CN108593830B - HPLC-MS/MS detection method for fluopicolide and metabolite thereof - Google Patents
HPLC-MS/MS detection method for fluopicolide and metabolite thereof Download PDFInfo
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Abstract
The invention discloses an HPLC-MS/MS detection method for fluopicolide and metabolites thereof. The method comprises pulverizing solid sample (onion, soil, etc.), adding acetonitrile containing 0.2% formic acid, homogenizing with high-speed homogenizer, ultrasonic extracting at 20-30 deg.C, and centrifuging; taking out the supernatant, adding an equal volume of 50% methanol aqueous solution, and filtering with a filter membrane to obtain a solution to be detected; and (3) qualitatively and/or quantitatively analyzing fluopicolide and metabolites M-01 and M-02 thereof by adopting a high performance liquid chromatography-triple quadrupole tandem mass spectrometer. The method is simple and convenient, is easy to operate, can meet the requirements of rapid detection and confirmation of residual amounts of fluopicolide and metabolites M-01 and M-02 thereof in the onions and the soil, and can provide theoretical basis for safe and scientific use of the fluopicolide on the onions and establishment of the maximum residual limit of the fluopicolide in the onions in China.
Description
Technical Field
The invention relates to a detection method, and particularly relates to an HPLC-MS/MS detection method for fluopicolide and metabolites thereof.
Background
Fluopyram (fluopicolide), chemical name 2, 6-dichloro-N- [ (3-chloro-5-trifluoromethyl-2-pyridyl) methyl ] benzamide, structural formula is shown as follows. Fluopyram is a novel benzamide bactericide which is developed by Bayer crop science companies and has a unique action mechanism, is a fluorine-containing bactericide with a brand-new action mechanism, has the characteristics of small relative dosage of a plurality of fluorine-containing pesticides in performance, low toxicity, high drug effect, strong metabolic capacity and the like, has very high biological activity on oomycetes, and is mainly used for preventing and treating common oomycete diseases on vegetables and grapes.
The current research on the toxicology of fluopicolide mainly focuses on fluopicolide parent (fluopicolide) and 2 major metabolites, namely M-01(2,6-dichlorobenzamide) and M-02(3-chloro-5- (trifluoromethyl) pyridine-2-carboxylic acid), wherein the structural formulas of M1 and M2 are shown as follows. The acute oral toxicity LD50 of M1 to rats is 2000mg/kg in male mice, 500mg/kg in female mice, and the acute oral toxicity LD50 of M2 to rats is more than 2000mg/kg, which are both more than 5000mg/kg.bw of the acute oral toxicity LD50 of fluopicolide parent to rats. Therefore, when detecting the residual fluopicolide, M1 and M2 should be detected simultaneously.
The residual detection of fluopicolide is reported at present, most of the fluopicolide is directed at fluopicolide precursors, and as long as the detection of the fluopicolide precursors and M1 is carried out at the same time, no report related to the detection of M2 is found. The maximum residual limit value of the fluopicolide on the onions is set by CAC to be 1mg/kg, and the maximum residual limit value of the fluopicolide on the onions is not set in China. Therefore, the simultaneous detection of the residual quantity of fluopicolide and metabolites M-01 and M-02 thereof is a problem to be solved at present.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides an HPLC-MS/MS detection method for fluopicolide and metabolites thereof in onions. The method establishes an analysis method for rapidly detecting residues of fluopicolide and metabolites M-01 and M-02 thereof in the onion by combining an improved QuEChER method with an HPLC-MS/MS technology. The method is simple, convenient and easy to operate, can meet the requirements of rapid detection and confirmation of residual amounts of fluopicolide and metabolites M-01 and M-02 thereof in onions and soil, and researches the residual and digestion characteristics of fluopicolide and metabolites thereof in onions and soil by adopting the method so as to provide theoretical basis for safe and scientific use of fluopicolide on onions and establishment of the maximum residual limit of fluopicolide in onions in China.
