CN107102076B - Method for detecting content of metamifop optical isomer in organism and environment - Google Patents
Method for detecting content of metamifop optical isomer in organism and environment Download PDFInfo
- Publication number
- CN107102076B CN107102076B CN201710262964.7A CN201710262964A CN107102076B CN 107102076 B CN107102076 B CN 107102076B CN 201710262964 A CN201710262964 A CN 201710262964A CN 107102076 B CN107102076 B CN 107102076B
- Authority
- CN
- China
- Prior art keywords
- metamifop
- optical isomer
- content
- sample
- detecting
- 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
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
- G01N30/89—Inverse chromatography
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)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention provides a method for detecting the content of an metamifop optical isomer in a living body and in the environment, which comprises the following specific steps: 1) preparing a sample; 2) determining chiral chromatographic separation conditions; 3) determining mass spectrum conditions; 4) and (4) measuring the content of the optical isomer. The method selects the chiral high performance liquid chromatography-mass spectrometry/mass spectrometry technology to quantitatively detect the content of the metamifop optical isomer in vivo/environment, has the advantages of simple operation, accurate quantification and low batch cost, is particularly suitable for the requirement of pesticide residue detection/monitoring, and provides a new idea and method for detecting the metamifop optical isomer in vivo/environment.
Description
Technical Field
The invention relates to a method for detecting and monitoring the contents of optical isomers of (R) -metamifop and (S) -metamifop in a biological or environmental sample based on a chiral high performance liquid chromatography-mass spectrometry/mass spectrometry technology, belonging to the field of pesticide analysis and pesticide residue detection/monitoring.
Background
Statistically, by 2015, 25% of the worldwide pesticides are chiral molecules, most of which are sold and used in the form of racemates, while the single isomer accounts for only 7%. Due to the asymmetric environment of receptors such as enzyme, protein, ion channel and the like, the combination of the chiral pesticide and the receptors has stereoselectivity; after it is absorbed by organisms, the processes of metabolism, transformation, excretion and the like are often selective. In most cases, one of the enantiomers has insecticidal or bactericidal activity against the target organism or is more toxic to non-target organisms, while the other enantiomer has no or very low potency. The total concentration of racemic pesticides obtained by achiral analysis may therefore not be consistent with the actual ecotoxicological effect as indicated. Only by studying the toxicity problem and the environmental problem of the chiral pesticide at the level of the enantiomer, the risk of human health and the risk of the ecosystem can be accurately evaluated.
Metamifop (Metamifop, CAS:256412-89-2) is an aryloxyphenoxypropionate herbicide, belonging to ACCase inhibitor. The drug has a chiral center and two optical isomers, namely (R) -metamifop and (S) -metamifop, and the existing toxicological, environmental influence and in vivo metabolism researches do not relate to the chiral center of metamifop. The influence of the "seal baby" event, it is very necessary and necessary to study the differences of different isomers of chiral compounds in vivo in great depth and detail; meanwhile, environmental factors may also cause conversion between optical isomers, and a new pesticide pollution problem is generated.
The method such as HPLC-PDA or HPLC-MS is commonly used for detecting the concentration in the metamifop environment, but the method can only detect the total concentration of the metamifop optical isomer, and cannot detect (R) and (S) -metamifop respectively. The tragedy of the last century "seal baby" has led to the growing recognition that the differences in the organism of the different enantiomers of chiral drugs and pesticides are very large. Therefore, it is necessary to establish a method for analyzing the concentration of the drug in (R) and (S) -metamifop organisms and the environment simultaneously.
The reversed-phase chiral high performance liquid chromatography-mass spectrum/mass spectrum technology combines the separation capability of the chiral chromatographic column on the optical isomer and the high sensitivity of the mass spectrum/mass spectrum technology, and can better solve the problem of detecting the optical isomer of the chiral drug. However, for different separation objects, it is necessary to optimize and screen a large number of conditions and parameters such as sample volume, column temperature, eluent (i.e. mobile phase), flow rate, parent/daughter ion selection, collision energy, and taper hole voltage, and it is extremely difficult to achieve the detection of trace or trace drugs in vivo in living beings or environments, as well as to ensure the separation of optical isomers.
