CN1766604A - The rapid assay methods of pesticide avermectin and toxic metabolite residue thereof - Google Patents
The rapid assay methods of pesticide avermectin and toxic metabolite residue thereof Download PDFInfo
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- CN1766604A CN1766604A CN 200510030028 CN200510030028A CN1766604A CN 1766604 A CN1766604 A CN 1766604A CN 200510030028 CN200510030028 CN 200510030028 CN 200510030028 A CN200510030028 A CN 200510030028A CN 1766604 A CN1766604 A CN 1766604A
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Abstract
The invention discloses the rapid assay methods of a kind of pesticide avermectin and toxic metabolite residue thereof, with the acetonitrile is extraction agent, the Avermectin that remains in the fruits and vegetables agricultural products is extracted, and utilize salting out to use organic phase and aqueous phase separation, Avermectin enters organic phase, omit purification process, directly the Avermectin of extracting is carried out the pre-column fluorescence derivatization with trifluoroacetic anhydride (TFAA)-N-methylimidazole (NMIM)-acetonitrile (ACN) method under anhydrous state, in this process, the derivant that has the light group that spreads out is given birth in the Avermectin reaction, and final sample carries out the Avermectin retention analysis at high performance liquid chromatography-fluorescence detector.That the inventive method has is easy and simple to handle, quick, detect advantages such as cost is low, testing result is accurate.
Description
Technical field
The present invention relates to a kind of assay method of residues of pesticides, relate in particular to the rapid assay methods of pesticide avermectin and toxic metabolite residue thereof.
Background technology
Because insecticidal activity is strong and characteristic of wide insecticidal spectrum, Avermectin is used in the agricultural production throughout the country widely as the substitute of acephatemet, the contour malicious organophosphorus insecticide in malathion.Though Avermectin is to belong to microbial pesticide, it is 10mgkg to the lethal dose of 50 value of rat
-1, with the lethal dose of 50 value (3.5-12.5mgkg of parathion
-1) similar, belong to high-toxic pesticide.In addition, Avermectin has the genotoxic potential effect to mammiferous breeding fecundity
[3], discover
]After feed dosage is the water in 1.19～2.13mg//sky, the vas deferens of male wister rat has tangible conjunctive tissue accumulation, and be attended by tangible angiorrbagia, the cortisol content water yield in the serum significantly descends, reproduction experiment proves that also the fertility fecundity of these male wister rats significantly descends, and the probability that stillborn foetus takes place the spouse obviously improves.Therefore, people are very strict to maximum residue limit(MRL) (MRL value) standard-required of Avermectin, and wherein the Ministry of Agriculture stipulates that its MRL value is 20 μ gkg in citrus
-1, leaf vegetables is 50 μ gkg
-1 [1]European Union's specified in more detail its MRL value in multiple agricultural product, mostly be 10 μ gkg in agricultural product MRL values such as fruit and vegetable food, cereal
-1Korea S stipulates that its MRL value is 20 μ gkg in apple
-1, celery is 50 μ gkg
-1The MRL value of Israel's regulation is 10 μ gkg in fruits and vegetables agricultural product such as cucumber, eggplant, peach, strawberry
-1The MRL value of Australia's regulation is 10 μ gkg on products such as apple, pears, tomato
-1]
The Avermectin molecular weight is big, extremely difficult gasification, and still do not have feasible GC derivatization method, and can't adopt GC to analyze, the residue detection research of Avermectin and toxic metabolite thereof great majority are that means are carried out with HPLC at present.Have the conjugated diolefine structure in the Avermectin molecular structure, strong uv absorption can be arranged at the 245nm place, but the sensitivity of ultraviolet detection is too low, can't satisfy the retention analysis requirement of present agricultural product Avermectin and toxic metabolite thereof; Fluorescence detector (FD) becomes the main means of retention analysis of present Avermectin and metabolin thereof owing to its good detection sensitivity and selectivity.Although on agricultural product such as fruits and vegetables are produced, use more and more, but the retention analysis of Avermectin and toxic metabolite thereof report is more common in the retention analysis on the livestock products at present, and less about the report of the retention analysis on the fruit and vegetable food, and sample pre-treatments mostly is loaded down with trivial details in institute's reported method.Patent retrieval finds that the patent that is relevant to Avermectin concentrates on product development application and the derived product Application and Development thereof mostly, does not retrieve as yet about the patent of Avermectin method for detecting residue on the fruits and vegetables agricultural products.
