CN113252824B - Gas chromatography-electronic capture detector method for determining content of trifluoro-phenylpyrimidine in water body - Google Patents
Gas chromatography-electronic capture detector method for determining content of trifluoro-phenylpyrimidine in water body Download PDFInfo
- Publication number
- CN113252824B CN113252824B CN202110671438.2A CN202110671438A CN113252824B CN 113252824 B CN113252824 B CN 113252824B CN 202110671438 A CN202110671438 A CN 202110671438A CN 113252824 B CN113252824 B CN 113252824B
- Authority
- CN
- China
- Prior art keywords
- sample
- gas chromatography
- water
- capture detector
- dichloromethane
- 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.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/70—Electron capture detectors
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
A gas chromatography-electronic capture detector method for determining the content of trifluoro-fluoropyrimidine in water body is characterized in that a water body sample is extracted by dichloromethane, then the volume is determined by acetone, and the gas chromatography-electronic capture detector method is utilized for determination. It was confirmed by experiment that the standard working solution in the concentration range of 0.01-1.0mg/L gave the standard curve equation of y-187085 x-2204.5, R2The linear dependence is very good at 0.9994. Under the addition concentrations of 0.01, 0.10 and 1.00mg/kg, the obtained addition recovery rate is 83.55 to 109.53 percent, the relative standard deviation is 8 to 11 percent, and the lowest detection concentration is 0.01 mg/kg. The method is simple to operate, rapid, accurate and low in cost, provides a rapid and reliable method for determining the residual quantity of the trifluoropyrimidine in the water body, and can meet the requirements of mass sample analysis on quality and progress.
Description
Technical Field
The invention belongs to the field of chemical analysis and detection, relates to detection and analysis of trifluoro-fluoropyrimidine, and particularly relates to a method for determining the content of trifluoro-fluoropyrimidine in a water body by a gas chromatography-electron capture detector method (GC-ECD).
Background
Trifluorobenzene pyrimidine, common english name: triflumzopyrim, chemical name 3, 4-dihydro-2, 4-dioxo-1- (pyrimidin-5-ylmethyl) -3- (. alpha.,. alpha. -trifluoro-m-tolyl) -2H-pyrido [1, 2-. alpha. -)]Pyrimidin-1-ium-3-ium salt having a relative molecular mass of 398.34 and a chemical formula of C20H13F3N4O2The pesticide is a mesoionic pesticide developed by DuPont in the United states and disclosed in 2013. Trifluoropyrimidine belongs to a novel pyrimidine compound, is mainly used for crops such as cotton, rice, corn, soybean and the like, and can prevent and control brown planthoppers, leafhoppers and the like. The action mechanism of the trifluoro-benzene pyrimidine is different from that of a neonicotinoid insecticide, and the trifluoro-benzene pyrimidine is used for competitively combining with a normal position on a nicotine phthalein choline receptor (nAChR) of an insect, inhibiting the combination site, reducing nerve impulse of the insect or blocking nerve transmission, and finally influencing physiological behaviors of pests such as feeding, reproduction and the like to cause death.
Trifluoropyrimidine, DuPont, U.S. 7 months in 2016, will be the first in China to obtain its first place. With the increase of the using amount of the trifluoro-benzene pyrimidine, the side effect is obvious day by day, and the problems such as environmental pollution, pesticide residue and the like are concerned and regarded by various countries. In order to ensure the environmental safety monitoring and reduce the pesticide pollution, the research on the analysis and detection technology of the trifluorophenylpyrimidine in different environmental matrixes (water bodies) is very necessary.