The technical scheme of the invention is as follows: an HPLC-MS/MS detection method for fluopicolide and metabolites thereof, which is characterized in that,
1) pretreatment
Crushing a solid sample, adding acetonitrile containing 0.2% (v/v) formic acid, uniformly mixing, homogenizing by a high-speed homogenizer, ultrasonically extracting, and centrifuging; taking out the supernatant, adding methanol aqueous solution with the equal volume concentration of 50% (v/v), and filtering with a filter membrane to obtain a solution to be detected;
the method specifically comprises the following steps: crushing 10g of solid sample, adding acetonitrile containing 0.2% (v/v) formic acid, uniformly mixing, homogenizing by a high-speed homogenizer (the rotating speed is more than or equal to 1000 revolutions/minute), ultrasonically extracting at normal temperature for 20min, centrifuging at 10000r/min for 10min, and taking out 1mL of supernatant; adding 1mL of 50% (v/v) methanol aqueous solution with concentration into the supernatant, and passing through a 0.22-micron organic membrane to obtain a solution to be detected;
the solid sample is preferably onion and soil.
2) Detection of
And (3) qualitatively and/or quantitatively analyzing fluopicolide and metabolites M-01 and M-02 thereof by adopting a high performance liquid chromatography-triple quadrupole tandem mass spectrometer.
The high performance liquid chromatography conditions of the step 2) are as follows: agilent ZORBAX Eclipse Plus C18; column temperature: 35 ℃; sample introduction amount: 3 mu L of the solution; the gradient elution conditions are shown in tables 1-2.
TABLE 1 Fluopyram, M-01 mobile phase gradient elution parameters
TABLE 2M-02 mobile phase gradient elution parameters
The mass spectrum conditions are as follows: an ion source: electrospray ion source ESI; capillary voltage: 4.0 KV; taper hole voltage: 35V; the monitoring mode is as follows: multiple Reaction Monitoring (MRM); flow rate of drying gas: 8.0L/min; the scanning mode is as follows: fluopicolide and M-01 are positive ion sources, and the temperature of the ion sources is 350 ℃; m-02 is a negative ion source, and the temperature of the ion source is 280 ℃;
the retention time and the qualitative ion pair are used for qualitative analysis, the quantitative ion pair is used for quantitative analysis, and the retention time, the qualitative ion pair, the quantitative ion and the declustering voltage/collision voltage of fluopicolide and metabolites (M-01 and M-02) are shown in a table 3.
TABLE 3 analysis parameters of Fluopyram and M-01, M-02 in tandem mass spectrometry multiple reaction monitoring mode
Furthermore, the mass concentration of the standard solution and the matrix of fluopicolide and M-01 and M-02 matched with the standard solution and the peak area of the monitored ion are taken as a standard curve, the linear equation shown in the table 4 is adopted to quantify the fluopicolide, the M-01 and the M-02 in the onion, and the standard curve shown in the table 5 is adopted to quantify the fluopicolide, the M-01 and the M-02 in the soil.
The invention has the beneficial effects that:
1) the invention simultaneously detects fluopicolide and metabolites M-01 and M-02 thereof for the first time
The invention establishes an analysis method for rapidly detecting fluopicolide and metabolite M-01 and M-02 residues thereof in onion and soil by combining an improved QuEChERS with an HPLC-MS/MS technology. The method is simple, convenient and easy to operate, can meet the requirements of rapid detection and confirmation of residual amounts of fluopicolide and metabolites M-01 and M-02 thereof in the onions, can be used for researching the residual and digestion characteristics of fluopicolide and metabolites thereof in the onions and soil, and is expected to provide theoretical basis for safe and scientific use of the fluopicolide on the onions and establishment of the maximum residual limit of the fluopicolide in the onions in China.
2) Rapid analysis, high sensitivity
The method adopts 1290-G6460C high performance liquid chromatography-tandem electrospray triple quadrupole mass spectrometer and AgilentZORBAX Eclipse Plus C18 chromatographic column, optimizes the detection parameters (such as mobile phase, qualitative ion pair and quantitative ion pair) of the high performance liquid chromatography-mass spectrometer, improves the separation efficiency, shortens the sample analysis period (the retention time of a target peak is 0.69-3.49min), and is suitable for the rapid analysis of the residues of fluopicolide and metabolites M-01 and M-02 thereof in onion or soil. The adding recovery rate of the method is not lower than 82%, the linear range is 0.005-1 mg/L, and the limit of quantitation (LOQ) is 0.01 mg/kg; the method is simple, high in sensitivity and good in selectivity.
Drawings
FIG. 1 is a total ion flow diagram for fluopicolide and M-01 assays;
FIG. 2 is a fluopicolide qualitative ion diagram (peak-off time: 3.49 min);
FIG. 3 is a fluopicolide quantitative ion diagram;
FIG. 4 is a qualitative ion diagram of M-01 (peak-out time: 0.69 min);
FIG. 5 is a quantitative ion diagram of M-01;
FIG. 6 is a total ion flow diagram for M-02 detection;
FIG. 7 is a qualitative ion diagram of M-02 (peak-off time: 3.45 min);
FIG. 8 is a quantitative ion diagram of M-02.
