CN115236243A - Method for detecting ethephon sclerotium - Google Patents
Method for detecting ethephon sclerotium Download PDFInfo
- Publication number
- CN115236243A CN115236243A CN202211032023.1A CN202211032023A CN115236243A CN 115236243 A CN115236243 A CN 115236243A CN 202211032023 A CN202211032023 A CN 202211032023A CN 115236243 A CN115236243 A CN 115236243A
- Authority
- CN
- China
- Prior art keywords
- sample
- vinclozolin
- detecting
- detected
- quantitative
- 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.)
- Pending
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
-
- 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
- G01N30/72—Mass spectrometers
-
- 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
- G01N30/86—Signal analysis
-
- 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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
-
- 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
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
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)
- Engineering & Computer Science (AREA)
- Library & Information Science (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for detecting ethephon sclerotium, and relates to the technical field of detection. The detection method disclosed by the invention realizes quantitative analysis of the vinclozolin by detecting the 3, 5-dichloroaniline which is a decomposition product of the vinclozolin. The method has the advantages of good linear relation, minimum quantitative limit, accuracy and/or precision and the like.
Description
Technical Field
The invention relates to the technical field of detection, in particular to a method for detecting ethephon sclerotium.
Background
Vinclozolin (Vinclozolin) is a broad-spectrum protective and contact fungicide developed successfully by basf company, germany in 1975, and has remarkable prevention and treatment effects on diseases caused by pathogenic bacteria of botrytis cinerea, sclerotinia, streptosclerotinia, and the like on plants such as fruit trees, vegetables, and the like. The residue of vinclozolin is defined as the sum of vinclozolin and all metabolites thereof containing a 3, 5-dichlorophenol moiety, expressed as vinclozolin. At present, few reports are reported on the detection of converting the vinclozolin into the 3, 5-dichlorophenol, but as the pesticide evaluation and technical support, the detection of the vinclozolin is important for reasonable use, residue evaluation and food safety.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for detecting vinclozolin. The detection method provided by the invention can be used for quantitatively analyzing the residual sclerotium of the ethylene bacterium in the sample, and has the advantages of good linear relation, minimum quantitative limit, accuracy and/or precision and the like.
The invention is realized by the following steps:
the invention provides a method for detecting ethephon sclerotium, which comprises the following steps:
a pretreatment step: pretreating a sample to be detected to decompose the vinclozolin in the sample to be detected into 3, 5-dichloroaniline to obtain a sample;
a detection step: detecting the sample with a gas chromatography-mass spectrometer to obtain the quantitative ion pair peak area of 3, 5-dichloroaniline;
a quantitative analysis step: and obtaining the content of the vinclozolin in the sample to be detected based on the peak area of the quantitative ion pair.
The detection method provided by the invention realizes quantitative analysis of the residual of the vinclozolin in the sample by detecting the decomposition product 3, 5-dichloroaniline of the vinclozolin, and has the advantages of good linear relation, minimum quantitative limit, accuracy and/or precision and the like.
The pretreatment step is primarily responsible for the decomposition of vinclozolin to 3, 5-dichloroaniline in the sample. Any reaction conditions having such effects may be applied to the present invention, and fall within the scope of the present invention.
Alternatively, in some embodiments of the invention, in the detecting step, the chromatographic conditions detected by the gas chromatography-mass spectrometer comprise the following:
and (3) chromatographic column: HP-5MS UI chromatographic column, 30.0m × 0.25mm × 0.25um;
column temperature: 70 ℃;
sample inlet temperature: 300 ℃;
gradient program: maintaining at 70 deg.C for 1min, heating to 160 deg.C at 10 deg.C/min, maintaining for 1min, heating to 280 deg.C at 30 deg.C/min, and maintaining for 3min;
carrier gas: nitrogen, flow rate: 1.66mL/min;
no shunt sampling;
sample introduction amount: 1 mu L of the solution;
the values of the above parameters may fluctuate within a range of ± 1%.