Disclosure of Invention
The invention aims to provide a method for detecting the content of an optical isomer of metamifop in a living body and in the environment, which is particularly suitable for detecting/monitoring the residue of chiral pesticide metamifop in the living body or the residue in the environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
1) preparation of samples: mixing the biological sample or the homogenate of the biological sample with acetonitrile to precipitate protein, performing centrifugal separation and precipitation, and drying supernatant obtained by centrifugation to obtain a sample to be analyzed; or directly extracting metamifop in the environmental sample by using acetonitrile, centrifuging, drying the supernatant obtained by centrifuging, and obtaining a sample to be analyzed;
2) determining chiral chromatographic separation conditions: according to the requirement that the separation degree of (R) -metamifop and (S) -metamifop is more than or equal to 1.5, a mobile phase adopted in chiral high performance liquid chromatography is a mixed solution of methanol or acetonitrile, water, volatile buffer salt and volatile acid, the concentration of the buffer salt in the mixed solution is 1-10mM, the volume fraction of the acid is 0.01-0.5%, and the volume ratio of the methanol or acetonitrile to the water is 1-9: 1; the column temperature is 5-50 ℃; the sample amount is 1-10 mu L; the flow rate of the mobile phase is 0.3-0.8mL/min, and isocratic elution is carried out;
3) determining mass spectrum/mass spectrum working conditions: a triple quadrupole mass spectrum and a multi-reaction monitoring scanning mode are adopted; the parent and daughter ions are 441.09 and 318.05, respectively; the voltage of the taper hole is 20-35V; the collision energy is 15-40 eV;
4) measuring the content of optical isomers: performing chiral high performance liquid chromatography-mass spectrometry/mass spectrometry on a sample to be analyzed, and then calculating the content of (R) -metamifop and (S) -metamifop in the sample by adopting an external standard method.
The biological sample is blood plasma, body fluid, tissue fluid or biological tissue (such as liver, kidney, heart, pancreas, brain, etc.).
The environmental sample is soil, water, crops or other samples which may be polluted.
In the step 1), the volume of acetonitrile used for precipitating the protein is at least 4 times of the volume of the biological sample.
The chiral high performance liquid chromatography adopts a reverse-phase coating type or bonding type chiral chromatographic column, and the chiral filler comprises polysaccharide derivative fillers.
The buffer salt comprises ammonium formate, ammonium acetate, ammonium carbonate or ammonium bicarbonate and the acid comprises formic acid, acetic acid or trifluoroacetic acid.
The working conditions of the mass spectrum/mass spectrum further comprise: the residence time is 0.15-0.17 s; the temperature of an ESI ion source is 120-150 ℃; the temperature of the drying gas is 280-300 ℃, and the flow rate of the drying gas is 600-900L/h; the capillary voltage is 2.5-3.5 KV.
The range of the standard curve adopted by the external standard method (namely preparing a standard solution of (R) -metamifop and (S) -metamifop, making a standard curve, and calculating the content of the (R) -metamifop and the (S) -metamifop in a sample to be analyzed by using the standard curve) is 0.1-150 ng/mL.
The invention has the beneficial effects that:
1) the optical isomer has high analysis sensitivity and low detection limit. The existing chiral HPLC method has poor sensitivity, the lowest detection limit is mu g/mL, and the analysis of trace and trace samples in organisms or in the environment is difficult to realize; the invention adopts the MRM scanning mode in the triple quadrupole, greatly improves the sensitivity while ensuring the separation of optical isomers, has the lowest detection limit of 0.2ng/mL, and can meet the requirement of biological or environmental sample detection.
2) Can simultaneously realize the detection of (R) -metamifop and (S) -metamifop. For the detection of the drug concentration in a biological or environmental sample, the existing method cannot separate and measure the optical isomers of metamifop, only can obtain the total concentration of one total racemic metamifop, and cannot detect the concentration of each optical isomer; according to the invention, conditions of chiral high performance liquid chromatography-mass spectrometry/mass spectrometry are optimized through a large number of experiments, key parameters such as parent ions and ionic ions, a taper hole voltage, an elution flow rate, a dry gas temperature and the like are determined, high sensitivity is ensured, and simultaneous detection of (R) -metamifop and (S) -metamifop is realized for the first time, so that technical support is provided for in vivo/environmental detection of metamifop optical isomers, and a new thought is provided for researching in vivo/environmental conversion of chiral pesticides.
