CN113406239B - Method for measuring fluoxastrobin and metabolite thereof in water - Google Patents
Method for measuring fluoxastrobin and metabolite thereof in water Download PDFInfo
- Publication number
- CN113406239B CN113406239B CN202110732215.2A CN202110732215A CN113406239B CN 113406239 B CN113406239 B CN 113406239B CN 202110732215 A CN202110732215 A CN 202110732215A CN 113406239 B CN113406239 B CN 113406239B
- Authority
- CN
- China
- Prior art keywords
- fluoxastrobin
- chromatographic
- sample
- weight
- concentration
- 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
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- 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
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
-
- 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
Abstract
The invention belongs to the technical field of substance detection, and provides a method for determining fluoxastrobin and metabolites thereof in water. The determination method provided by the invention has the advantages of simple pretreatment and high detection sensitivity on fluoxastrobin and metabolites thereof in water. The invention adopts APCI ‑ The linear range of the detection of the o-chlorophenol is 0.0005 to 0.05mg/L, the LOQ is 0.001mg/L, and the LOD is 1.00 multiplied by 10 ‑2 ng, the response degree of ESI source detection is higher than that of the prior art; LODs of fluoxastrobin, fluoxastrobin metabolite M48-E, and fluoxastrobin M40 were 1.00X 10, respectively ‑3 ng、1.00×10 ‑3 ng and 2.5X 10 ‑3 ng; the minimum detectable concentration (LOQ) of fluoxastrobin, fluoxastrobin metabolite M48-E, and fluoxastrobin M40 in water was 0.00200 mg.L ‑1 。
Description
Technical Field
The invention relates to the technical field of substance detection, in particular to a method for determining fluoxastrobin and metabolites thereof in water.
Background
The fluoxastrobin is a broad-spectrum dihydrooxazine (dihydro-dioxazines) systemic stem and leaf treatment bactericide variety developed by Bayer company in Germany, and the product has the advantages of quick absorption, rain wash resistance, long application adaptation period, more applicable crops and excellent prevention and treatment. The fluoxastrobin is mainly used for preventing and controlling all fungoid germs in potatoes, vegetables, cereals and coffee, has the dual characteristics of quick sterilization and long lasting time, and has good compatibility to crops. Is relatively safe to crops, underground water and environment under the condition of recommended dosage. Has good activity on almost all diseases of fungi (Basidiomycetes, ascomycetes, fungi known as fungi and oomycetes) such as rust disease, net blotch, downy mildew and other dozens of diseases.
The fluoxastrobin metabolites include o-chlorophenol, M48-E and M40. The fluoxastrobin metabolite o-chlorophenol has great harm to the environment, and can cause serious pollution to water and soil in particular. If the fluoxastrobin is not properly applied, the fluoxastrobin can pollute underground water to a certain extent and further has certain harm to human bodies. At present, only synthesis, residual detection in fruits and beverages, influence of soil microorganisms and soil enzyme activity and residual detection on rice plants are reported on fluoxastrobin, and no related report is found on an aquatic detection method of fluoxastrobin and metabolites thereof.
Disclosure of Invention
In view of this, the present invention aims to provide a method for measuring fluoxastrobin and metabolites thereof in water. The determination method provided by the invention can accurately detect fluoxastrobin and metabolites thereof in water.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for measuring fluoxastrobin and metabolites thereof in water, wherein the fluoxastrobin metabolites comprise o-chlorophenol, M48-E and M40, and the method comprises the following steps:
mixing a water sample to be detected with acetonitrile to obtain a fluoxastrobin-M48-E-M40 on-machine sample;
filtering a water sample to be detected to obtain an on-machine sample of o-chlorophenol;
performing first ultra performance liquid chromatography tandem mass spectrometry on the fluoxastrobin-M48-E-M40 computer sample to obtain the chromatographic information of fluoxastrobin and M48-E;
performing second ultrahigh liquid chromatography tandem mass spectrometry on the fluoxastrobin-M48-E-M40 computer sample to obtain M40 chromatographic information;
performing third ultrahigh liquid chromatography tandem mass spectrometry detection on the o-chlorophenol on-machine sample to obtain o-chlorophenol chromatographic information;
substituting the fluoxastrobin chromatographic information, the chromatographic information of M48-E, the chromatographic information of M40 and the o-chlorophenol chromatographic information into a fluoxastrobin concentration-peak area standard curve, an M48-E concentration-peak area standard curve, an M40 concentration-peak area standard curve and an o-chlorophenol concentration-peak area standard curve to obtain the content of fluoxastrobin and metabolites thereof in the water;
the parameters of the first ultra performance liquid chromatography tandem mass spectrometry detection comprise a first mass spectrometry detection parameter and a first chromatographic detection parameter;
the first mass spectrometry detection parameter comprises: an ion source: ESI + (ii) a Capillary voltage: 5.5kV; ion source temperature: 550 ℃; air curtain air: 35psi; and (3) air blasting: 7psi; auxiliary heating gas: 50psi; spraying mist: 50psi; is injected intoVoltage: 10V; collision cell emission voltage: 16V;