The chromatographic conditions are optimized and adjusted by the inventor, so that the method is suitable for quantitative analysis of the residual of the sclerotium rolfsii in most plant samples, and has good linear relation, minimum quantitative limit, accuracy and precision.
Alternatively, in some embodiments of the present invention, in the detecting step, the mass spectrometry conditions detected by the gas chromatography-mass spectrometer include the following:
an ion source: EI;
ion source temperature: 200 ℃;
GC-MS interface temperature: 300 ℃;
the detection mode is as follows: multiple Reaction Monitoring (MRM);
the collision energy is as follows:
mass spectrometry scan time: 9.1-10.0min;
the values of the above parameters may fluctuate within a range of ± 1%.
The above conditions are optimized and adjusted by the inventor, are suitable for quantitative analysis of the residual vinclozolin in most samples (such as plant sources or liquid beverage sources), and have good linear relation, minimum quantitative limit, accuracy and precision.
Optionally, in some embodiments of the present invention, in the step of pretreating, the method of pretreating comprises: mixing the sample to be detected with acetonitrile, performing oscillation extraction, adding a solid phase extraction salt bag, centrifuging, taking the supernatant, drying by blowing, adding ethanol and hydrazine hydrate for reaction so as to decompose the vinclozolin in the sample to be detected into 3, 5-dichloroaniline, and thus obtaining the sample to be loaded.
In a reaction system of ethanol and hydrazine hydrate, the vinclozolin is decomposed into 3, 5-dichloroaniline after being derived, and the residual quantity of the vinclozolin can be quantified by detecting the residual quantity of the 3, 5-dichloroaniline.
Optionally, in some embodiments of the present invention, the sample to be tested is a solid form sample or a liquid form sample.
Optionally, in some embodiments of the present invention, 10ml of acetonitrile is used for every 5g of the sample to be tested; the values of the above parameters may fluctuate within a range of ± 1%.
Optionally, in some embodiments of the present invention, in the quantitative analysis step, based on the quantitative ion pair peak area, an external standard method is used to obtain the content of vinclozolin in the sample to be tested.
It should be noted that, when the quantification is performed by external standard method, a standard curve can be prepared in advance by those skilled in the art based on the disclosure of the present invention, and the relevant results can be obtained by substituting the quantification ion pair peak area into the standard curve. The present invention is not limited to the formula of the standard curve, and any standard curve is within the scope of the present invention as long as it is made based on the disclosure of the present invention.
As an exemplary standard curve, reference is made to table 1 in example 1.
Alternatively, in some embodiments of the invention, the quantitative ion pair is 161.00/99.10 (m/z).
Optionally, in some embodiments of the invention, the sample to be tested is from a plant or a liquid drink.
Alternatively, in some embodiments of the invention, the plant includes, but is not limited to, miscellaneous cereals, vegetables, and fruits.
Alternatively, in some embodiments of the invention, the miscellaneous cereals include, but are not limited to, rice, millet, miscellaneous cereals, wheat, corn, and soybean;
the vegetables include, but are not limited to, chinese cabbage, cucumber, tomato, carrot, leek, spinach, green vegetables, lettuce, bean sprouts, pumpkin, white gourd, cucumber, oyster mushroom, and needle mushroom;
the fruit includes, but is not limited to, strawberry, blueberry, apple, banana, kiwi, grape, lemon, citrus, mango, peach, plum, pear, pineapple, and watermelon.
The liquid beverage may be milk or other liquid-like beverage.
It should be noted that the detection object of the method provided by the present invention is not limited to the above-mentioned types, and any object that may contain vinclozolin is suitable for the present invention, and the application of the method of the present invention to the detection of these objects also falls within the scope of the present invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a total ion flow diagram of a standard of a product of the decomposition of vinclozolin (3, 5-dichloroaniline).
FIG. 2 is a standard mass spectrum of a product of the decomposition of vinclozolin (3, 5-dichloroaniline).