Summary of the invention
At the deficiency that prior art exists, the object of the present invention is to provide the liquid phase-fluorescence detection method rapidly and efficiently of a kind of pesticide avermectin and toxic metabolite residue thereof, this method is simple to operate, cost is low, quick, accurate.
The technical scheme that realizes objects of the present invention is as follows:
The rapid assay methods of a kind of pesticide avermectin and toxic metabolite residue thereof, its step is as follows:
A, specimen preparation: gather the fruits and vegetables sample earlier with the cutter chopping, use tissue mashing machine's homogenate again, and freezing preservation;
B, sample pre-treatments: the sample thief homogenate places container, add acetonitrile, mixing the back filters, filtrate collecting is equipped with in the tool plug graduated cylinder of sodium chloride, static behind the concuss, make acetonitrile mutually and the water layering, then with acetonitrile mutually in solution move to test tube and dry up, the adding anhydrous acetonitrile is dissolved in the acetonitrile solution Avermectin attached to test tube wall in test tube.
C, pre-column derivatization: under lucifuge, room temperature condition, treating in the derivatization sample of acetonitrile dissolving, add the N-methylimidazole earlier: the derivative reagent that acetonitrile (volume ratio 3: 7～5: 5) is formed, add trifluoroacetic anhydride again: the derivative reagent that acetonitrile (volume ratio 3: 7～5: 5) is formed, after vibration shakes up reaction 30-35min, add methyl alcohol again and shake up reaction 60-70min, enter high performance liquid chromatography-fluorescence detector (HPLC-FD) behind the reacting liquid filtering and measure.
The proportional range of sample homogenization liquid and acetonitrile is 1/2.5～1/3 (volume ratio) in the described B step.
The volume ratio of each component is in the described C step: acetonitrile dissolving treat the derivatization sample: N-methylimidazole: the derivative reagent that acetonitrile (volume ratio 3: 7～5: 5) is formed: trifluoroacetic anhydride: the derivative reagent that acetonitrile (volume ratio 3: 7～5: 5) is formed: methyl alcohol=1: 0.5: 0.5: 1～1: 0.5: 0.5: 2.
Acetonitrile phase sample extraction solution is placed on the Nitrogen evaporator and dries up in the described B step.
The present invention is extraction agent with the acetonitrile, the Avermectin that remains in the fruits and vegetables agricultural products is extracted, and utilize salting out to use organic phase and aqueous phase separation, Avermectin enters organic phase, omit purification process, directly the Avermectin of extracting is carried out the pre-column fluorescence derivatization with trifluoroacetic anhydride (TFAA)-N-methylimidazole (NMIM)-acetonitrile (ACN) method under anhydrous state, in this process, the derivant that has the light group that spreads out is given birth in the Avermectin reaction, and final sample carries out the Avermectin retention analysis at high performance liquid chromatography-fluorescence detector.
The inventive method has following advantage;
1, the inventive method is directly carried out pre-column derivatization with acetonitrile after to sample extraction, has omitted the process of SPE column purification, and this pre-treating method operation is more easy, save time, and has saved the use of analytical reagent and SPE post simultaneously, has greatly reduced the detection cost.
2, the inventive method can also detect its toxic metabolite 8,9-Z-B except detecting Avermectin self
1(see figure 1), 8,9-Z-B
1Be Avermectin B
1The photoisomerization product, the product and the B of gained behind its process NMIM-TFAA-CAN method fluorescence derivatization reaction
1aDerivative products be same substance.
3, the detectability of the inventive method is lower than one of existing maximum residue limit value more than the order of magnitude, and accuracy and precision meet the residue detection requirement.
4, the inventive method is after derivatization reaction is finished, add a certain amount of methyl alcohol again and place certain hour, make the ester type structure derivative products of Avermectin all be converted to stable pure formula structure, when data processing, only need carry out integration and just can accurately measure Determination of Abamectin Residue the peak value of pure formula structure product, the problem that technical method has only been omitted pure formula structure product to ester type structure product integration before avoiding, thus the inventive method helps accurately measuring Determination of Abamectin Residue more.
Figure of description
Fig. 1 is liquid chromatography (HPLC-FD) figure of Avermectin standard specimen;
Fig. 2 is liquid chromatography (HPLC-FD) figure of blank wild cabbage;
Fig. 3 is for adding wild cabbage sample liquid chromatography (HPLC-FD) figure of Avermectin standard specimen.