the first chromatographic detection parameters include: a chromatographic column: ACQUITY UPLC TM BEH C 18 Column, 1.7 μm,2.1 mm. Times.100 mm, waters corporation, USA; temperature of the column: 40 ℃; sample introduction amount: 2.00 mu L; flow rate: 0.3 mL/min -1 (ii) a The mobile phase A is a formic acid-ammonium acetate aqueous solution, the volume concentration of formic acid in the formic acid-ammonium acetate aqueous solution is 0.1%, and the concentration of ammonium acetate is 2mmol/L; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,65% by weight A; 0.5-2.0 min,65% by weight A-15% by weight A;2.0 to 4.0min, and 15% to A to 2% of A; 4.0-4.5min, 2%; 4.5-4.6 min,2% -65% A; 4.6-6.5min, 65% by weight;
the parameters of the second ultra performance liquid chromatography tandem mass spectrometry detection comprise second mass spectrometry detection parameters and second chromatographic detection parameters;
the second mass spectrometry detection parameters include: an ion source: ESI - (ii) a Capillary voltage: -4.5kV; ion source temperature: 550 ℃; air curtain air: 35psi; and (3) collision gas spraying: 7psi; auxiliary heating gas: 50psi; spraying mist: 50psi; injection voltage: -10V, collision cell ejection voltage: -16V;
the second chromatographic detection parameters include: and (3) chromatographic column: ACQUITY UPLC TM BEH C 18 Column, 1.7 μm,2.1mm × 100mm, waters corporation, USA; temperature of the column: 40 ℃; sample injection amount: 5.00 mu L; flow rate: 0.3 mL/min -1 (ii) a The mobile phase A is formic acid-ammonium acetate aqueous solution, the volume concentration of formic acid in the formic acid-ammonium acetate aqueous solution is 0.1%, and the concentration of ammonium acetate is 2mmol/L; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,55% A; 0.5-3.5 min,55% by weight A-5% by weight A; 3.5-4.0min, 5 percent; 4.0-4.1min, 5% -55% A; 4.1-6.0min, 55 percent;
the third ultra performance liquid chromatography tandem mass spectrometry detection parameters comprise a third mass spectrometry detection parameter and a third chromatography detection parameter;
the third mass spectrometric detection parameter comprises: an ion source: APCI - (ii) a Needle current: -3.5mA; ion source temperature: 350 ℃; air curtain air: 25psi; spraying nozzleAir collision: 8psi; spraying mist: 50psi; injection voltage: -10V; collision cell emission voltage: -14V;
the third spectral detection parameters include: and (3) chromatographic column:
Omega Polar C 18 column, 3 μm,2.1mm by 50mm, phenomenex, USA; flow rate: 0.40mL/min; column temperature: at 40 ℃; sample introduction volume: 20.0 mu L; the mobile phase A is 2mmol/L ammonium acetate water solution; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,80% by weight A; 0.5-2.0min, 80% by (a-40); 2.0 to 3.0min,40% to A to 20% of A;3.0 to 3.5min,20% by weight A;3.5 to 3.6min,20% by weight A to 80% by weight A;3.6 to 5.5min,80% by weight.
Preferably, in the process of preparing the fluoxastrobin-M48-E-M40 computer sample, the volume ratio of the water sample to be detected to the acetonitrile is 1:1.
preferably, after the water sample to be detected and acetonitrile are mixed, filtering the obtained mixed solution, wherein the aperture of the filtered filter membrane is 0.22 μm.
Preferably, the aperture of the filter membrane for filtering the water sample to be detected is 0.22 μm.
The invention provides a method for measuring fluoxastrobin and metabolites thereof in water, and the method has the advantages of simple pretreatment method, high detection accuracy and high sensitivity for fluoxastrobin and metabolites thereof in water. The linear range of the detection of the o-chlorophenol by adopting an APCI-source is 0.0005-0.05 mg/L, the LOQ is 0.001mg/L, and the LOD is 1.00 multiplied by 10 - 2 ng, the response (linear range is 0.05-10 mg/L, LOQ is 0.03-1.5 mg/kg) is higher than that of ESI source detection in the prior art; the LODs of fluoxastrobin, fluoxastrobin metabolite M48-E and fluoxastrobin M40 were 1.00X 10, respectively -3 ng、 1.00×10 -3 ng and 2.5X 10 -3 ng; the minimum detected concentration (LOQ) of fluoxastrobin, fluoxastrobin metabolite M48-E, and fluoxastrobin M40 in water was 0.00200 mg.L -1 。
Drawings
FIG. 1 is a regression equation of the fluoxastrobin standard curve;
FIG. 2 is a regression equation of the M48-E standard curve for fluoxastrobin metabolites;
FIG. 3 is a regression equation of the M40 standard curve for fluoxastrobin metabolites;
FIG. 4 is a regression equation of the fluoxastrobin metabolite o-chlorophenol standard curve;
FIG. 5 is a graph of the peak area response results for different ion source temperatures.
Detailed Description
The invention provides a method for measuring fluoxastrobin and metabolites thereof in water, wherein the fluoxastrobin metabolites comprise o-chlorophenol, M48-E and M40, and the method comprises the following steps:
mixing a water sample to be detected with acetonitrile to obtain a fluoxastrobin-M48-E-M40 on-machine sample;
filtering a water sample to be detected to obtain an o-chlorophenol on-machine sample;
performing first ultra performance liquid chromatography tandem mass spectrometry on the fluoxastrobin-M48-E-M40 on-machine sample to obtain the chromatographic information of fluoxastrobin and M48-E;
performing second ultrahigh liquid chromatography tandem mass spectrometry on the fluoxastrobin-M48-E-M40 computer sample to obtain M40 chromatographic information;
performing third ultrahigh liquid chromatography tandem mass spectrometry detection on the o-chlorophenol on-machine sample to obtain o-chlorophenol chromatographic information;
substituting the fluoxastrobin chromatographic information, the chromatographic information of M48-E, the chromatographic information of M40 and the o-chlorophenol chromatographic information into a fluoxastrobin concentration-peak area standard curve, an M48-E concentration-peak area standard curve, an M40 concentration-peak area standard curve and an o-chlorophenol concentration-peak area standard curve to obtain the content of fluoxastrobin and metabolites thereof in the water.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
According to the invention, a water sample to be detected is mixed with acetonitrile to obtain the fluoxastrobin-M48-E-M40 on-machine sample.