At present, the detection method of trifluoro-benzene pyrimidine at home and abroad mainly adopts a liquid chromatogram and liquid chromatogram-mass spectrum combined instrument. The pesticide science management 2019,40(6) discloses a high performance liquid chromatography analysis method research of 20% trifluoro-benzene pyrimidine water dispersible granules. High performance liquid chromatography analysis of 10% trifluoro-phenylpyrimidine suspension is disclosed in 2019,11(58) pesticides. Among the three publications mentioned in Jiangsu agricultural science, 2021, 49(2), dynamic degradation and residual analysis of trifluoropyrimidine in paddy field were disclosed, and liquid chromatography-mass spectrometry was used for detection. Disclosed is a method for analyzing residues of trifluoro-phenylpyrimidine in rice, soil and field water, wherein a liquid chromatograph is used for detection. However, no research report on the determination of trifluoro-phenylpyrimidine by gas chromatography is found. Compared with a gas phase and a liquid phase, the gas phase and the liquid phase have the advantages of better separation degree, higher sensitivity of the detector and low use cost. Therefore, gas chromatography is still the first choice method for analyzing the residual quantity of the trifluorobenzene pyrimidine in environmental media and various crops in most laboratories in China.
Disclosure of Invention
The invention aims to provide a gas chromatography-electron capture detector (GC-ECD) method for determining the content of the trifluoropyrimidine in the water body so as to rapidly and accurately determine the residual amount of the trifluoropyrimidine in the water body, aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that: a gas chromatography-electron capture detector method for measuring the content of trifluoro-fluoropyrimidine in water comprises the following steps:
(1) sample extraction: filtering the water sample to remove impurities, adding a NaCl solution with the mass concentration of 10-20% into the water sample after removing the impurities, wherein the volume ratio of the water sample after removing the impurities to the NaCl solution is 5: and 2, adding dichloromethane after shaking, wherein the volume ratio of the dichloromethane to the water body sample after impurity removal is 4: 5, shaking and standing, and collecting a lower dichloromethane phase; adding dichloromethane into the water phase, extracting twice, wherein the volume ratio of the dichloromethane added each time to the water body sample after impurity removal is 2: collecting the lower dichloromethane phase, and combining all dichloromethane phases; wherein the shaking time is 1-2 min; standing for 8-12 min.
(2) And (3) fixing the volume of the sample: concentrating the combined dichloromethane phase to near dryness, performing constant volume with acetone, and filtering to obtain a sample solution; wherein, the concentration is performed by adopting a rotary evaporator at the temperature of 55 ℃; the filtration was performed using a 0.22 μm organic filter.
(3) And (3) measuring the content of the trifluoro-phenylpyrimidine in the sample solution by using a gas chromatograph.
The gas chromatography conditions when the gas chromatograph is adopted are as follows: DB1701 column, 30 m.times.320. mu.m.times.1 μm; temperature programming: maintaining the initial temperature at 180 deg.C for 5min, increasing to 280 deg.C at 20 deg.C/min, and maintaining for 3 min; the temperature of a sample inlet is 260 ℃; the carrier gas is nitrogen; sampling without shunting, wherein the sampling amount is 1 mu L; the flow rate is 2 mL/min; the tail gas blowing is nitrogen with the flow rate of 45 mL/min; the detector is an electron capture detector and the detector temperature is 300 ℃.
The standard working curve equation of the trifluoro-phenylpyrimidine drawn under the gas chromatography condition is that y is 187085x-2204.5, R20.9994, and is obtained by drawing a standard curve with the chromatographic peak area as the ordinate and the concentration of the standard solution of the trifluoropyrimidine as the abscissa and fitting the standard curve, and the standard value of the trifluoropyrimidine is prepared when a standard working curve equation is drawnThe working solution concentration is 0.01, 0.05, 0.10, 0.50, 1.00 mg/L.
The invention establishes a method for detecting the residual quantity of the trifluorobenzene pyrimidine in the water body by optimizing a gas chromatography-electronic capture detector instrument and preparation conditions of a sample to be detected, and proved by methodological verification test research, standard working solutions with the concentrations of 0.01, 0.05, 0.10, 0.50 and 1.00mg/L respectively obtain a standard curve equation of y-187085 x-2204.5 (correlation coefficient R is 187085 x-2204.5)20.9994), its linear dependence is very good. At concentrations of the three additions of 0.01, 0.10, 1.00mg/kg, the addition recoveries and relative standard deviations obtained were between 83.55% -109.53% and 8% -11%, respectively. The lowest detection concentration was 0.01 mg/kg. Meets the requirement of the pesticide residue detection method. The established method has high accuracy, strong specificity and good reproducibility, and can effectively detect the residual quantity of the trifluoropyrimidine in the water body. Experiments prove that the method can be used for various water bodies with larger property difference, and the recovery rate, the sensitivity, the detection limit and the like of the method have better accuracy and precision in various batches of water bodies.