FIG. 3 is a chromatogram of cucumber matrix as a standard of Byctolterium vinum decomposition product (3, 5-dichloroaniline).
FIG. 4 is a cucumber matrix ion mass spectrum of a standard product of vinclozolin decomposition product (3, 5-dichloroaniline).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Materials used in the examples below:
1.1 Instrument
1.1.1 gas chromatography-mass spectrometer: GCMS-TQ8040 (statistical analysis software: GCMS solution 4.20).
1.1.2 automatic vortex instrument: talboys digital display multi-tube vortex mixer.
1.1.4 ultrasonic oscillator: a desk type numerical control ultrasonic cleaning machine KQ-5200DE.
1.1.5 pipette: 100-1000 μ L, 20-200 μ L.
1.2 reagents and materials
1.2.1 acetonitrile: and (4) carrying out chromatographic purification.
1.2.2 methanol: and (4) carrying out chromatographic purification.
1.2.3 ethanol: and (4) carrying out chromatographic purification.
1.2.4 hydrazine hydrate: 85% and analytically pure.
1.2.5 solid phase extraction salt package: SHIMSEN QuEChERS Extraction Salts packs only,6g MgSO4,1.5g NaOAc.
1.2.6 solid phase extraction cartridge: waters Oasis HLB solid phase extraction cartridge 60mg/1mL.
1.2.7 reference (Standard) information
Ethephon sclerotium: 1000. Mu.g/mL, supplied by Beijing Shaxiang science and technology, inc. Solvent: acetone; the production date is as follows: 2020.09.23; the fixed value date: 2020.09.23; the validity period is as follows: 2022.09.23; batch number: d0017875; receiving date: 2021.10.18; storage conditions were as follows: 20 +/-4 ℃.
3, 5-dichloroaniline: 99.9% by Beijing vibrato science and technology, inc. Appearance: white powder; the production date is as follows: 2020.02.28; the fixed value date: 2020.02.28; the validity period is as follows: 2023.02.28; batch number: d0009616; receiving date: 2021.09.17; storage conditions were as follows: storing at 0-8 deg.C in dark.
Example 1
The method for detecting the vinclozolin residue provided by the embodiment comprises the following steps:
(1) Pretreatment: extraction and purification
Weighing 5.00g of a sample to be detected (if the solid sample is firstly crushed uniformly, if the liquid sample is directly sampled) into a 50mL centrifuge tube, adding 10mL acetonitrile, oscillating and extracting for 20min, adding a solid phase extraction salt bag, and carrying out vortex 30s and centrifugation at 5000rpm for 5min. Taking 6mL to 20mL of supernatant, blowing nitrogen to be nearly dry at 30 ℃ in a glass test tube screw-thread graduated tube, adding 2mL of ethanol and 20 mu L of hydrazine hydrate into the graduated tube, and carrying out water bath at 80 ℃ for 30min. Taking out, cooling to room temperature, adding 2mL of water, and mixing uniformly until the mixture is purified.
Using 3mL acetonitrile and 3mL 50% ethanol: activating a solid phase extraction column by 50% water, loading the mixed solution, then eluting by using 3mL of 50% methanol aqueous solution and then using 1.5mL of acetonitrile, and collecting acetonitrile eluent as a loading sample.
The sources of the samples to be detected are mainly plant sources and food, and can be different in different embodiments, and a person skilled in the art can select a suitable detection object according to the detection purpose. The present embodiment is described by taking strawberry, cucumber, blueberry, tomato, common cabbage, rice and milk as examples.
(2) Detection of
Detecting by gas chromatography-mass spectrometer
A chromatographic column: HP-5MS UI column (30.0 m × 0.25mm, 0.25um);
column temperature: 70 ℃;
sample inlet temperature: 300 ℃;
gradient program: maintaining at 70 deg.C for 1min, heating to 160 deg.C at 10 deg.C/min, maintaining for 1min, heating to 280 deg.C at 30 deg.C/min, and maintaining for 3min.