In the invention, the volume ratio of the water sample to be detected to acetonitrile is preferably 1:1. in the invention, after the water sample to be detected is mixed with acetonitrile, preferably, the obtained mixed system is subjected to vortex and filtration, wherein the vortex time is preferably 30s; the pore size of the filtration membrane is preferably 0.22 μm. In the present invention, the concentration range of each substance in the fluoxastrobin-M48-E-M40 machine sample is preferably in the concentration range when a standard curve is established, and when the concentration of each substance in the fluoxastrobin-M48-E-M40 machine sample is higher than the concentration range when the standard curve is established, the method preferably further comprises: diluting the fluoxastrobin-M48-E-M40 computer sample and then filtering; the diluted reagent is preferably deionized water and acetonitrile in a volume ratio of 1:1.
The method filters a water sample to be detected to obtain an on-machine sample of o-chlorophenol. In the invention, the pore diameter of the filter membrane for filtering the water sample to be detected is preferably 0.22 μm. In the present invention, the concentration range of the o-chlorophenol in the o-chlorophenol on-machine sample is preferably within the concentration range when the standard curve is established, and when the concentration of the o-chlorophenol in the o-chlorophenol on-machine sample is higher than the concentration range when the standard curve is established, the method further preferably includes: diluting the o-chlorophenol sample on a machine and then filtering; the diluted reagent is preferably purified drinking water.
After the fluoxastrobin-M48-E-M40 on-machine sample is obtained, the invention carries out first ultra performance liquid chromatography tandem mass spectrometry detection on the fluoxastrobin-M48-E-M40 on-machine sample to obtain the chromatographic information of fluoxastrobin and M48-E.
In the invention, the parameters of the first ultra performance liquid chromatography tandem mass spectrometry detection comprise a first mass spectrometry detection parameter and a first chromatographic detection parameter.
In the present invention, the first mass spectrometric detection parameters comprise: an ion source: ESI + (ii) a Capillary voltage: 5.5kV; ion source temperature: 550 ℃; air curtain air: 35psi; and (3) collision gas spraying: 7psi; auxiliary heating gas: 50psi; spraying mist: 50psi; injection voltage: 10V; collision cell emission voltage: 16V.
In the present invention, the first color spectrum detection parameters include: a chromatographic column: ACQUITYUPLC TM BEH C 18 Column, 1.7 μm,2.1mm × 100mm, waters corporation, USA; temperature of the column: 40 ℃; intoSample size: 2.00 mu L; flow rate: 0.3 mL/min -1 (ii) a The mobile phase A is formic acid-ammonium acetate aqueous solution, the volume concentration of formic acid in the formic acid-ammonium acetate aqueous solution is 0.1%, and the concentration of ammonium acetate is 2mmol/L; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,65% by weight of A; 0.5-2.0 min,65% by weight A-15%; 2.0 to 4.0min, and 15% to A to 2% of A;4.0 to 4.5min,2% by weight A; 4.5-4.6 min,2% -65% A;4.6 to 6.5min,65% by volume A.
After the fluoxastrobin-M48-E-M40 on-machine sample is obtained, the invention carries out second ultrahigh liquid chromatography tandem mass spectrometry detection on the fluoxastrobin-M48-E-M40 on-machine sample to obtain M40 chromatographic information.
In the invention, the second parameter for the ultra performance liquid chromatography tandem mass spectrometry detection comprises a second mass spectrometry detection parameter and a second chromatography detection parameter.
In the present invention, the second mass spectrometry detection parameters include: an ion source: ESI - (ii) a Capillary voltage: -4.5kV; ion source temperature: 550 ℃; air curtain air: 35psi; and (3) collision gas spraying: 7psi; auxiliary heating gas: 50psi; spraying mist: 50psi; injection voltage: -10V, collision cell ejection voltage: -16V.
In the present invention, the second spectrum detection parameters include: and (3) chromatographic column: ACQUITYUPLC TM BEH C 18 Column, 1.7 μm,2.1mm × 100mm, waters corporation, USA; temperature of the column: at 40 ℃; sample introduction amount: 5.00 mu L; flow rate: 0.3 mL/min -1 (ii) a The mobile phase A is formic acid-ammonium acetate aqueous solution, the volume concentration of formic acid in the formic acid-ammonium acetate aqueous solution is 0.1%, and the concentration of ammonium acetate is 2mmol/L; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,55% A; 0.5-3.5 min,55% by weight A-5% by weight A; 3.5-4.0min, 5 percent; 4.0-4.1min, 5% -55% A; 4.1-6.0min, 55 percent.
And performing third ultrahigh liquid chromatography tandem mass spectrometry detection on the o-chlorophenol on-machine sample to obtain o-chlorophenol chromatographic information.
In the invention, the parameters of the third ultra performance liquid chromatography tandem mass spectrometry detection comprise a third mass spectrometry detection parameter and a third chromatography detection parameter.
In the present invention, the third mass spectrometric detection parameters comprise: an ion source: APCI - (ii) a Needle current: -3.5mA; ion source temperature: 350 ℃; air curtain air: 25psi; and (3) collision gas spraying: 8psi; spraying mist: 50psi; injection voltage: -10V; collision cell emission voltage: -14V.
In the present invention, the third spectrum detection parameters include: a chromatographic column:
Omega Polar C 18 column, 3 μm,2.1mm × 50mm, phenomenex, USA; flow rate: 0.40mL/min; column temperature: 40 ℃; sample injection volume: 20.0 mu L; the mobile phase A is 2mmol/L ammonium acetate aqueous solution; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,80% by weight A; 0.5-2.0 min,80% by weight A-40% A;2.0 to 3.0min,40% to A to 20% of A;3.0 to 3.5min,20% by weight A; 3.5-3.6 min,20% A-80% A;3.6 to 5.5min,80% by weight.
In the present invention, the qualitative and quantitative modes of fluoxastrobin and its metabolites are both MRM multi-reaction monitoring modes, and table 1 is the quantitative and qualitative parameters of fluoxastrobin and its metabolites under the MRM multi-reaction monitoring mode.
