume.Adopt ultra high efficiency liquid phase-mass spectrum/GC-MS to measure.
The result who measures by above-mentioned condition is and does not detect.
Claims (2)
1. one kind contains the preceding disposal route of the residual sample determination of 2-cyano-3-amino-3-phenylancryic acetate, it is characterized in that: take by weighing sample 20.0g in triangular flask, add 150-200ml methyl alcohol and soaked 24-48 hour; Suction filtration then, the separation of will filtrating is with 50-100ml normal hexane washing 2 times; Discard the normal hexane phase, in methanol layer, add 2.5% aqueous sodium persulfate solution 100-200ml, use the 40-80ml dichloromethane extraction respectively; The combined dichloromethane phase; Through anhydrous sodium sulfate drying and filter, be evaporated to dried, to be measured with the acetone constant volume; Wherein said sample is wheat and plantation wheat soil.
2. the disposal route before the described sample determination of claim 1, the wherein said sample 20.0g that takes by weighing adds 150ml methyl alcohol soaked overnight, then suction filtration in triangular flask; Filtrating is transferred to separating funnel,, discards the normal hexane phase with 50ml normal hexane washing 2 times; In methanol layer, add 2.5% aqueous sodium persulfate solution 100ml, use the 40ml dichloromethane extraction respectively 3 times, the combined dichloromethane phase; Through anhydrous sodium sulfate drying and be filtered in the triangular flask, be evaporated to dried, to be measured with the acetone constant volume.
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| CN201010596914A CN102121926B (en) | 2010-12-20 | 2010-12-20 | Treatment method used before measurement of 2-cyanoacrylate residue-containing sample |
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| CN201010596914A CN102121926B (en) | 2010-12-20 | 2010-12-20 | Treatment method used before measurement of 2-cyanoacrylate residue-containing sample |
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| CN102121926B true CN102121926B (en) | 2012-09-26 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
Non-Patent Citations (1)
| Title |
|---|
| 曹斌 等.气相色谱法测定氰烯菌酯在小麦中的残留.《现代农药》.2009,第8卷(第3期),全文. * |
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