Carrier gas: nitrogen is more than or equal to 99.999%, flow rate: 1.66mL/min;
no shunt sampling;
sample introduction amount: 1 mu L of the solution;
an ion source: electron bombardment ion source EI;
ion source temperature: 200 ℃;
GC-MS interface temperature: 300 ℃;
the detection mode is as follows: multiple Reaction Monitoring (MRM) is shown in the following table:
the scanning time of the mass spectrum is 9.1-10.0min. The scanning ranges are qualitative ion pairs, namely 161.00/99.10, 161.00/90.10 and 161.00/126.10 (m/z).
(3) Qualitative and quantitative determination
Quantitative determination by external standard method, ready for use (quantitative by matrix standard solution)
Weighing a proper amount of 3, 5-dichloroaniline reference substance, and dissolving the reference substance by using methanol to prepare a 3, 5-dichloroaniline stock solution with the concentration of 1000 mg/L. Taking a proper amount of the ethephon sclerotium stock solution, and preparing 10mg/L ethephon sclerotium working solution by using methanol. Diluting with blank matrix (strawberry, cucumber, blueberry, tomato, common cabbage, rice or milk) to obtain 0.01, 0.05, 0.1, 0.5, 1mg/L matrix standard solution. The determination is carried out under the condition of the gas chromatography mass spectrometry, the concentration of the matrix standard solution of the product of the decomposition of the vinclozolin (3, 5-dichloroaniline) and the area of the monitored ion peak are used as a standard curve, the determination is carried out for three times, and the determination result is shown in the following table 1 and the equation of the standard curve: x represents concentration and Y represents peak area.
TABLE 1 Standard curves for different substrates of the product of the decomposition of vinclozolin (3, 5-dichloroaniline)
And after the instrument is stabilized, detecting the sample loaded under the condition of the gas chromatography-mass spectrometry. The retention time of the compound in the sample, the fragment ion equivalent, was consistent with the product of the vinclozolin decomposition (3, 5-dichloroaniline) in the standard solution. The relevant chromatographic and mass spectrometric results are shown in FIGS. 1-4.
And (3) obtaining the quantitative ion pair peak area of the 3, 5-dichloroaniline of the sample according to the result, substituting the quantitative ion pair peak area into the standard curve of the same plant source in the table 1, and converting to obtain the quantitative result of the residual vinclozolin. Conversion formula:
vinclozolin content = (concentration of 3, 5-dichloroaniline measured/3, 5-dichloroaniline molecular weight) = (concentration of 3, 5-dichloroaniline measured/162.01) = 286.1.
Minimum detected amount: under the above gas chromatography-mass spectrometry conditions, the minimum detectable amount of the product of the decomposition of vinclozolin (3, 5-dichloroaniline) was 5X 10 -3 ng。
Example 2
Accuracy and precision measurements
Three different concentration levels were set at 0.02mg/kg (minimum limit of quantitation), 0.5mg/kg and 3mg/kg, 3 standard solutions of vinclozolin at different concentrations were added to the blank medium (strawberry, cucumber, blueberry, tomato, common cabbage and milk), each concentration was repeated 5 times, and the recovery was determined by the method of example 1, and the results are shown in tables 2-7.
TABLE 2 percent recovery (accuracy) and precision (RSD) of addition of vinclozolin to strawberries
TABLE 3 recovery (accuracy) and precision (RSD) of addition of vinclozolin in cucumber
TABLE 4 percent recovery (accuracy) and precision (RSD) of addition of vinclozolin to blueberries
TABLE 5 recovery (accuracy) and precision (RSD) of addition of vinclozolin to tomato
TABLE 6 percent recovery (accuracy) and precision (RSD) of addition of vinclozolin to common cabbage
TABLE 7 recovery (accuracy) and precision (RSD) of addition of vinclozolin to milk
Minimum limit of quantitation (LOQ): the minimum adding level is taken as the minimum quantitative limit of an analysis method, the minimum quantitative limit of the vinclozolin in the common Chinese cabbage is 0.02mg/kg, and the maximum residual limit of the vinclozolin in the tomatoes, which is formulated in GB2763-2021, is 3mg/kg respectively.