TABLE 1 Fluoroazoxystrobin and its metabolites quantitative and qualitative parameters in MRM multiple reaction monitoring mode
* Quantitative ion (quality ion)
After the fluoxastrobin chromatographic information, the M48-E chromatographic information, the M40 chromatographic information and the o-chlorophenol chromatographic information are obtained, the fluoxastrobin chromatographic information, the M48-E chromatographic information, the M40 chromatographic information and the o-chlorophenol chromatographic information are substituted into a fluoxastrobin concentration-peak area standard curve, an M48-E concentration-peak area standard curve, an M40 concentration-peak area standard curve and an o-chlorophenol concentration-peak area standard curve, so that the content of fluoxastrobin and metabolites thereof in water is obtained.
In the present invention, the obtaining manner of the fluoxastrobin concentration-peak area standard curve, the M48-E concentration-peak area standard curve and the M40 concentration-peak area standard curve preferably comprises the following steps:
0.0120g of fluoxastrobin standard substance is weighed, acetonitrile is used for fixing the volume to 10.00mL, and the concentration is 1.19 multiplied by 10 3 A standard stock solution of fluoxastrobin in mg/L; the purity of the fluoxastrobin standard product is preferably 99.33%;
weighing 0.0183g of fluoxastrobin metabolite M48-E, and diluting to 10.00mL with acetonitrile to obtain the concentration of 1.73 × 10 3 A standard stock solution of the fluoxastrobin metabolite M48-E in mg/L; the purity of the fluoxastrobin metabolite M48-E is preferably 94.6%;
weighing fluoxastrobin metabolite M400.0120 g, diluting to 10.00mL with acetonitrile to obtain the concentration of 1.11 × 10 3 A standard stock solution of fluoxastrobin metabolite M40 in mg/L; the purity of the fluoxastrobin metabolite M40 is preferably 92.45%;
diluting the fluoxastrobin standard stock solution, the fluoxastrobin metabolite M48-E standard stock solution and the fluoxastrobin metabolite M40 standard stock solution with acetonitrile to obtain fluoxastrobin, fluoxastrobin metabolite M48-E and fluoxastrobin metabolite M40, wherein the concentration of the fluoxastrobin, the fluoxastrobin metabolite M48-E and the fluoxastrobin metabolite M40 is 10.0mg L -1 Mixed standard working solution of (1);
the volume ratio of acetonitrile to deionized water is 1:1, diluting by 10.0 mg.L step by step -1 Mixing the standard working solutions to give concentrations of 1.00, 0.100, 0.0500, 0.0100, 0.00500, 0.00100, and 0.000500 mg. L -1 Mixed standard working solution of (1);
performing first ultra performance liquid chromatography tandem mass spectrometry detection on the series of mixed standard working solutions to obtain the chromatographic information of fluoxastrobin and fluoxastrobin metabolite M48-E; fitting the fluoxastrobin chromatographic information and the fluoxastrobin concentration to obtain a fluoxastrobin concentration-peak area standard curve; fitting the chromatographic information of the fluoxastrobin metabolite M48-E and the concentration of the fluoxastrobin metabolite M48-E to obtain an M48-E concentration-peak area standard curve.
In the present invention, the parameters of the first hplc-ms detection are preferably consistent with the above technical solutions and are not described herein again.
And performing second ultra performance liquid chromatography tandem mass spectrometry detection on the series of mixed standard working solutions to obtain chromatographic information of the fluoxastrobin metabolite M40, and fitting the chromatographic information of the fluoxastrobin metabolite M40 and the concentration of the fluoxastrobin metabolite M40 to obtain a fluoxastrobin metabolite M40 concentration-peak area standard curve.
In the present invention, the parameters of the second hplc-tandem mass spectrometry detection are preferably consistent with the above technical solution, and are not described herein again.
In the present invention, the method for obtaining the o-chlorophenol concentration-peak area standard curve preferably comprises the following steps:
weighing 0.0116g of o-chlorophenol standard substance, and fixing the volume to 10.00mL by acetonitrile to obtain the concentration of 1.16 multiplied by 10 3 mg/L of o-chlorophenol standard stock solution; the purity of the o-chlorophenol standard product is preferably 99.8%;
diluting the o-chlorophenol standard stock solution with drinking purified water to obtain o-chlorophenol standard working solution with the concentrations of 10.0, 1.00, 0.100, 0.0500, 0.0100, 0.00500, 0.00100 and 0.000500 mg/L;
and performing third ultrahigh liquid chromatography-tandem mass spectrometry detection on the series of o-chlorophenol standard working solutions to obtain the chromatographic information of the o-chlorophenol, and fitting the chromatographic information of the o-chlorophenol and the concentration of the o-chlorophenol to obtain an o-chlorophenol concentration-peak area standard curve.
In the present invention, the parameters of the third hplc-tandem mass spectrometry detection are preferably consistent with the above technical solutions and are not described herein again.
The method for measuring fluoxastrobin and its metabolites in water according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
1.1 instruments and reagents
Instruments and devices: ABSciex5500 liquid chromatography tandem mass spectrometer (ABSciex, USA), ACQUITY UPLC TM BEH C 18 Chromatographic column (1.7 μm,2.1 mm. Times.100 mm, waters corporation, USA), BSA224S electronic balance (sensitivity 0.0001g, sidorist group, germany), MX-S adjustable mixer (Peking DarongXingIng laboratory instruments, ltd.), 50mL PPTE centrifuge tube, 0.22 μm organic syringe filter membrane.
Reagent: fluoxastrobin (purity: 99.33%, dr. Ehrenstorfer GmbH), o-chlorophenol (purity: 99.8%), fluoxastrobin metabolite M48-E (purity: 94.6%), fluoxastrobin metabolite M40 (purity: 92.45%), all three metabolites supplied by beijing kefa vash pesticide technology center, acetonitrile (chromatographically pure, merck corporation), formic acid and ammonium acetate (chromatographically pure, anaqua Chemicals Supply, inc.), and purified drinking water (guan hou drochen food and beverage, ltd).