Embodiment
How further specify the present invention below by specific embodiment realizes:
Embodiment 1
1 sample pre-treatments
1.1 specimen preparation: the about 200g of collected specimens, with the cutter chopping, use tissue mashing machine's homogenate more earlier, be placed in-20 ℃ of refrigerators and preserve.
1.2 sample pre-treatments: accurately take by weighing sample homogenization liquid 20g and place the flat vial of 250mL, add the 50mL acetonitrile, sample is at 14000rmin
-1Behind the even matter 2min of at a high speed even matter device, use filter paper filtering, filtrate collecting is equipped with in the 100mL tool plug graduated cylinder of 5g～7g sodium chloride, collects filtrate, covers stopper, concuss 2min, and at room temperature static 30min makes acetonitrile phase and water layering.Draw 10mL solution from acetonitrile mutually and be transferred to 10mL scale test tube, the test tube that sample liquid is housed is placed on blows near doing on the Nitrogen evaporator, add the 0.5mL anhydrous acetonitrile in the test tube, ultrasonic 1min on supersonic wave cleaning machine then, make Avermectin be dissolved in acetonitrile solution fully, treat derivatization attached to test tube wall.
2 pre-column derivatizations
Derivative reagent A:N-methylimidazole (NMIM) and acetonitrile (the two volume ratio 3: 7), now with the current;
Derivative reagent B: trifluoroacetic anhydride (TFAA) and acetonitrile (the two volume ratio 3: 7), now with the current;
Concrete operations step: under lucifuge, room temperature environment condition, in the test tube for the treatment of derivatization sample or standard specimen that the dissolving of 0.5mL acetonitrile is housed, successively add 0.25mL derivative reagent A and 0.25mL derivative reagent B respectively, covering the vibration of test tube plug immediately shakes up, behind the reaction 30min, add 1mL methyl alcohol in the test tube again and shake up, react 1h again after, reactant liquor is crossed and is carried out HPLC-FD behind the 0.45 μ m filter membrane and measure.
3 chromatographic conditions
Chromatographic column: Waters-C
18(150mm * 4.6mm, 5 μ m); Moving phase: water: acetonitrile=5: 95, flow velocity are 1.0mLmin
-1Detect wavelength: fluorescence exciting wavelength 365nm, emission wavelength 475nm; Column temperature: 40 ℃; Sample size: 10 μ l; Quantivative approach: external standard method (peak area).
Embodiment 2
1 sample pre-treatments
1.1 specimen preparation: the about 200g of collected specimens, with the cutter chopping, use tissue mashing machine's homogenate more earlier, be placed in-20 ℃ of refrigerators and preserve.
1.2 sample pre-treatments: accurately take by weighing sample homogenization liquid 25g and place the flat vial of 250mL, add the 60mL acetonitrile, sample is at 14000rmin
-1Behind the even matter 2min of at a high speed even matter device, use filter paper filtering, filtrate collecting is equipped with in the 100mL tool plug graduated cylinder of 5g～7g sodium chloride, collects filtrate, covers stopper, concuss 2min, and at room temperature static 35min makes acetonitrile phase and water layering.Draw 10mL solution from acetonitrile mutually and be transferred to 10mL scale test tube, the test tube that sample liquid is housed is placed on blows near doing on the Nitrogen evaporator, add the 0.5mL anhydrous acetonitrile in the test tube, ultrasonic 1min on supersonic wave cleaning machine then, make Avermectin be dissolved in acetonitrile solution fully, treat derivatization attached to test tube wall.
2 pre-column derivatizations
Derivative reagent A: derivative reagent A:N-methylimidazole (NMIM) and acetonitrile (the two volume ratio 5: 5), now with the current;
Derivative reagent B: trifluoroacetic anhydride (TFAA) and acetonitrile (the two volume ratio 5: 5), now with the current;
Concrete operations step: under lucifuge, room temperature environment condition, in the test tube for the treatment of derivatization sample or standard specimen that the dissolving of 0.5mL acetonitrile is housed, successively add 0.25mL derivative reagent A and 0.25mL derivative reagent B respectively, covering the vibration of test tube plug immediately shakes up, behind the reaction 35min, add 0.5mL methyl alcohol in the test tube again and shake up, react 70min again after, reactant liquor is crossed and is carried out HPLC-FD behind the 0.45 μ m filter membrane and measure.