Detailed Description
1 materials and methods
1.1 test materials
99.2% Fluopyram (fluoropolylide), 96.2% M-01(2, 6-dicholobenzamide) and 98.5% M-02(3-chloro-5- (trifluoromethyl) pyridine-2-carboxylic acid) available from Bayer crop science (China) Co., Ltd.; acetonitrile: chromatographically pure, fish; methanol: superior pure, fish; formic acid: chromatographically pure, CNW; ultrapure water: child haha; QuEChERS material: agilent.
1.2 Main instruments
1290-G6460C high Performance liquid chromatography-tandem electrospray triple quadrupole Mass spectrometer (Agilent, USA); G6460C mass spectrometry system (Agilent, USA); an ultrasonic extractor (ultrasonic instruments ltd, kunshan); high speed homogenizers (IKA WORK INC T25Basic, Germany); rotary evaporator (Heidolph LABOROTA 4001, germany); high speed centrifuges (heel Force, hong Kong); laboratory glassware is commonly used.
1.3 conditions of instrumental detection
1.3.1 Fluopyram, metabolite M-01
A chromatographic column: agilent ZORBAX Eclipse Plus C18(50 mm. times.2.1 mm, 1.8 μm); column temperature: 35 ℃; sample introduction amount: 3 mu L of the solution; an ion source: electrospray ion source ESI; the scanning mode is as follows: a source of positive ions; capillary voltage: 4.0 KV; taper hole voltage: 35V; ion source temperature: at 350 ℃. The detection mode is as follows: multiple Reaction Monitoring (MRM); flow rate of drying gas: 8.0L/min. The gradient elution conditions are shown in table 1, above.
The information was qualitatively analyzed by comparing retention time and ion pair, quantitatively analyzed by parent ion and daughter ion with the highest response value, and the retention time, monitored ion, cleavage voltage and collision energy of fluopicolide and metabolite M-01 are shown in Table 3 as described above.
1.3.2 metabolite M-02
A chromatographic column: agilent ZORBAX Eclipse Plus C18(50 mm. times.2.1 mm, 1.8 μm); column temperature: 35 ℃; sample introduction amount: 3 mu L of the solution; an ion source: electrospray ion source ESI; the scanning mode is as follows: a negative ion source; capillary voltage: 4.0 KV; taper hole voltage: 35V; ion source temperature: 280 ℃. The detection mode is as follows: multiple Reaction Monitoring (MRM); flow rate of drying gas: 8.0L/min. The gradient elution conditions are shown in table 2, above.
The information was qualitatively analyzed by comparing retention time with ion pair, quantitatively analyzed by parent ion and daughter ion with the highest response value, and retention time, monitor ion, cleavage voltage and collision energy of fluopicolide and metabolites (M-01, M-02) were shown in Table 3 as described above.
1.4 preparation of Standard solution and drawing of Standard Curve
Accurately weighing 0.001g (accurate to 0.0001 g) of fluopicolide and M-01 standard substance in a 10mL volumetric flask, and diluting with methanol and blank reference solution of matrix (onion and soil) to obtain 0.005, 0.01, 0.05, 0.1 and 0.5 mu g/mL series of standard solutions; accurately weighing 0.0025g (accurate to 0.0001 g) M-02 standard substance into a 10mL volumetric flask, and diluting with methanol and blank control solution of matrix (onion and soil) respectively to obtain 0.01, 0.05, 0.1, 0.5 and 1 mu g/mL series of standard solutions. And (3) measuring according to the condition of 1.3, and making a standard curve by matching the mass concentration of the standard solution and the matrix of fluopicolide and M-01 and M-02 with the mass concentration of the standard solution and the peak area of the monitored ion.
1.5 sample pretreatment method
1.51 onion
Weighing 10g of onion sample, crushing, adding 20mL of 0.2% formic acid acetonitrile (volume ratio) by a QuEChERS method, uniformly mixing, homogenizing by a high-speed homogenizer, ultrasonically extracting at normal temperature for 20min, centrifuging at 10000r/min for 10min, and taking out 1mL of supernatant. 1mL of aqueous methanol (1+1, V/V) was added to the supernatant, and the mixture was passed through a 0.22 μm organic membrane.