1.2 preparation of Standard solution
0.0120g of fluoxastrobin standard substance (the purity is 99.33%) is weighed, and the volume is determined to be 10.00mL by acetonitrile, so that the concentration is 1.19 multiplied by 10 3 mg/L of standard stock solution; 0.0183g of fluoxastrobin metabolite M48-E (the purity is 94.6%) is weighed, and the volume is determined to be 10.00mL by using acetonitrile, so that the concentration is 1.73 multiplied by 10 3 mg/L of standard stock solution; weighing fluoxastrobin metabolite M400.0120 g (purity is 92.45%), adding acetonitrile to constant volume to 10.00mL to obtain concentration of 1.11 × 10 3 mg/L of standard stock solution; 0.0116g of o-chlorophenol standard substance (purity is 99.8%) is weighed, and acetonitrile is used for fixing the volume to 10.00mL to obtain the concentration of 1.16 multiplied by 10 3 And (4) refrigerating and storing the standard stock solution of mg/L at 0-5 ℃ for later use.
Diluting fluoxastrobin and its metabolites (M48-E and M40) standard stock solution with acetonitrile to obtain a concentration of 10.0 mg.L -1 Mixed standard working solution of (4); by V Acetonitrile :V Water (W) 1 dilution by stages of 10.0mg · L -1 Mixing the standard working solutions to give concentrations of 1.00, 0.100, 0.0500, 0.0100, 0.00500, 0.00100, and 0.000500 mg. L -1 Mixed standard working solution of (2)(ii) a Diluting the o-chlorophenol standard stock solution by using purified drinking water to obtain the o-chlorophenol standard working solution with the concentrations of 10.0, 1.00, 0.100, 0.0500, 0.0100, 0.00500, 0.00100 and 0.000500 mg/L.
1.3 sample pretreatment
Fixing the volume of a 5.000mL sample to 10.00mL by acetonitrile in a water sample to be detected, and performing vortex for 30s; passing through 0.22 μm filter or V Acetonitrile (ACN) ：V Water (W) Diluting the mixed solvent of =1, and filtering the diluted mixed solvent through a 0.22-micron filter membrane to obtain the fluoxastrobin-M48-E-M40 computer sample.
O-chlorophenol: and (3) filtering the water sample to be detected through a 0.22-micron filter membrane, or diluting the water sample with drinking purified water and then filtering the water sample through the 0.22-micron filter membrane to obtain the o-chlorophenol sample on the computer.
1.4 Mass Spectrometry conditions
Fluoxastrobin, fluoxastrobin metabolite M48-E: an ion source: ESI + (ii) a The capillary voltage is 5.5kV, the ion source temperature is 550 ℃, the gas curtain gas is 35psi, the jet collision gas is 7psi, the auxiliary heating gas is 50psi, the spray gas is 50psi, the injection voltage is 10V, and the injection voltage of the collision chamber is 16V;
fluoxastrobin metabolite M40: an ion source: ESI - (ii) a Capillary voltage is-4.5 kV, ion source temperature is 550 ℃, gas curtain gas is 35psi, spraying collision gas is 7psi, auxiliary heating gas is 50psi, spraying gas is 50psi, injection voltage is-10V, and injection voltage of a collision chamber is-16V;
o-chlorophenol: an ion source: APCI - (ii) a The needle current is minus 3.5mA, the ion source temperature is 350 ℃, the air curtain air is 25psi, the spraying air is 8psi, the spraying air is 50psi, the injection voltage is minus 10V, and the injection voltage in the collision chamber is minus 14V.
The qualitative and quantitative modes of fluoxastrobin and metabolites thereof are MRM multi-reaction monitoring modes, and qualitative parameters are shown in Table 1.
1.5 chromatographic conditions
Fluoxastrobin, fluoxastrobin metabolite M48-E: and (3) chromatographic column: ACQUITYUPLC TM BEH C 18 Columns (1.7 μm,2.1 mm. Times.100 mm, waters, USA); the temperature of the chromatographic column is 40 ℃; the sample injection amount is 2.00 mu L; the flow rate was 0.3 mL/min -1 (ii) a The mobile phase A is 0.1 percent formic acid and 2mmol/L ammonium acetate aqueous solution; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: the time is 0-0.5 min,65％A； 0.5～2.0min，65％A～15％A；2.0～4.0min，15％A～2％A；4.0～4.5min，2％A； 4.5～4.6min，2％～65％A；4.6～6.5min，65％A。
fluoxastrobin metabolite M40: and (3) chromatographic column: ACQUITYUPLC TM BEH C 18 Columns (1.7 μm,2.1 mm. Times.100 mm, waters Corp.); the temperature of the chromatographic column is 40 ℃; the sample injection amount is 5.00 mu L; the flow rate was 0.3 mL/min -1 (ii) a The mobile phase A is 0.1 percent formic acid and 2mmol/L ammonium acetate aqueous solution; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,55% by weight A; 0.5-3.5 min,55% by weight A-5% by weight A; 3.5-4.0min, 5 percent; 4.0 to 4.1min,5 to 55% by weight of A;4.1 to 6.0min,55% by weight.
O-chlorophenol: a chromatographic column:
OmegaPolar C 18 chromatography columns (3 μm,2.1 mm. Times.50 mm, phenomenex, USA); the flow rate is 0.40mL/min; the column temperature was 40 ℃; the injection volume is 20.0 mu L; the mobile phase A is 2mmol/L ammonium acetate aqueous solution; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,80% by weight A; 0.5-2.0min, 80% by (a-40); 2.0-3.0 min,40% by weight A-20% by weight A;3.0 to 3.5min,20% by weight A;3.5 to 3.6min,20% by weight A to 80% by weight A; 3.6-5.5 min,80% A.