The results of the linear curve measurements, the three levels and the five repeated addition recovery tests show that the concentration of vinclozolin decomposition product (3, 5-dichloroaniline) in all the above blank matrices is in a good linear relationship with its instrumental response with a correlation coefficient of 1.000 in the concentration range of 0.005-1 mg/L. The addition recovery rate (accuracy) and precision of the vinclozolin in the blank matrix are 73.5-96.8% and 1.3-16.5%, respectively, and the result shows that the residue analysis method of the example 1 meets the requirements of the pesticide residue experimental criteria in crops.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for detecting vinclozolin, comprising the steps of:
a pretreatment step: pretreating a sample to be detected to decompose the vinclozolin in the sample to be detected into 3, 5-dichloroaniline to obtain a sample;
a detection step: detecting the sample with a gas chromatography-mass spectrometer to obtain a quantitative ion pair peak area of the 3, 5-dichloroaniline;
a quantitative analysis step: and obtaining the content of the vinclozolin in the sample to be detected based on the peak area of the quantitative ion pair.
2. The method according to claim 1, wherein in the detecting step, the chromatographic conditions detected by the gas chromatography-mass spectrometer include the following:
and (3) chromatographic column: HP-5MS UI chromatographic column, 30.0m × 0.25mm × 0.25um;
column temperature: 70 ℃;
sample inlet temperature: 300 ℃;
gradient program: maintaining at 70 deg.C for 1min, heating to 160 deg.C at 10 deg.C/min, maintaining for 1min, heating to 280 deg.C at 30 deg.C/min, and maintaining for 3min;
carrier gas: nitrogen, flow rate: 1.66mL/min;
no shunt sampling;
sample injection amount: 1 mu L of the solution;
the values of the above parameters may fluctuate within a range of ± 1%.
3. The method of claim 2, wherein in the detecting step, the mass spectrometry conditions detected with the gas chromatograph-mass spectrometer comprise the following:
an ion source: EI;
ion source temperature: 200 ℃;
GC-MS interface temperature: 300 ℃;
the detection mode is as follows: multiple Reaction Monitoring (MRM);
the collision energy is as follows:
mass spectrometry scan time: 9.1-10.0min;
the values of the above parameters may fluctuate within a range of ± 1%.
4. A method according to any one of claims 1 to 3, wherein, in the step of pre-treating, the method of pre-treating comprises: mixing the sample to be detected with acetonitrile, performing oscillation extraction, adding a solid phase extraction salt bag, centrifuging, taking the supernatant, drying by blowing, adding ethanol and hydrazine hydrate, and reacting to obtain the sample to be loaded.
5. The method according to claim 4, characterized in that the sample to be tested is a solid form sample or a liquid form sample.
6. The method according to claim 5, characterized in that 10ml of acetonitrile is used for every 5g of the sample to be tested; the values of the above parameters may fluctuate within a range of ± 1%.
7. The method according to any one of claims 1 to 3, wherein in the quantitative analysis step, the content of vinclozolin in the sample to be tested is obtained by an external standard method based on the quantitative ion pair peak area.
8. The method of claim 7, wherein the quantitative ion pair is 161.00/99.10 (m/z).
9. The method according to any one of claims 1 to 3, wherein the sample to be tested is from a plant or a liquid drink;
preferably, the plant is selected from the group consisting of coarse cereals, vegetables and fruits;
preferably, the liquid beverage is milk.