Drawings
FIG. 1 is a graph of the standard working curve for trifluorobenzene pyrimidine of the present invention.
FIG. 2 is a GC-ECD chromatogram of a trifluorobenzene pyrimidine standard solution (0.5mg/L) of the present invention.
FIG. 3 is a GC-ECD chromatogram of a blank sample of a water body according to the invention.
FIG. 4 is a GC-ECD chromatogram of a blank water sample added with 0.1mg/kg of trifluoropyrimidine.
The abscissa in fig. 2 to 4 represents time (unit: minute) and the ordinate represents the response value.
Detailed Description
The following examples are intended to illustrate the invention in further detail, but are not intended to limit the scope of the invention.
Example 1 establishment of the method
The instrument comprises the following steps: Agilent-6890N gas chromatograph (Agilent corporation, Engelle, USA) ECD detector.
Chromatographic conditions are as follows: DB1701 gas chromatography column, 30m × 320 μm × 1 μm; temperature programming: maintaining the initial temperature at 180 deg.C for 5min, increasing to 280 deg.C at 20 deg.C/min, and maintaining for 3 min; the temperature of a sample inlet is 260 ℃; the carrier gas is nitrogen (purity 99.999%); sampling without shunting, wherein the sampling amount is 1 mu L; the flow rate is 2 mL/min; the tail gas blowing is nitrogen with the flow rate of 45 mL/min; the detector is an electron capture detector and the detector temperature is 300 ℃.
1) Preparation of test sample solutions
Filtering the water sample by using filter paper to remove impurities, accurately measuring 50mL of the water sample, putting the water sample into a 250mL separating funnel, adding 20mL of 20% NaCl solution with mass concentration, shaking, adding 40mL of dichloromethane, shaking for 1min, standing for 10min, and collecting a lower dichloromethane phase; adding dichloromethane into the water phase, extracting twice, wherein the addition amount of dichloromethane is 20mL each time, collecting the lower dichloromethane phase, and combining all dichloromethane phases; the combined dichloromethane phases were concentrated to near dryness on a rotary evaporator (55 ℃ C.), made up to volume with 2.0mL of acetone and filtered through a 0.22 μm organic filter to give a test sample solution.
2) Drawing a standard curve
0.0100g (accurate to 0.0001g) of the trifluorobenzene pyrimidine standard substance (with the purity of 99.4%) is accurately weighed, placed in a 100mL brown volumetric flask, dissolved by acetone and prepared into the trifluorobenzene pyrimidine standard mother liquor with the mass concentration of 1000.0 mg/L. Then, a standard mother solution of the trifluoro-benzene pyrimidine is respectively taken by adopting a gradient dilution method to prepare a standard working solution, so that the mass concentration of the trifluoro-benzene pyrimidine is 0.01, 0.05, 0.10, 0.50 and 1.00 mg/L. Detection was performed using a gas chromatography-electron capture detector (GC-ECD) instrument according to the aforementioned chromatographic conditions. The peak area of the obtained trifluoropyrimidine is shown in table 1, a standard working curve of the trifluoropyrimidine is drawn by taking the mass concentration (x, mg/L) of the trifluoropyrimidine as an abscissa and the corresponding peak area (y) as an ordinate, and the standard curve equation of the trifluoropyrimidine is that y is 187085x-2204.5(R is 187085 x-2204.5)20.9994), see fig. 1 for the standard graph.
TABLE 1 Standard curves for trifluoropyrimidines
As shown in Table 1, the peak area of trifluorobenzene pyrimidine in a certain linear range has a good linear relation with mass concentration, and the correlation coefficient is 0.9994.