2 results and analysis
2.1 regression equation
Mixing the mixture at concentrations of 1.00, 0.100, 0.0500, 0.0100, 0.00500, 0.00100 and 0.000500 mg.L -1 The mixed standard working solution and the o-chlorophenol standard working solution with the concentration of 10.0, 1.00, 0.100, 0.0500, 0.0100, 0.00500, 0.00100 and 0.000500mg/L are detected and analyzed according to the mass spectrum condition-chromatographic condition, and a standard curve is constructed by using the concentration-peak area; the results are shown in fig. 1 to 4, specifically:
fluoxastrobin: y =415730151x+82490 2 ＝0.9999；
Fluoxastrobin metabolite M48-E: y =65518514x-5619,r 2 ＝1.0000；
Fluoxastrobin metabolite M40: y =1964557x-381,R 2 ＝0.9996；
fluoxastrobin metabolite o-chlorophenol: y =9337889x C5757 2 ＝0.9995。
2.2 recovery and precision
Fluoxastrobin and its metabolites (M48-E and M40) were at 3 spiked levels (0.002 mg. Multidot.L) -1 、 0.100mg·L -1 And 10.0 mg. L -1 ) The average recovery and relative standard deviation at 5 replicates are shown in table 2. O-chlorophenol at 3 spiking levels (0.001, 0.100, and 10.0 mg. Multidot.L) -1 ) The average recovery and relative standard deviation are shown in table 2, with 5 replicates per concentration.
TABLE 2 recovery and relative standard deviation of fluoxastrobin and its metabolites in water
As can be seen from table 2: samples were at 0.00200, 0.100 and 10.0 mg.L -1 At the addition level, the average recovery rate of fluoxastrobin and metabolites (M48-E and M40) is 81.8-109%, and the relative standard deviation RSD (n = 5) is 1.72-7.38%; 0.00100 and 92.8 mg.L of o-chlorophenol -1 At the addition level, the average recovery was 89.6% and 102%, and the relative standard deviation RSD (n = 3) was 6.06% and 8.84%.
2.3 detection and quantitation limits
The lowest first-grade concentration of the standard curve is multiplied by the sample injection amount to be taken as the minimum detection amount (LOD) of the instrument, and the LODs of the fluoxastrobin, the fluoxastrobin metabolite M48-E and the fluoxastrobin M40 are respectively 1.00 multiplied by 10 -3 ng、1.00×10 -3 ng and 2.5X 10 - 3 ng; the minimum detected concentration (LOQ) of fluoxastrobin, fluoxastrobin metabolite M48-E, and fluoxastrobin M40 in water was 0.00200 mg.L -1 (ii) a The minimum amount of o-chlorophenol detected by the instrument (LOD) is 1.00X 10 -2 ng, o-chlorobenzeneThe lowest detectable concentration (LOQ) of phenol in water was 0.00100 mg.L -1 。
2.4 optimization of the pretreatment method
Fluoxastrobin and its metabolites (M48-E and M40): the results of three pretreatment methods of extracting by two organic solvents (ethyl acetate and acetonitrile) and diluting by acetonitrile show that the recovery rates of fluoxastrobin extracted by ethyl acetate and metabolites (M48-E and M40) (n = 3) thereof are respectively 84.5% -94.4%, 39.8% -46.9%, 39.0% -39.7%, and the recovery rates of M48-E and M40 do not meet the requirements; the recovery rates of fluoxastrobin and metabolites thereof (M48-E and M40) extracted from acetonitrile (n = 3) are respectively 98.2% -103%, 89.3% -97.2% and 104% -112%, and the recovery rates can meet the requirements; the recovery rates of the fluoxastrobin diluted by acetonitrile and metabolites (M48-E and M40) (n = 3) thereof are respectively 99.3% -118%, 99.5% -104% and 100% -107%, and the recovery rates can meet the requirements; since the standard curve of the standard working solution for preparing M40 from acetonitrile is not linear, in order to eliminate the solvent effect, the method of diluting acetonitrile is selected as the optimal pretreatment method
2.5 selection of Mass Spectrometry conditions for ortho-chlorophenol
O-chlorophenol: comparative ESI - Source and APCI - Source, same concentration sample, APCI - The source response value is high, so APCI is selected - And (4) detecting a source.
Optimizing ion source parameters: the peak area response values for the comparative air curtain air at 25psi, 30psi and 35psi, respectively, are: the peak area is 253347 at 25psi for air curtain, 145218 at 30psi for air curtain, and 170770 at 35psi for air curtain. It can be seen that: the air curtain air response value is the highest at 25psi, and the air curtain air is selected to be 25psi.
Ion source temperature: the results of comparing the peak area response values at 400 deg.C, 350 deg.C, 300 deg.C and 250 deg.C of the ion source are shown in FIG. 5. As can be seen from fig. 5: when the ion source temperature is 350 ℃, the peak area response value is the highest, and for o-chlorophenol, the sensitivity is greatly improved by optimizing mass spectrum parameters.
2.6 chromatographic Condition optimization
The three conditions of 0.1% formic acid aqueous solution-acetonitrile, 2mmol/L ammonium acetate aqueous solution-acetonitrile and 0.1% formic acid +2mmol/L ammonium acetate aqueous solution-acetonitrile are respectively used as elution solvents, compared with the response and peak shape of a target object, the fluoxastrobin and metabolites thereof (M48-E and M40) have higher sensitivity, moderate retention time and better peak shape under the elution conditions of 0.1% formic acid +2mmol/L ammonium acetate aqueous solution and acetonitrile; the o-chlorophenol has higher response value and better peak shape under the elution condition of 2mmol/L ammonium acetate water solution and acetonitrile.