10. The method of claim 9, wherein the miscellaneous cereals are selected from rice, millet, miscellaneous cereals, wheat, corn and soybean;
the vegetables are selected from Chinese cabbage, cucumber, tomato, carrot, leek, spinach, green vegetable, lettuce, bean sprout, pumpkin, wax gourd, cucumber, oyster mushroom and needle mushroom;
the fruit is selected from strawberry, blueberry, apple, banana, kiwi, grape, lemon, orange, mango, peach, plum, pear, pineapple and watermelon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211032023.1A CN115236243A (en) | 2022-08-26 | 2022-08-26 | Method for detecting ethephon sclerotium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211032023.1A CN115236243A (en) | 2022-08-26 | 2022-08-26 | Method for detecting ethephon sclerotium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115236243A true CN115236243A (en) | 2022-10-25 |
Family
ID=83681117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211032023.1A Pending CN115236243A (en) | 2022-08-26 | 2022-08-26 | Method for detecting ethephon sclerotium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115236243A (en) |
-
2022
- 2022-08-26 CN CN202211032023.1A patent/CN115236243A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lee et al. | Gas‐phase products and secondary aerosol yields from the ozonolysis of ten different terpenes | |
| Coll et al. | Organic chemistry in Titan's atmosphere: new data from laboratory simulations at low temperature | |
| Abdulra’uf et al. | Applications of solid-phase microextraction for the analysis of pesticide residues in fruits and vegetables: A review | |
| Steimer et al. | Synthesis and characterisation of peroxypinic acids as proxies for highly oxygenated molecules (HOMs) in secondary organic aerosol | |
| Wang et al. | Solid-phase microextraction coupled with high performance liquid chromatography: a complementary technique to solid-phase microextraction-gas chromatography for the analysis of pesticide residues in strawberries | |
| Lehotay et al. | Use of a quality control approach to assess measurement uncertainty in the comparison of sample processing techniques in the analysis of pesticide residues in fruits and vegetables | |
| CN115236243A (en) | Method for detecting ethephon sclerotium | |
| CN114487155A (en) | Indirect determination method for impurity content in torasemide injection | |
| CN114384168A (en) | Method for measuring residual quantity of dazomet and metabolite methyl isothiocyanate thereof in plant-derived food | |
| CN112098535B (en) | Method for detecting 1-methylcyclopropene in crops and application thereof | |
| CN113109471B (en) | LCMSMS (liquid crystal display module medium) method for rapidly and simultaneously detecting chlorothalonil and metabolites thereof in vegetables and fruits | |
| Brenna et al. | High-precision deuterium and 13C measurement by continuous flow-IRMS: organic and position-specific isotope analysis | |
| CN105651870B (en) | The remaining method of pesticide in a kind of gas chromatography-mass spectrum detection liquid beverage | |
| Amelynck et al. | SIFT ion chemistry studies underpinning the measurement of volatile organic compound emissions by vegetation | |
| CN110632218B (en) | Method for detecting residual quantity of meptyldinocap and metabolites thereof in tobacco | |
| CN112444591B (en) | Liquid chromatography tandem mass spectrometry for determining residual quantity of flumetsulam in vegetable food | |
| Brill et al. | Selective determination of pentafluorobenzyl ester derivatives of carboxylic acids by GC using microwave plasma and mass selective detection | |
| Byrne et al. | Determination of adulterated natural ethyl butyrate by carbon isotopes | |
| CN109212076B (en) | Method for detecting oxyfluorfen in water by using HPLC-MS/MS method | |
| Chupka et al. | Mass Spectrometric Studies of High Temperature Systems | |
| CN110873769B (en) | Method for rapidly detecting residual quantity of azinam in vegetables and fruits | |
| Isaacman-VanWertz et al. | Impact of structure on the estimation of atmospherically relevant physicochemical parameters | |
| CN110907566B (en) | Detection method of fenbutatin oxide in food | |
| CN112114066B (en) | Method for detecting flonicamid and metabolite thereof in botanical agricultural products by combining common radical method with UPLC-MSMS | |
| CN118032994A (en) | Method for measuring residual quantity of cyromazine in vegetable food |
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 |