1.52 soil
Weighing 10g of soil sample, crushing, adding 20mL of 0.2% formic acid acetonitrile (volume ratio) by a QuEChERS method, uniformly mixing, homogenizing by a high-speed homogenizer, ultrasonically extracting at normal temperature for 20min, centrifuging at 10000r/min for 10min, and taking out 1mL of supernatant. 1mL of aqueous methanol (1+1, V/V) was added to the supernatant, and the mixture was passed through a 0.22 μm organic membrane.
2 results and analysis
2.1 determination of pretreatment method
Fluopyram is an amide compound, and in most established LC-MS/MS detection methods, acetonitrile is commonly used for extracting the amide compound from vegetables and fruits. Therefore, the present study also extracted fluopicolide and its metabolites from onions and soil using acetonitrile as solvent, comparing acetonitrile and its mixture with water, formic acid (0.1%), formic acid (0.2%) as extractant. The addition of formic acid to acetonitrile results in a better peak profile of the chromatographic peak. The recovery rate when 0.2% by volume formic acid was added as extractant was higher than that when 0.1% by volume formic acid was added, and 0.2% formic acid acetonitrile (by volume) was finally selected as extractant.
2.2 Linear Range and detection limits of the method
In the range of 0.005-0.5 mg/L, a good linear relationship is formed between the peak areas of fluopicolide and M-01 and the mass concentration of the fluopicolide, and the linear equation, the correlation coefficient and the lowest detection limit of the fluopicolide, the M-01 and the M-02 in the onion are shown in tables 4-5. The peak area of M-02 in the range of 0.01-1 mg/L and the mass concentration thereof have a good linear relationship, and the linear equation, the correlation coefficient and the lowest detection limit of M-02 in soil are shown in the table 4-5. The quantitative Limits (LOQ) of fluopicolide, M-01 and M-02 in onion and soil are all 0.01mg/kg, and the MRM total ion flow diagram, the qualitative ion diagram and the quantitative ion diagram of the standard solution are respectively shown in figures 1-8.
TABLE 4 Linear equation, correlation coefficient and minimum detection limit of Fluopyram and M-01, M-02 in onion
TABLE 5 Linear equation, correlation coefficient and minimum detection limit of Fluopyram and M-01, M-02 in soil
2.2.2 accuracy and precision
Standard solutions (n ═ 3) of 0.01 μ g/mL, 0.1 μ g/mL and 1 μ g/mL were added to the blank onion and the soil sample, respectively, and the recovery rate and precision of the experimental method were examined. The specific results are shown in Table 6.
TABLE 6 addition recovery of Fluopyram, M-01 and M-02 to onion
As can be seen from Table 6, under the three addition levels of 0.01, 0.1 and 1mg/kg, the average addition recovery rate of fluopicolide and metabolites M-01 and M-02 thereof in onions and soil is 82-108%, the variation coefficient RSD is 1.3-5.4%, the requirement of pesticide residue analysis is met, and the method can be applied to actual residues.
2.3 detection of actual samples
The invention is tested in 2016-2017 in onion growing area of Shandong Jinnan and Jiangsu Yizheng, the growing area adopts Yinfuli (compound liquid preparation of fluopicolide and propamocarb) produced by Germany Bayer crop science to prevent and treat the downy mildew of onion, and the application method comprises the following steps: in the early stage of disease occurrence, spraying 60-100 ml of 68.75% silver method suspending agent with water for each mu, applying the pesticide for 3-4 times, and harvesting in 14 days; detecting fluopicolide and metabolites M-01 and M-02 in the onions and the soil at intervals of 7 days, 14 days and 21 days, repeating the detection for 3 times, and calculating an average value; the time, place and dose of administration are shown in tables 7-8.
2.31 sample pretreatment method
Onion: weighing 10g of onion sample, crushing, adding 20mL of 0.2% formic acid acetonitrile (volume ratio) by a QuEChERS method, uniformly mixing, homogenizing by a high-speed homogenizer, ultrasonically extracting at normal temperature for 20min, centrifuging at 10000r/min for 10min, and taking out 1mL of supernatant. The supernatant was added with 1mL of aqueous methanol (1+1, V/V) and passed through a 0.22 μm organic membrane to be assayed.