3) Can realize automatic detection, accord with the needs of large sample size in the pesticide residue detects: the invention can realize unattended operation by utilizing the automatic sample introduction function of HPLC; manpower and material resources are greatly saved, and the requirements of multi-sample and big data processing are met.
Detailed Description
The present invention will be further described with reference to the following examples.
EXAMPLE 1 detection of the concentration of racemic Oxazolecarboxamide in plasma
By way of example, but the scope of the present invention is not limited to this experiment, the following steps are specifically performed: the method comprises the following specific steps: 1) preparing a sample; 2) determining chiral chromatographic separation conditions; 3) determining mass spectrum conditions; 4) and (4) measuring the content of the optical isomer.
First, sample preparation
Taking 100 mu L of SD rat plasma injected with racemic metamifop (blood sampling time point is 1.5h), adding 400 mu L of acetonitrile, carrying out rotary mixing for 30s, centrifuging for 10min at 12500 r, taking supernatant, carrying out liquid nitrogen blow-drying at room temperature, and obtaining a sample to be analyzed, and freezing and storing at-80 ℃;
secondly, determining chiral chromatographic separation conditions
The above samples were reconstituted in 50. mu.L of mobile phase and analyzed by Waters TQD Xevo for (R) and (S) -metamifop, under the following conditions;
a chromatographic column: xylonite
OJ-3R chromatography column (150mm 2.1mm 3 um).
Chromatographic conditions are as follows:
① automatic sample injection, volume 5 μ L;
② the mobile phase is acetonitrile-water (90: 10 by volume) mixed solvent (containing 0.1% by volume of formic acid and 10mM ammonium formate), the flow rate is 0.3mL/min, and the elution is carried out isocratically;
③ the temperature of the column incubator is 25 ℃;
under the condition, the retention time of (R) -metamifop and (S) -metamifop is respectively as follows: 18.22 and 19.92min, with a resolution of 1.8.
Thirdly, determining the mass spectrum condition
Multiple response monitoring scan mode (MRM) with Waters TQD, conditions were as follows:
the parent and daughter ions are 441.09 and 318.05, respectively;
the voltage of the taper hole is 20V;
the collision energy is 40 eV;
residence time 0.161 s;
ESI ion source temperature is 150 ℃;
N2the temperature and flow rate of the (drying gas) were 300 ℃ and 900L/h;
the capillary voltage was 3.5 KV.
IV, determination of optical isomer content
Data acquisition and processing was performed using Mass Lynx software (Version 4.1), and quantitative calculations were performed using TargetLynxTMsoftware。
Preparing a standard solution (acetonitrile water solution with volume fraction of 50%) of racemic metamifop, wherein the concentrations are respectively as follows: 0.1ng/mL, 0.5ng/mL, 1ng/mL, 5ng/mL, 10ng/mL, 20ng/mL, 40ng/mL, 80ng/mL, 150 ng/mL; the standard solution sample and the sample to be analyzed are analyzed by the chromatographic and mass spectrometric conditions in the embodiment, and Target LynxTMsoftware automatically calculates the content of (R) -and (S) -metamifop in the sample to be tested.
In this example, the blood concentrations of (R) -metamifop and (S) -metamifop were 26.55ng/mL and 29.39ng/mL, respectively; there are differences in absorption, distribution and metabolism between the (R) and (S) isomers.
EXAMPLE 2 detection of the concentration of (R) -Oxazolecarboxamide in urine
The conditions were the same as in example 1 except for the following conditions:
① taking 100 μ L (24h total urine) of SD rat urine injected with (R) -metamifop;
② chromatographic column of xylonite
IC chromatography columns (150mm 4.6mm 5 um);
③ the mobile phase is methanol and water mixed solvent (containing 0.5% volume fraction of acetic acid and 1mM ammonium acetate) at flow rate of 0.8mL/min, and is eluted at equal rate;
④ automatic sample injection, volume 10 u L;
⑤ the temperature of the column incubator is 40 ℃;
⑥ the voltage of the taper hole is 35V;
⑦ the collision energy was 15 eV.
In this example, the retention times of (R) -metamifop and (S) -metamifop are respectively: 9.49 and 10.98 min; the urine drug concentrations are respectively 5.18ng/mL and 0.66 ng/mL; the (R) -isomer can be partially converted to the (S) -isomer in rats.