3) Measurement of
And (3) sucking the standard working solution and the sample solution to be tested, injecting the standard working solution and the sample solution into a gas chromatography-electron capture detector (GC-ECD) instrument to obtain a chromatogram, wherein the GC-ECD chromatogram of the trifluoro-fluoropyrimidine standard solution (0.5mg/L) is shown in figure 2, the retention time of the trifluoro-fluoropyrimidine is about 12.05min according to the peak time qualification, and the residual quantity of the trifluoro-fluoropyrimidine is quantitatively calculated by an external standard method.
Example 2 additive recovery test for method validation
Adding a standard working solution of trifluoropyrimidine into a blank sample of a water body (without the trifluoropyrimidine), setting 3 addition levels with the concentrations of 0.01, 0.1 and 1mg/kg respectively, repeating each addition level for 5 times, simultaneously setting the blank sample (namely the blank sample of the water body without the standard working solution of the trifluoropyrimidine, requiring no chromatographic peak in the time when the trifluoropyrimidine appears in the spectrum of the blank sample, namely the method has good specificity) as a control, extracting and fixing the volume by using the preparation method of the sample solution for test in the embodiment 1 to obtain a solution to be tested of the added and recovered test sample and a solution to be tested of the blank sample, and determining by using the chromatographic conditions of the embodiment 1.
The formula for calculating the residual quantity of trifluoro-benzene pyrimidine is as follows: x ═ C × V)/m, where X: adding the residual quantity of the trifluoro-benzene pyrimidine in the recovered sample, mg/kg; c: calculating sample injection concentration of mg/L according to the peak area of the sample through a standard curve; v: adding the final constant volume (mL) of the recovered experimental sample; m: the amount of the recovered test sample, g, was added.
The addition recovery was calculated according to the conventional technique and the measurement results are shown in Table 2. Typical chromatograms for the addition recovery test of trifluorfluoropyrimidine in water samples are shown in fig. 3 and 4.
As can be seen from Table 2, at the 3 levels of spiking, the recovery of the trifluorfluoropyrimidine addition on the water samples ranged from 83.55 to 109.53% with a relative standard deviation of 9.3 to 10.2%; as can be seen from FIGS. 3-4, no peak appears in the time of appearing the peak of the trifluorobenzene pyrimidine in the blank sample of the water body, which indicates that the specificity of the method is good. According to the experiment of adding and recovering rate, the lowest detected concentration of the trifluoro-fluoropyrimidine in the water body sample under the chromatographic conditions is 0.01 mg/kg. The correlation coefficient of the linear equation is 0.9994, which shows that the sensitivity, accuracy, precision and specificity of the established detection method all meet the requirements of pesticide residue detection, and the established method can be used for detecting the residual quantity of the trifluorobenzene pyrimidine in the water body.
TABLE 2 recovery rate and relative standard deviation table of trifluorobenzene pyrimidine in water
Example 3 application
(1) Determination of residual quantity of trifluoro-fluoropyrimidine in paddy field water body applied with trifluoro-fluoropyrimidine medicament
The field test was carried out in 2019 in the experimental base of Hunan agriculture university in Hibiscus region of Changsha, Hunan, with the area of each cell being 30m2. The pesticide application dosage form is 20% of trifluoro-benzene pyrimidine water dispersible granules, the pesticide application dosage is 27 g/hectare (the dosage of the preparation is 9.0 g/mu), a paddy field without paddy rice is selected at the edge of the paddy field with the paddy rice planted (the depth of irrigating water is 3-5 cm), the direct spraying method is adopted for pesticide application, paddy field water is collected 2h, 1 h, 3, 5, 7, 10, 14, 21, 28, 35 and 42d after pesticide application, and the test is repeated three times.