Soil: weighing 10g of soil sample, crushing, adding 20mL of 0.2% formic acid acetonitrile (volume ratio) by a QuEChERS method, uniformly mixing, homogenizing by a high-speed homogenizer, ultrasonically extracting at normal temperature for 20min, centrifuging at 10000r/min for 10min, and taking out 1mL of supernatant. The supernatant was added with 1mL of aqueous methanol (1+1, V/V) and passed through a 0.22 μm organic membrane to be assayed.
2.32 detection
And (3) quantifying fluopicolide and metabolites M-01 and M-02 in soil and onions by adopting 1290-G6460C high performance liquid chromatography-tandem electrospray triple quadrupole mass spectrometer (instrument detection conditions are shown as 1.3) and adopting a standard curve matched with matrixes shown in tables 4-5.
2.33 results of detection
The final residual amounts of fluopicolide, M-01, M-02 in onions and soil are shown in tables 7-8. From the test results, it can be seen that: the detection results do not exceed the specification that the maximum residual limit value of fluopicolide on the onions formulated by CAC is 1mg/kg, and the detection results meet the requirements. Meanwhile, as seen from comparison of data in tables 7 and 8, the content of fluopicolide in the onion is low, and therefore, the food safety of the onion is not affected. The content of fluopicolide in the soil is obviously higher than that of onion, which indicates that the metabolism speed in the soil is slow, so that attention should be paid.
TABLE 7 Final residual amount of Fluopyram in onions
TABLE 8 Final residual amount of fluopicolide in soil
Claims (4)
1. An HPLC-MS/MS detection method for fluopicolide and metabolites thereof, which is characterized in that,
1) pretreatment
Pulverizing onion or soil sample, adding acetonitrile containing 0.2% formic acid, mixing, homogenizing with high speed homogenizer, ultrasonic extracting, and centrifuging; taking out the supernatant, adding an equal volume of 50% methanol aqueous solution, and filtering with a filter membrane to obtain a solution to be detected;
2) detection of
Qualitative and/or quantitative analysis is carried out on fluopicolide and metabolites M-01 and M-02 thereof by adopting a high performance liquid chromatography-triple quadrupole tandem mass spectrometer;
said M-01 is
M-02 is
The high performance liquid chromatography conditions were as follows: agilent ZORBAX Eclipse Plus C18; column temperature: 35 ℃; sample introduction amount: 3 mu L of the solution;
fluopicolide and M-01 mobile phase gradient elution parameters are as follows:
the M-02 mobile phase gradient elution parameters were as follows:
the mass spectrum conditions are as follows: an ion source: electrospray ion source ESI; capillary voltage: 4.0 KV; taper hole voltage: 35V; the monitoring mode is as follows: monitoring multiple reactions; flow rate of drying gas: 8.0L/min; the scanning mode is as follows: fluopicolide and M-01 are positive ion sources, and the temperature of the ion sources is 350 ℃; m-02 is a negative ion source, and the temperature of the ion source is 280 ℃;
the analysis parameters of fluopicolide, M-01 and M-02 in the tandem mass spectrum multi-reaction monitoring mode are as follows:
2. the HPLC-MS/MS detection method for fluopicolide and its metabolites as claimed in claim 1, wherein linear equation is used to quantify fluopicolide, M-01, M-02 in onion; the linear equation is as follows:
3. the HPLC-MS/MS detection method for fluopicolide and its metabolites as claimed in claim 1, wherein linear equation is used to quantify fluopicolide, M-01, M-02 in soil; the linear equation is as follows:
4. the HPLC-MS/MS detection method for fluopicolide and metabolites thereof according to claim 1, wherein the step 1) is specifically as follows: pulverizing 10g onion or soil sample, adding acetonitrile containing 0.2% formic acid, mixing, homogenizing with high speed homogenizer, ultrasonic extracting at room temperature for 20min, centrifuging at 10000r/min for 10min, and taking out 1mL supernatant; adding 1mL of 50% methanol aqueous solution into the supernatant, and passing through a 0.22 μm organic membrane to obtain a solution to be detected.
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| CN105158382A (en) * | 2015-06-04 | 2015-12-16 | 上海市农业技术推广服务中心 | Method for detecting fluopicolide in fruits and vegetables |
| CN107814759A (en) * | 2017-11-24 | 2018-03-20 | 常州沃腾化工科技有限公司 | The preparation method of fluopicolide |
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| CN107814759A (en) * | 2017-11-24 | 2018-03-20 | 常州沃腾化工科技有限公司 | The preparation method of fluopicolide |
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