Example 3 detection of the concentration of (S) -Oxazolecarboxamide in the liver
The conditions were the same as in example 1 except for the following conditions:
① taking 0.1g of SD rat liver injected with (S) -metamifop (neck breaking and death 12 hours after administration, liver taking out by quick dissection), adding 0.5mL of PBS buffer solution, homogenizing at 4 ℃, centrifuging, taking 100 μ L of supernatant (homogenate), adding 400 μ L of acetonitrile into the homogenate, carrying out vortex mixing for 30S, 12500 r/min separating for 5min, taking supernatant, and drying with nitrogen at room temperature to obtain a sample to be analyzed;
② chromatographic column of xylonite
IA chromatography columns (150mm 4.6mm 5 um);
③ the mobile phase is acetonitrile-water (70: 30 by volume) mixed solvent (containing 0.5% by volume of trifluoroacetic acid and 5mM ammonium bicarbonate), the flow rate is 0.4mL/min, and the elution is carried out isocratically;
④ automatic sample injection, volume 1 uL;
⑤ the temperature of the column incubator is 50 ℃;
⑥ the voltage of the taper hole is 30V;
⑦ the collision energy was 30 eV.
In this example, the retention times of (R) -metamifop and (S) -metamifop are respectively: 14.28 and 15.65 min; the liver drug concentration is respectively 8.55ng/mL and 65.58 ng/mL; the (S) -isomer can be partially converted to the (R) -isomer in rat liver.
Example 4 detection of (R) -Oxazolecarboxamide in soil
The conditions were the same as in example 1 except for the following conditions:
① A soil sample (0.1 g) after spraying (R) -metamifop (20 g/mu) for 48 hours is taken, 0.5mL PBS buffer solution and 1.2mL acetonitrile are added, mixed for 30s, centrifuged to take 1mL supernatant, N2Drying, and redissolving 20 mu L of mobile phase;
② chromatographic column of xylonite
IB chromatography column (150mm 4.6mm 5 um);
③ the mobile phase is acetonitrile-water (50: 50 volume ratio) mixed solvent (containing 0.2% volume fraction of trifluoroacetic acid and 10mM ammonium bicarbonate), the flow rate is 0.8mL/min, and the elution is carried out isocratically;
④ automatic sample injection, volume 10 u L;
⑤ the temperature of the column incubator is 5 ℃;
⑥ the collision energy was 15 eV.
In this example, the retention times of (R) -metamifop and (S) -metamifop are respectively: 8.44 and 9.95 min; the environmental residual concentration is 3.89ng/mL and 0.22ng/mL respectively; there is a phenomenon of chiral conversion in the environment.
The invention aims at the detection of the optical pure isomer of metamifop, biological or environmental samples from different sources are interfered by other substances in the samples, and the chromatographic separation conditions, mass spectrum detection parameters and the like of the samples are different, so that the condition range in the invention is obtained.
The invention selects a method for quantitatively detecting the content of the metamifop optical isomer by using a reversed-phase chiral high performance liquid chromatography-mass spectrometry/mass spectrometry technology, aims to solve the problems of detection/monitoring of the metamifop optical isomer in practical scientific research and pesticide residue monitoring, and provides a new thought and method for conversion and detection of the metamifop optical isomer in organisms and in the environment.
Claims (8)
1. A method for detecting the content of the optical isomer of metamifop in organisms and in the environment is characterized in that: the method comprises the following steps:
1) preparation of samples: mixing the biological sample or homogenate thereof with acetonitrile to precipitate protein, performing centrifugal separation and precipitation, and drying supernatant obtained by centrifugation to obtain a sample to be analyzed; or directly extracting metamifop in the environmental sample by using acetonitrile, centrifuging, drying the supernatant obtained by centrifuging, and obtaining a sample to be analyzed;
2) determining chiral chromatographic separation conditions: according to the requirement that the separation degree of (R) -metamifop and (S) -metamifop is more than or equal to 1.5, a mobile phase adopted in chiral high performance liquid chromatography is a mixed solution of methanol or acetonitrile, water, volatile buffer salt and volatile acid, the concentration of the buffer salt in the mixed solution is 1-10mM, the volume fraction of the acid is 0.01-0.5%, and the volume ratio of the methanol or acetonitrile to the water is 1-9: 1; the column temperature is 5-50 ℃; the sample amount is 1-10 mu L; the flow rate of the mobile phase is 0.3-0.8mL/min, and isocratic elution is carried out;
the chiral high performance liquid chromatography adopts a reverse-phase coating type or bonding type chiral chromatographic column, and the chiral packing adopts polysaccharide derivative packing;
3) determining mass spectrum/mass spectrum working conditions: a triple quadrupole mass spectrum and a multi-reaction monitoring scanning mode are adopted; the parent and daughter ions are 441.09 and 318.05, respectively; the voltage of the taper hole is 20-35V; the collision energy is 15-40 eV;
4) measuring the content of optical isomers: performing chiral high performance liquid chromatography-mass spectrometry/mass spectrometry on a sample to be analyzed, and then calculating the contents of (R) -metamifop and (S) -metamifop in the sample by adopting an external standard method, wherein a standard solution is prepared by using racemic metamifop.