Randomly collecting paddy field water (not less than 10 points) in each test cell, wherein the sample volume of each cell is not less than 1L, uniformly mixing, reserving 500mL, and placing in a clean sealed plastic bottle to be used as a paddy field water body sample; then filtering with filter paper, accurately measuring 50mL of water body sample after filtering, transferring the water body sample into a 250mL separating funnel filled with 20mL of 20% NaCl solution, adding 40mL of dichloromethane after shaking, standing for 10min after shaking for 1min, collecting a lower dichloromethane phase, adding 20mL of dichloromethane and 20mL of dichloromethane into a water phase respectively, extracting twice, and collecting the lower dichloromethane phase. All dichloromethane phases are combined and concentrated on a rotary evaporator (55 ℃) to be nearly dry, 2.0mL acetone is used for constant volume, then a test sample solution is obtained through an organic film with the thickness of 0.22 mu m, and finally the GC-ECD detection condition is adopted to detect the solution to be detected of the water body sample, and the result is shown in Table 3.
TABLE 3 digestion dynamic test results of trifluorobenzene pyrimidine in paddy field water
(2) Determination of natural water body and living water body
The method provided by the invention is used for detecting 5 parts of water quality of river water near a riverside community, running water in the community, near rice field water, teacher's tap water, teaching building tap water and supermarket purified water of Hunan agriculture university, and no trifluoropyrimidine is detected in the result.
Claims (7)
1. A gas chromatography-electron capture detector method for measuring the content of trifluoro-fluoropyrimidine in water is characterized by comprising the following steps:
(1) sample extraction: filtering the water sample to remove impurities, adding a NaCl solution with the mass concentration of 10-20% into the water sample after removing the impurities, wherein the volume ratio of the water sample after removing the impurities to the NaCl solution is 5: and 2, adding dichloromethane after shaking, wherein the volume ratio of the dichloromethane to the water body sample after impurity removal is 4: 5, shaking and standing, and collecting a lower dichloromethane phase; adding dichloromethane into the water phase, extracting twice, wherein the volume ratio of the dichloromethane added each time to the water body sample after impurity removal is 2: collecting the lower dichloromethane phase, and combining the dichloromethane phases;
(2) and (3) fixing the volume of the sample: concentrating the combined dichloromethane phase to near dryness, performing constant volume with acetone, and filtering to obtain a sample solution;
(3) determining the content of trifluoro-benzene pyrimidine in the sample solution by adopting a gas chromatograph;
wherein, the gas chromatography conditions are as follows: DB1701 column, 30 m.times.320. mu.m.times.1 μm; temperature programming: maintaining the initial temperature at 180 deg.C for 5min, increasing to 280 deg.C at 20 deg.C/min, and maintaining for 3 min; the temperature of a sample inlet is 260 ℃; the carrier gas is nitrogen; sampling without shunting, wherein the sampling amount is 1 mu L; the flow rate is 2 mL/min; the tail gas blowing is nitrogen with the flow rate of 45 mL/min; the detector is an electron capture detector and the detector temperature is 300 ℃.
2. The gas chromatography-electron capture detector method for determining the content of trifluoropyrimidine in water according to claim 1, wherein the standard working curve equation of trifluoropyrimidine plotted under the gas chromatography condition is y-187085 x-2204.5, R2＝0.9994。
3. The gas chromatography-electron capture detector method for determining the content of trifluorobenzene pyrimidine in water body according to claim 2, wherein the concentration of the prepared trifluorobenzene pyrimidine standard working solution is 0.01, 0.05, 0.10, 0.50 and 1.00mg/L when the standard working curve equation is drawn.
4. The gas chromatography-electron capture detector method for determining the content of trifluorobenzene pyrimidine in water according to claim 1, wherein the filtration in step (2) is performed with a 0.22 μm organic filter membrane.
5. The gas chromatography-electron capture detector method for determining the content of trifluoropyrimidine in an aqueous body according to claim 1, wherein the concentration in the step (2) is performed by using a rotary evaporator at a temperature of 55 ℃.
6. The gas chromatography-electron capture detector method for determining the content of trifluoropyrimidine in water according to claim 1, wherein the shaking time in the step (1) is 1 to 2 min.