Example 2
Actual sample detection
Actual samples collected at 5 sites of Hangzhou west lake water, qiantang river water, yun river water, odolaga crossing pond river water and river water near laboratories in 2021, 2 months, were screened, and the detected concentration of fluoxastrobin at the 5 sites was 0.00000717-0.0000226 mg.L -1 In the meantime, all were less than the lowest detected concentration, and 3 metabolites of fluoxastrobin were not detected.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for measuring fluoxastrobin and metabolites thereof in water, the fluoxastrobin metabolites comprise o-chlorophenol, M48-E and M40, and the method comprises the following steps:
mixing a water sample to be detected with acetonitrile to obtain a fluoxastrobin-M48-E-M40 on-machine sample;
filtering a water sample to be detected to obtain an o-chlorophenol on-machine sample;
performing first ultra performance liquid chromatography tandem mass spectrometry on the fluoxastrobin-M48-E-M40 on-machine sample to obtain the chromatographic information of fluoxastrobin and M48-E;
performing second ultra performance liquid chromatography tandem mass spectrometry on the fluoxastrobin-M48-E-M40 computer sample to obtain M40 chromatographic information;
performing third ultra-high performance liquid chromatography tandem mass spectrometry detection on the o-chlorophenol on-machine sample to obtain o-chlorophenol chromatographic information;
substituting the fluoxastrobin chromatographic information, the chromatographic information of M48-E, the chromatographic information of M40 and the o-chlorophenol chromatographic information into a fluoxastrobin concentration-peak area standard curve, an M48-E concentration-peak area standard curve, an M40 concentration-peak area standard curve and an o-chlorophenol concentration-peak area standard curve to obtain the content of fluoxastrobin and metabolites thereof in the water;
the parameters of the first ultra performance liquid chromatography tandem mass spectrometry detection comprise a first mass spectrometry detection parameter and a first chromatographic detection parameter;
the first mass spectrometry detection parameters comprise: an ion source: ESI + (ii) a Capillary voltage: 5.5kV; ion source temperature: 550 ℃; air curtain air: 35psi; and (3) air blasting: 7psi; auxiliary heating gas: 50psi; spraying mist: 50psi; injection voltage: 10V; collision cell emission voltage: 16V;
the first chromatographic detection parameters include: and (3) chromatographic column: ACQUITY UPLC TM BEH C 18 Column, 1.7 μm,2.1mm × 100mm, waters corporation, USA; temperature of the column: 40 ℃; sample introduction amount: 2.00 mu L; flow rate: 0.3 mL/min -1 (ii) a The mobile phase A is a formic acid-ammonium acetate aqueous solution, the volume concentration of formic acid in the formic acid-ammonium acetate aqueous solution is 0.1%, and the concentration of ammonium acetate is 2mmol/L; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,65% by weight A;0.5 to 2.0min,65% to A to 15% by weight; 2.0-4.0min, 15% by (a) -2% by weight; 4.0-4.5min, 2%; 4.5-4.6 min,2% -65% by weight of A;4.6 to 6.5min,65% by weight;
the parameters of the second ultra performance liquid chromatography tandem mass spectrometry detection comprise a second mass spectrometry detection parameter and a second chromatographic detection parameter;
the second mass spectrometry detection parameters include: an ion source: ESI - (ii) a Capillary voltage: -4.5kV; ion source temperature: 550 ℃; air curtain air: 35psi; and (3) collision gas spraying: 7psi; auxiliary heating gas: 50psi; spraying mist: 50psi; injection voltage: -10V, collision cell ejection voltage: -16V;
the second chromatographic detection parameters include: a chromatographic column: ACQUITY UPLC TM BEH C 18 Column, 1.7 μm,2.1 mm. Times.100 mm, USAWaters corporation; temperature of the column: 40 ℃; sample injection amount: 5.00 mu L; flow rate: 0.3 mL/min -1 (ii) a The mobile phase A is a formic acid-ammonium acetate aqueous solution, the volume concentration of formic acid in the formic acid-ammonium acetate aqueous solution is 0.1%, and the concentration of ammonium acetate is 2mmol/L; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,55% by weight A;0.5 to 3.5min,55% by weight A to 5% by weight A; 3.5-4.0min, 5 percent; 4.0-4.1min, 5% -55% A; 4.1-6.0min, 55% by weight;
the third ultra performance liquid chromatography tandem mass spectrometry detection parameters comprise a third mass spectrometry detection parameter and a third chromatography detection parameter;
the third mass spectrometric detection parameter comprises: an ion source: APCI - (ii) a Needle current: -3.5mA; ion source temperature: 350 ℃; air curtain air: 25psi; and (3) collision gas spraying: 8psi; spraying mist: 50psi; injection voltage: -10V; collision cell emission voltage: -14V;
the third spectral detection parameters include: a chromatographic column:
Omega Polar C 18 column, 3 μm,2.1mm × 50mm, phenomenex, USA; flow rate: 0.40mL/min; column temperature: at 40 ℃; sample introduction volume: 20.0 mu L; the mobile phase A is 2mmol/L ammonium acetate aqueous solution; the mobile phase B is chromatographic pure acetonitrile; gradient elution procedure: 0 to 0.5min,80% by weight of A; 0.5-2.0min, 80% by (a-40); 2.0 to 3.0min,40% to A to 20% of A;3.0 to 3.5min,20% by weight A;3.5 to 3.6min,20% by weight A to 80% by weight A; 3.6-5.5min, 80%.
2. The determination method according to claim 1, wherein in the process of preparing the fluoxastrobin-M48-E-M40 on-machine sample, the volume ratio of the water sample to be determined to the acetonitrile is 1:1.
3. the method according to claim 1, wherein the mixture of the sample of water to be tested and acetonitrile is filtered, and the pore size of the filter membrane is 0.22 μm.