3 chromatographic conditions
Chromatographic column: Waters-C
18(150mm * 4.6mm, 5 μ m); Moving phase: water: acetonitrile=5: 95, flow velocity are 1.0mLmin
-1Detect wavelength: fluorescence exciting wavelength 365nm, emission wavelength 475nm; Column temperature: 40 ℃; Sample size: 10 μ l; Quantivative approach: external standard method (peak area).
With the inventive method respectively to wild cabbage, cucumber, broccoli, green onion, spinach, strawberry, pears, these 8 kinds of fruit and vegetable foods of apple at 0.001mgkg
-1, 0.01mgkg
-1, 0.1mgkg
-1Three variable concentrations levels have carried out adding the recovery experiment, the result shows, tangible impurity peaks (as shown in Figure 1-Figure 3) does not all appear through these 8 the sample chromatogram figure after this pre-treatment, the interpolation recovery scope of these samples has reached the requirement of retention analysis fully at 83.1%～110.8% (as shown in table 1).
The interpolation recovery (n=4) of table 1 Avermectin in fruit and vegetable food
| Fruit and vegetable food title Vegetable | Add concentration (mgkg -1) Fortified level | Average recovery rate (%) Recovery | Relative standard deviation (%) |
| Wild cabbage cabbage | 0.001 0.01 0.1 | 106.3 102.5 84.5 | 10.1 6.7 8.6 |
| Cucumber, cucumber | 0.001 0.01 0.1 | 97.5 92.3 83.1 | 9.0 8.9 12.8 |
| Broccoli cauliflower | 0.001 0.01 0.1 | 86.9 107.8 95.5 | 12.8 7.7 7.9 |
| Green onion shallot | 0.001 0.01 0.1 | 90.7 86.4 84.6 | 12.3 8.1 6.7 |
| Spinach spinach | 0.001 0.01 0.1 | 89.6 93.8 104.8 | 9.3 8.7 8.9 |
| Strawberry strawberry | 0.001 0.01 0.1 | 86.8 94.7 91.8 | 9.5 1.9 3.5 |
| Pears pear | 0.001 0.01 0.1 | 87.7 93.6 110.8 | 8.2 6.6 5.5 |
| Apple apple | 0.001 0.01 0.1 | 84.2 102.6 91.2 | 7.3 9.4 3.7 |
The range of linearity of method, detection limit and minimal detectable concentration:
Under optimum experimental condition, this experimental technique range of linearity upper limit can reach 1.0 * 10
4μ gL
-1,, be limited to 0.5 μ gL under the detection of Avermectin with the detection lower limit of 4 times of signal to noise ratio (S/N ratio)s (S/N=3) as method
-1, its linear coefficient reaches more than 0.999; The minimal detectable concentration of this method can reach 1 μ gkg
-1, be lower than minimum MRL value (10 μ gkg
-1) order of magnitude, meet Avermectin retention analysis requirement fully.
The precision of experimental technique:
Add and reclaim experimental result as seen, the relative standard deviation scope of the parallel sample of 8 kinds of samples under three variable concentrations levels meets Avermectin retention analysis requirement 1.9%～12.3% in the experiment.
Claims (5)
1, the rapid assay methods of a kind of pesticide avermectin and toxic metabolite residue thereof, its step is as follows:
A, specimen preparation: gather the fruits and vegetables sample earlier with the cutter chopping, use tissue mashing machine's homogenate again, and freezing preservation;
B, sample pre-treatments: the sample thief homogenate places container, add acetonitrile, mixing the back filters, filtrate collecting is equipped with in the tool plug graduated cylinder of sodium chloride, static behind the concuss, make acetonitrile mutually and the water layering, then the middle mutually solution of acetonitrile is moved to test tube and dry up, adding anhydrous acetonitrile in test tube is dissolved in the acetonitrile solution Avermectin attached to test tube wall
C, pre-column derivatization: under lucifuge, room temperature condition, treating in the derivatization sample of acetonitrile dissolving, add the derivative reagent that N-methylimidazole and acetonitrile are formed earlier, add the derivative reagent that trifluoroacetic anhydride and acetonitrile are formed again, after vibration shakes up reaction 30-35min, add methyl alcohol again and shake up reaction 60-70min, enter high performance liquid chromatography-fluorescence detector behind the reacting liquid filtering and measure.
2, the rapid assay methods of a kind of pesticide avermectin according to claim 1 and toxic metabolite residue thereof is characterized in that: the volume ratio of sample homogenization liquid and acetonitrile is 1: 2.5～1: 3 in the described B step.
3, the rapid assay methods of a kind of pesticide avermectin according to claim 1 and toxic metabolite residue thereof, it is characterized in that: the volume ratio of N-methylimidazole and acetonitrile is 3: 7～5: 5 in the described C step, and the volume ratio of trifluoroacetic anhydride and acetonitrile is 3: 7～5: 5.
4, according to the rapid assay methods of claim 1 or 3 described a kind of pesticide avermectins of any claim and toxic metabolite residue thereof, it is characterized in that: the volume ratio of each component is in the described C step: acetonitrile dissolving treat the derivatization sample: the derivative reagent that N-methylimidazole and acetonitrile are formed: the derivative reagent of trifluoroacetic anhydride and acetonitrile composition: methyl alcohol=1: 0.5: 0.5: 1～1: 0.5: 0.5: 2.
5, the rapid assay methods of a kind of pesticide avermectin according to claim 1 and toxic metabolite residue thereof is characterized in that: acetonitrile phase sample extraction solution is placed on the Nitrogen evaporator and dries up in the described B step.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101893570A (en) * | 2010-03-24 | 2010-11-24 | 上海市农业技术推广服务中心 | Method for detecting avermectins pesticide multi-residues in cereal agricultural products |
| CN103543224A (en) * | 2013-11-06 | 2014-01-29 | 吉林省水产科学研究院 | Detection method for residues of abamectin and ivermectin |
| CN106226444A (en) * | 2016-10-14 | 2016-12-14 | 佛山海悦智达科技有限公司 | The high-efficiency liquid chromatography method for detecting of avilamycin content in a kind of edible vegetable oil |
| CN106885853A (en) * | 2017-02-14 | 2017-06-23 | 湖北省农业科学院农业质量标准与检测技术研究所 | The quick pre-treating method for determining AVM pesticide residue in edible oil and quantitative analysis method |
| CN113030296A (en) * | 2021-02-09 | 2021-06-25 | 上海市食品药品检验研究院 | Method for screening abamectin and emamectin benzoate degradation products in honeysuckle and planting soil thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281900A (en) * | 2000-07-25 | 2001-01-31 | 高东卫 | Extraction method of abamectin |
| JP2002311010A (en) * | 2001-04-11 | 2002-10-23 | Teikoku Hormone Mfg Co Ltd | Method for determining dihydroavermectine |
-
2005
- 2005-09-27 CN CNB2005100300280A patent/CN100378455C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101893570A (en) * | 2010-03-24 | 2010-11-24 | 上海市农业技术推广服务中心 | Method for detecting avermectins pesticide multi-residues in cereal agricultural products |
| CN101893570B (en) * | 2010-03-24 | 2015-04-22 | 上海市农业技术推广服务中心 | Method for detecting avermectins pesticide multi-residues in cereal agricultural products |
| CN103543224A (en) * | 2013-11-06 | 2014-01-29 | 吉林省水产科学研究院 | Detection method for residues of abamectin and ivermectin |
| CN103543224B (en) * | 2013-11-06 | 2014-08-13 | 吉林省水产科学研究院 | Detection method for residues of abamectin and ivermectin |
| CN106226444A (en) * | 2016-10-14 | 2016-12-14 | 佛山海悦智达科技有限公司 | The high-efficiency liquid chromatography method for detecting of avilamycin content in a kind of edible vegetable oil |
| CN106885853A (en) * | 2017-02-14 | 2017-06-23 | 湖北省农业科学院农业质量标准与检测技术研究所 | The quick pre-treating method for determining AVM pesticide residue in edible oil and quantitative analysis method |
| CN113030296A (en) * | 2021-02-09 | 2021-06-25 | 上海市食品药品检验研究院 | Method for screening abamectin and emamectin benzoate degradation products in honeysuckle and planting soil thereof |
| CN113030296B (en) * | 2021-02-09 | 2023-03-21 | 上海市食品药品检验研究院 | Method for screening abamectin and emamectin benzoate degradation products in honeysuckle and planting soil thereof |
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