7. The gas chromatography-electron capture detector method for determining the content of trifluoropyrimidine in water according to claim 1, wherein the standing time in the step (1) is 8 to 12 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110671438.2A CN113252824B (en) | 2021-06-17 | 2021-06-17 | Gas chromatography-electronic capture detector method for determining content of trifluoro-phenylpyrimidine in water body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110671438.2A CN113252824B (en) | 2021-06-17 | 2021-06-17 | Gas chromatography-electronic capture detector method for determining content of trifluoro-phenylpyrimidine in water body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113252824A CN113252824A (en) | 2021-08-13 |
| CN113252824B true CN113252824B (en) | 2022-04-19 |
Family
ID=77188393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110671438.2A Active CN113252824B (en) | 2021-06-17 | 2021-06-17 | Gas chromatography-electronic capture detector method for determining content of trifluoro-phenylpyrimidine in water body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113252824B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103163265A (en) * | 2013-03-18 | 2013-06-19 | 中国农业科学院烟草研究所 | Method for determining residual quantity of myclobutanil by SPE-GC/ECD (Solid Phase Extraction-Gas Chromatography-Electron Capture Detector) |
| CN108072727A (en) * | 2016-11-05 | 2018-05-25 | 天士力医药集团股份有限公司 | Method that is a kind of while measuring 23 kinds of organic chlorine agriculture chemicals residual quantities in Radix Notoginseng |
| CN108593802A (en) * | 2018-05-25 | 2018-09-28 | 天津大学 | The gas chromatography-electron capture detector detection method of halogenated benzoquinones |
| CN108680687A (en) * | 2018-04-19 | 2018-10-19 | 浙江省海洋水产研究所 | The detection method of Polychlorinated biphenyls in a kind of marine product |
| CN109071545A (en) * | 2016-04-15 | 2018-12-21 | 拜耳动物保健有限责任公司 | New Pyrazolopyrimidine derivative |
| TW202012418A (en) * | 2018-09-28 | 2020-04-01 | 德商巴地斯顏料化工廠 | Pyrimidinium compounds and their mixtures for combating animal pests |
| CN111592539A (en) * | 2020-06-03 | 2020-08-28 | 江西农业大学 | Preparation method of trifluoro-benzene pyrimidine |
| CN112285245A (en) * | 2020-11-17 | 2021-01-29 | 湖南农业大学 | Gas chromatography-mass spectrometry method for detecting content of fluazinam in paddy field water body |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5576217A (en) * | 1995-02-28 | 1996-11-19 | Mallinckrodt Baker, Inc. | Solid phase microextraction of trace amounts of organic analytes |
| CN102914608B (en) * | 2012-11-12 | 2013-10-30 | 天津出入境检验检疫局动植物与食品检测中心 | Method for quickly detecting pesticide multiple residues in traditional Chinese medicine through membrane separation and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometer |
| CN102998407B (en) * | 2012-12-04 | 2015-03-18 | 漳州片仔癀药业股份有限公司 | Method for detecting pesticide residues in anti-inflammatory and analgesic bolus |
| CN112969697A (en) * | 2019-10-31 | 2021-06-15 | 组合化学工业株式会社 | Process for producing herbicide and intermediate thereof |
-
2021
- 2021-06-17 CN CN202110671438.2A patent/CN113252824B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103163265A (en) * | 2013-03-18 | 2013-06-19 | 中国农业科学院烟草研究所 | Method for determining residual quantity of myclobutanil by SPE-GC/ECD (Solid Phase Extraction-Gas Chromatography-Electron Capture Detector) |
| CN109071545A (en) * | 2016-04-15 | 2018-12-21 | 拜耳动物保健有限责任公司 | New Pyrazolopyrimidine derivative |
| CN108072727A (en) * | 2016-11-05 | 2018-05-25 | 天士力医药集团股份有限公司 | Method that is a kind of while measuring 23 kinds of organic chlorine agriculture chemicals residual quantities in Radix Notoginseng |
| CN108680687A (en) * | 2018-04-19 | 2018-10-19 | 浙江省海洋水产研究所 | The detection method of Polychlorinated biphenyls in a kind of marine product |