4. The method according to claim 1, wherein the pore size of the filter for filtering the sample to be tested is 0.22 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110732215.2A CN113406239B (en) | 2021-06-30 | 2021-06-30 | Method for measuring fluoxastrobin and metabolite thereof in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110732215.2A CN113406239B (en) | 2021-06-30 | 2021-06-30 | Method for measuring fluoxastrobin and metabolite thereof in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113406239A CN113406239A (en) | 2021-09-17 |
| CN113406239B true CN113406239B (en) | 2023-03-10 |
Family
ID=77680317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110732215.2A Active CN113406239B (en) | 2021-06-30 | 2021-06-30 | Method for measuring fluoxastrobin and metabolite thereof in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113406239B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543163A (en) * | 2016-11-08 | 2017-03-29 | 佛山市飞时达新材料科技有限公司 | A kind of haptenic preparation method and applications of fluoxastrobin |
| CN112051125A (en) * | 2020-09-16 | 2020-12-08 | 浙江省农业科学院 | Pretreatment method for determining multiple pesticide residues in white paeony root |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014525424A (en) * | 2011-09-02 | 2014-09-29 | ビーエーエスエフ ソシエタス・ヨーロピア | Agricultural mixture containing arylquinazolinone compounds |
-
2021
- 2021-06-30 CN CN202110732215.2A patent/CN113406239B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543163A (en) * | 2016-11-08 | 2017-03-29 | 佛山市飞时达新材料科技有限公司 | A kind of haptenic preparation method and applications of fluoxastrobin |
| CN112051125A (en) * | 2020-09-16 | 2020-12-08 | 浙江省农业科学院 | Pretreatment method for determining multiple pesticide residues in white paeony root |
Non-Patent Citations (5)
| Title |
|---|
| Alleviating the Reference Standard Dilemma Using a Systematic Exact Mass Suspect Screening Approach with Liquid Chromatography-High Resolution Mass Spectrometry;Christoph Moschet et al;《Anal. Chem.》;20131231;第85卷;10312-10320 * |
| Behaviour of Fluoxastrobin (HEC 5725) in plants and animals;H. Reiner et al;《Pflanzenschutz-Nachrichten Bayer》;20041231;第57卷(第3期);391-414 * |
| Determination of fifteen priority phenolic compounds in environmental samples from Andalusia (Spain) by liquid chromatography-mass spectrometry;J. L. MartínezVidal et al;《Anal Bioanal Chem》;20041231;第379卷;125-130 * |
| Summary of the ecotoxicological studies for Fluoxastrobin;Bayer;《Bayer CropScience》;20160131;1-70 * |
| 饮用水中3种一氯酚异构体的液相色谱-质谱联用法测定研究;金米聪 等;《中国卫生检验杂志》;20061231;第16卷(第5期);519-521 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113406239A (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Freitas et al. | Quantification of the new triketone herbicides, sulcotrione and mesotrione, and other important herbicides and metabolites, at the ng/l level in surface waters using liquid chromatography–tandem mass spectrometry | |
| Moreno-González et al. | Evaluation of nanoflow liquid chromatography high resolution mass spectrometry for pesticide residue analysis in food | |
| JP2021512292A (en) | Triple quadrupole mass spectrometer configured to detect pesticide residue MRM transitions | |
| CN107037149B (en) | Fipronil and its metabolite residue amount method for measuring in a kind of egg | |
| Niu et al. | Simultaneous quantitative determination of major plant hormones in pear flowers and fruit by UPLC/ESI-MS/MS | |
| Wang et al. | Solid phase microextraction combined with thermal-desorption electrospray ionization mass spectrometry for high-throughput pharmacokinetics assays | |
| CN103728407B (en) | A kind of assay method of Pyrifluquinazon residual quantity | |
| CN110146616A (en) | The remaining detection method of pesticide in a kind of rice, rice stem | |
| Zhang et al. | Disposable pipette extraction (DPX) coupled with liquid chromatography–tandem mass spectrometry for the simultaneous determination of pesticide residues in wine samples | |
| Liu et al. | Simultaneous determination of 19 plant growth regulator residues in plant-originated foods by QuEChERS and stable isotope dilution-ultra performance liquid chromatography-mass spectrometry | |
| CN105548431A (en) | Method for simultaneously detecting residual quantities of oxamyl and oxamyl oxime in vegetable/fruits | |
| CN112858542B (en) | Liquid chromatography mass spectrometry method for measuring atrazine, imidacloprid and metabolites thereof in leaves | |
| CN109239226B (en) | A method of it improves while 10 kinds of gibberellin of detection detects stability | |
| CN108445128B (en) | Method for measuring residual amount of carbamate drugs in eggs | |
| CN113406239B (en) | Method for measuring fluoxastrobin and metabolite thereof in water | |
| CN105486775A (en) | Method for detecting content of various components in pills for treating kidney-yang deficiency | |
| CN103412077A (en) | Method for measuring indazole flusulfamide residue amount | |
| Chen et al. | Determination of yohimbine in yohimbe bark and related dietary supplements using UHPLC-UV/MS: Single-laboratory validation | |
| Abdelwahed et al. | Polar reversed-phase liquid chromatography coupled with triple quadrupole mass spectrometer method for simple and rapid determination of maleic hydrazide residues in some fruits and vegetables | |
| Zhang et al. | Determination of chlormequat and mepiquat residues and their dissipation rates in tomato cultivation matrices by ultra-performance liquid chromatography-tandem mass spectrometry | |
| Vázquez et al. | Application of coupled-column liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection to the determination of pyrethroid insecticides in vegetable samples | |
| CN112444591B (en) | Liquid chromatography tandem mass spectrometry for determining residual quantity of flumetsulam in vegetable food | |
| CN103776934A (en) | Determination method for residual amount of metrafenone | |
| Zhao et al. | Determination of monosulfuron-ester residues in grains, straw, green plants and soil of wheat by modified QuEChERS and LC-MS/MS | |
| CN110726787B (en) | LC-MS/MS negative ion mode detection method for analyzing seven mogrosides |
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 |