2. The method for detecting the content of the optical isomer of metamifop in organisms and in the environment according to claim 1, which is characterized in that: the biological sample is selected from a body fluid or a biological tissue.
3. The method for detecting the content of the optical isomer of metamifop in organisms and in the environment according to claim 2, which is characterized in that: the body fluid is selected from plasma or interstitial fluid.
4. The method for detecting the content of the optical isomer of metamifop in organisms and in the environment according to claim 1, which is characterized in that: the environmental sample is selected from soil, water, crops or other samples which may be contaminated.
5. The method for detecting the content of the optical isomer of metamifop in organisms and in the environment according to claim 1, which is characterized in that: in the step 1), the volume of acetonitrile used for precipitating the protein is at least 4 times of the volume of the biological sample.
6. The method for detecting the content of the optical isomer of metamifop in organisms and in the environment according to claim 1, which is characterized in that: the buffer salt is selected from ammonium formate, ammonium acetate, ammonium carbonate or ammonium bicarbonate, and the acid is selected from formic acid, acetic acid or trifluoroacetic acid.
7. The method for detecting the content of the optical isomer of metamifop in organisms and in the environment according to claim 1, which is characterized in that: the working conditions of the mass spectrum/mass spectrum further comprise: the residence time is 0.15-0.17 s; the temperature of an ESI ion source is 120-150 ℃; the temperature of the drying gas is 280-300 ℃, and the flow rate of the drying gas is 600-900L/h; the capillary voltage is 2.5-3.5 KV.
8. The method for detecting the content of the optical isomer of metamifop in organisms and in the environment according to claim 1, which is characterized in that: the standard curve adopted by the external standard method is in the range of 0.1-150 ng/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710262964.7A CN107102076B (en) | 2017-04-20 | 2017-04-20 | Method for detecting content of metamifop optical isomer in organism and environment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710262964.7A CN107102076B (en) | 2017-04-20 | 2017-04-20 | Method for detecting content of metamifop optical isomer in organism and environment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107102076A CN107102076A (en) | 2017-08-29 |
| CN107102076B true CN107102076B (en) | 2020-06-05 |
Family
ID=59657096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710262964.7A Active CN107102076B (en) | 2017-04-20 | 2017-04-20 | Method for detecting content of metamifop optical isomer in organism and environment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107102076B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108918709B (en) * | 2018-07-12 | 2021-05-18 | 河北医科大学 | Screening and quantitative detection method for common herbicides in blood and application |
| CN109342623A (en) * | 2018-12-25 | 2019-02-15 | 安徽华辰检测技术研究院有限公司 | A kind of method that gas chromatography mass spectrometry detects aryloxyphenoxypropanoates class herbicide in rice |
| CN111595979A (en) * | 2020-06-15 | 2020-08-28 | 湖南农业大学 | Ultra-high performance liquid chromatography-tandem mass spectrometry method for simultaneously determining content of metamifop and metabolite thereof |
| CN111735899B (en) * | 2020-08-04 | 2020-11-20 | 天津汉一医药科技有限公司 | Analysis method of naphthalene ring containing substituent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353740A (en) * | 2011-06-03 | 2012-02-15 | 中国农业科学院农业质量标准与检测技术研究所 | Method for synchronous determination of content of triazole chiral pesticide enantiomers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2897475C (en) * | 2004-04-30 | 2018-07-10 | Dow Agrosciences Llc | Novel herbicide resistance genes |
-
2017
- 2017-04-20 CN CN201710262964.7A patent/CN107102076B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353740A (en) * | 2011-06-03 | 2012-02-15 | 中国农业科学院农业质量标准与检测技术研究所 | Method for synchronous determination of content of triazole chiral pesticide enantiomers |
Non-Patent Citations (3)
| Title |
|---|
| Development of a multi-residue enantiomeric analysis method for 9 pesticides in soil and water by chiral liquid chromatography/tandem mass spectrometry;Yuanbo Li等;《Journal of Hazardous Materials》;20130204;第250-251卷;第9-18页 * |
| Enantioselective toxicity and degradation of chiral herbicide fenoxaprop-ethyl in earthworm Eisenia fetida;Xu Jing等;《Ecological Indicators》;20161227;第75卷;第128-129页第2.4节和图2 * |
| 农药禾草灵在键合型手性固定相上的拆分;刘万良等;《化学试剂》;20091031;第31卷(第10期);第825-827页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107102076A (en) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107102076B (en) | Method for detecting content of metamifop optical isomer in organism and environment | |
| Pan et al. | Stereoselective analysis of novel chiral fungicide pyrisoxazole in cucumber, tomato and soil under different application methods with supercritical fluid chromatography/tandem mass spectrometry | |
| Li et al. | Simultaneous determination of clenbuterol, salbutamol and ractopamine in milk by reversed-phase liquid chromatography tandem mass spectrometry with isotope dilution | |
| Zhang et al. | Application and enantioselective residue determination of chiral pesticide penconazole in grape, tea, aquatic vegetables and soil by ultra performance liquid chromatography-tandem mass spectrometry | |
| Qu et al. | Rapid determination of underivatized pyroglutamic acid, glutamic acid, glutamine and other relevant amino acids in fermentation media by LC-MS-MS | |
| CN107525866B (en) | Method for extracting and analyzing beta-receptor agonist clenbuterol by using DPX gun head type dispersed solid phase microextraction column | |
| Elmongy et al. | Determination of metoprolol enantiomers in human plasma and saliva samples utilizing microextraction by packed sorbent and liquid chromatography–tandem mass spectrometry | |
| Fumes et al. | Determination of pesticides in sugarcane juice employing microextraction by packed sorbent followed by gas chromatography and mass spectrometry | |
| CN106124678A (en) | Perfluorochemical and the quick screening method of precursor substance thereof in the flesh of fish | |
| CN105784894B (en) | Pesticide residue detection method for traditional Chinese medicine | |
| CN105758946A (en) | Method for determining residual quantity of 15 kinds of triazole type pesticides in fruit | |
| Vu-Duc et al. | Multiresidue pesticides analysis of vegetables in Vietnam by ultrahigh-performance liquid chromatography in combination with high-resolution mass spectrometry (UPLC-Orbitrap MS) | |
| Warren | Development of online microdialysis-mass spectrometry for continuous minimally invasive measurement of soil solution dynamics | |
| Sin et al. | Determination of quinoxaline-2-carboxylic acid, the major metabolite of carbadox, in porcine liver by isotope dilution gas chromatography–electron capture negative ionization mass spectrometry | |
| Rocío-Bautista et al. | Direct coupling of bio-SPME to liquid electron ionization-MS/MS via a modified microfluidic open interface | |
| Wu et al. | Determination of ractopamine in pig hair using liquid chromatography with tandem mass spectrometric detection | |
| Kimura et al. | Simple and rapid determination of 1‐deoxynojirimycin in mulberry leaves | |
| CN101334386B (en) | Determination method for plant medicine blood plasma amygdalin for strengthening the body resistance | |
| Hashiguchi et al. | Quantitative analysis of seven plant hormones in Lotus japonicus using standard addition method | |
| CN105548431A (en) | Method for simultaneously detecting residual quantities of oxamyl and oxamyl oxime in vegetable/fruits | |
| CN106645477A (en) | Method for detecting florfenicol amine residue and application | |
| Lu et al. | A rapid liquid chromatography‐electrospray ionization‐ion mobility spectrometry method for monitoring nine representative metabolites in the seedlings of cucumber and wheat | |
| Schmeer et al. | Rapid pharmacokinetic screening of salbutamol in plasma samples by column-switching high-performance liquid chromatography–electrospray mass spectrometry | |
| CN110806458A (en) | Method for simultaneously detecting leucine, isoleucine and valine contents in blood | |
| CN108663464B (en) | Method for detecting fenhexamid in fruits, vegetables or soil |
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 |