| CN108593802A (en) * | 2018-05-25 | 2018-09-28 | 天津大学 | The gas chromatography-electron capture detector detection method of halogenated benzoquinones |
| TW202012418A (en) * | 2018-09-28 | 2020-04-01 | 德商巴地斯顏料化工廠 | Pyrimidinium compounds and their mixtures for combating animal pests |
| CN111592539A (en) * | 2020-06-03 | 2020-08-28 | 江西农业大学 | Preparation method of trifluoro-benzene pyrimidine |
| CN112285245A (en) * | 2020-11-17 | 2021-01-29 | 湖南农业大学 | Gas chromatography-mass spectrometry method for detecting content of fluazinam in paddy field water body |
Non-Patent Citations (2)
| Title |
|---|
| Uptake and Translocation of Triflumezopyrim in Rice Plants;Tianle Fan et al.;《Journal of Agricultural and Food Chemistry》;20201231;第1-7页 * |
| 三氟苯嘧啶在水稻、土壤和田水中的残留分析方法;彭家慧 等;《农药》;20180131;第57卷(第1期);第50-53页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113252824A (en) | 2021-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Msagati et al. | Comparative study of sample preparation methods; supported liquid membrane and solid phase extraction in the determination of benzimidazole anthelmintics in biological matrices by liquid chromatography–electrospray–mass spectrometry | |
| CN106706830A (en) | Method for determining perfluorocarboxylic acid compound in crops | |
| CN105372353A (en) | Method for detecting residual quantities of glyphosate and phosphonic acid being metabolite of glyphosate in food | |
| CN105037276B (en) | A kind of cefoperazone sodium hydrolysate and its production and use | |
| CN101865898A (en) | Method for determining phthalate ester in soil | |
| CN104237402A (en) | Extracting and measuring method of perfluorinated compounds in bark and leaves | |
| CN113252824B (en) | Gas chromatography-electronic capture detector method for determining content of trifluoro-phenylpyrimidine in water body | |
| Lin | Inorganic selenium speciation in groundwaters by solid phase extraction on Dowex 1X2 | |
| Doucette et al. | Phytoremediation of dissolved phase trichloroethylene using mature vegetation | |
| CN105911184A (en) | Method of detecting residue of abamectin in water | |
| CN112285245A (en) | Gas chromatography-mass spectrometry method for detecting content of fluazinam in paddy field water body | |
| CN108132309B (en) | Analysis method for determining residual quantity of thiediazole copper in dendrobium officinale | |
| CN102520107B (en) | Method for measuring matrine pesticide residual quantity in tobacco | |
| CN105334284B (en) | It is a kind of to identify and remove the method that carboxylic acids disturbs in perfluorobutyric acid detection | |
| CN104237393B (en) | The detection method of impurity in a kind of Penequine hydrochloride | |
| CN107966506A (en) | The detection method of N-ethylaniline content in a kind of Rubber ＆ Rubber Products | |
| CN104237394B (en) | The detection method of impurity in a kind of penehyclidine hydrochloride injection | |
| CN109142589B (en) | Method for determining tetramycin residual quantity in soil by using high performance liquid chromatograph | |
| CN106932511A (en) | The detection method of different valence state antimony in a kind of environment water | |
| CN103175906A (en) | Qualitative and quantitative detection method for each component of validamycin | |
| CN110208405A (en) | A kind of remaining method of dinotefuran on detection rice | |
| CN110057949A (en) | The method for measuring avermectin in soil | |
| CN109557220A (en) | The pre-treating method and its detection method of 8 kinds of Residual Levels of Organochlorine Pesticides test samples in a kind of soil | |
| CN114965804B (en) | Method for simultaneously determining ipratropium and metabolite PPA residues of ipratropium in soil | |
| CN103163246B (en) | Method for detecting residual quantity of methyl thiadiazole induced amine in tobacco and fruits and vegetables by SPE-HPLC/UV (Solid Phase Extraction-High Performance Liquid Chromatography/ultraviolet) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |