CN111830185A - Ultra-high performance liquid chromatography tandem mass spectrometry detection method of quinclorac - Google Patents
Ultra-high performance liquid chromatography tandem mass spectrometry detection method of quinclorac Download PDFInfo
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- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
Abstract
The invention discloses an ultra-high performance liquid chromatography tandem mass spectrometry detection method for residual amount of quinclorac in tobacco, which comprises the following steps: 1) preparing standard working solution and matrix standard solution; 2) preparing a sample working solution: 3) detecting and analyzing by ultra-high performance liquid chromatography tandem mass spectrometry; 4) and (5) detecting condition formation. The method combines the QuEChERS method with the ultra-high performance liquid chromatography-tandem mass spectrometry, and can efficiently and accurately detect quinclorac in tobacco, so that the component detection and analysis are quicker, the time is saved, the detection sensitivity is high, the detection data is accurate, the cost is saved, and the detection efficiency is improved.
Description
Technical Field
The invention belongs to the field of analysis and detection, and particularly relates to a high performance liquid chromatography tandem mass spectrometry detection method for quinclorac.
Background
Quinclorac is a systemic herbicide with strong selectivity popularized by German Passion company in 1984, and is mainly used for preventing and controlling monocotyledonous weeds such as barnyard grass, crabgrass and the like in rice fields and part of broadleaf weeds. Has the characteristics of low dosage, long pesticide effect duration, long use interval and the like, and is widely applied to paddy fields. The growth and metabolism of weeds are inhibited mainly by interfering the activity of hormone regulatory enzymes in plants, so that leaves are yellowed, become small and shrink, and symptoms firstly appear on young leaves and then the whole plant withers and necroses.
Tobacco is a crop which is sensitive to quinclorac, the quinclorac is a pesticide with strong stability and long residual effect period, and due to the wide application of the quinclorac to various crops, the tobacco is frequently damaged by the quinclorac. The report shows that the abnormal growth of tobacco leaves in parts of Guangdong province is caused by quinclorac used in the previous rice planting process, and researches show that tobacco is extremely sensitive to quinclorac and is easy to cause the abnormal growth of tobacco plants. According to statistics, the annual rate of Jiangxi province is about 66.7hm2The tobacco field can be damaged by the phytotoxicity of different degreesThe miserability is serious.
At present, the pre-treatment of the residue detection of quinclorac in tobacco is complex, and the analysis method mainly comprises a gas chromatography, a liquid chromatography, a capillary electrophoresis method and the like. Wangyihru et al adopt boric acid buffer solution for extraction, and high performance liquid chromatography and gas chromatography are carried out after column enrichment, elution and derivatization, and the process is complicated; zhengxiong et al extract with sodium hydroxide solution to determine the residual amount of quinclorac in tobacco and tobacco planting soil, but have the disadvantages of complicated pretreatment, time consumption, large organic reagent dosage and the like; yan Chetai et al extract with borax buffer solution and methanol at a ratio of 1:2(v/v), adjust to acidity with concentrated sulfuric acid, extract with dichloromethane, concentrate and exchange phase, and analyze with high performance liquid chromatography. In particular, in the case of tobacco, the tobacco matrix is complicated, the amount of pigments is large, the requirement for the pretreatment method is high as compared with soil and rice matrix, and the method for detecting the residual quinclorac in tobacco is difficult. The liquid chromatogram tandem mass spectrometry has the advantages of high sensitivity, simple and convenient operation, good reproducibility and the like, and is widely applied to the detection of pesticide residues.
Disclosure of Invention
The invention aims to provide a method for detecting quinclorac in tobacco by using an ultra-high performance liquid chromatography tandem mass spectrometry, aiming at the current situation that the quinclorac is unreasonably used and a small amount of residues cause crop phytotoxicity but the analysis method is absent, and the method has the characteristics of high sensitivity, good reproducibility, small organic solvent consumption and the like and can meet the analysis requirement of the quinclorac residues.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ultra-high performance liquid chromatography tandem mass spectrometry method for detecting residual amount of quinclorac in tobacco comprises the following steps:
(1) preparing a tobacco substrate mixed standard working solution of quinclorac:
weighing 3.00g of blank tobacco sample which is determined not to contain quinclorac, adding 20mL of ultrapure water and 30mL of extracting solution (V formic acid: V acetonitrile is 0.5: 99.5), 5g of sodium chloride, performing vortex extraction for 5min, centrifuging for 3min at 4000rmp, and taking supernatant;
putting 1.5mL of the supernatant into a centrifuge tube which is added with 100mg of C18 in advance, uniformly mixing for 5min in a vortex manner, centrifuging for 3min at 11000rmp, transferring the supernatant after centrifugation, and filtering the supernatant through a 0.22 mu m filter membrane to obtain a blank matrix extraction purified solution; preparing a tobacco matrix standard working solution of quinclorac by taking the blank matrix extraction purification solution as a solvent;
(2) determining the peak area of extracted ions of pesticide components in a matrix standard working solution of quinclorac by using an ultra-high performance liquid chromatography tandem mass spectrometry, and drawing a standard working curve of the quinclorac by taking the concentration as a horizontal coordinate and the peak area of the extracted ions as a vertical coordinate;
wherein the determination conditions are as follows: ionization source mode: ESI; ionization source polarity: positive; atomizing: nitrogen gas; sheath gas pressure: 276 kPa; ion transfer tube temperature: 320 ℃; temperature of the spray needle: 300 ℃; ion spray voltage: 3500V; column Hypersil GOLD C18(2.1 mm. times.100 mm1.9 μm), column temperature: 35 ℃; flow rate: 0.3 mL/min; sample introduction amount: 5 mu L of the solution; other specific mass spectrometry conditions are shown in table 1. The mobile phase B was methanol solution, the mobile phase C was 0.1% formic acid in water (v/v), and the gradient elution conditions are shown in Table 2 (the ratio of the two solvents in mobile phase B, C in Table 2 is volume ratio).
TABLE 1 Mass Spectrometry conditions for Quinclorac
TABLE 2 gradient elution conditions
(3) The method for detecting the residual amount of quinclorac in the tobacco sample comprises the following steps: extracting a tobacco sample; weighing 3.00g of tobacco sample, adding 20mL of ultrapure water, 30mL of extracting solution (V formic acid: V acetonitrile: 0.5: 99.5), continuously adding 5g of sodium chloride, performing vortex extraction for 5min, centrifuging for 3min at 4000rmp, and taking supernatant;
purifying the tobacco sample extracting solution to be purified; putting 1.5mL of the supernatant into a centrifuge tube which is added with 100mg of C18 in advance, uniformly mixing for 5min in a vortex manner, centrifuging for 3min at 11000rmp, transferring the supernatant after centrifugation, and filtering the supernatant through a 0.22-micron filter membrane to obtain a tobacco sample extraction purification solution for measuring the residual dichloroquinacrinic acid;
(4) determining the residual amount of quinclorac in the tobacco sample extraction purification solution by using an ultra-high performance liquid chromatography-tandem mass spectrometry method, recording the peak area of a chromatogram, and quantifying by using a matrix external standard method to obtain the determined value of quinclorac in the tobacco sample extraction purification solution; then bringing the measured value into a quantitative calculation formula to finally obtain the residual amount of quinclorac to be measured in the tobacco sample;
quantitative calculation formula: r ═ C × V1 × V3)/m × V2, where: r is the residual quantity (mg/kg) of the pesticide in the sample; c, obtaining sample injection concentration (mg/L) through standard curve or single-point quantitative calculation according to the peak area of the sample; m is a weighed amount (g); v1 is extract volume (mL); v2 is the volume of the aliquot (mL); v3 constant volume (mL);
wherein the chromatographic conditions of the quinclorac in the tobacco sample extraction purification solution are the same as the chromatographic conditions of the quinclorac in the step (2).
Compared with the prior art, the invention has the beneficial effects that:
(1) the pretreatment method has the advantages of simple operation steps, strong qualitative and quantitative capability, high extraction rate of target pesticides, small using amount of extraction solvent and qualified addition recovery rate;
(2) the ultra-high performance liquid chromatography tandem mass spectrometry used in the invention has high accuracy and sensitivity; the sample detection time is short, and the detection efficiency is high.
Drawings
FIG. 1 is a chromatogram of 0.1mg/L quinclorac in a matrix solution.
FIG. 2 is a chromatogram of quinclorac in a tobacco sample.
Detailed Description
The following examples further describe embodiments of the present invention in detail. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the examples, quinclorac (purity 99.8%) was purchased from Tanzhi ink quality testing, science and technology, Inc.; octadecyl bonded silica gel (C18) adsorbent was purchased from Shanghai' an spectral laboratory science and technology, Inc.
An embodiment of an ultra-high performance liquid chromatography tandem mass spectrometry method for detecting residual amount of quinclorac in tobacco comprises the following steps:
the method for analyzing quinclorac in tobacco by collecting tobacco samples comprises the following steps:
(1) preparing a tobacco substrate mixed standard working solution of quinclorac:
weighing 3.00g of blank tobacco sample which is determined not to contain quinclorac, adding 20mL of ultrapure water and 30mL of extracting solution (V formic acid: V acetonitrile is 0.5: 99.5), mixing uniformly, adding 5g of sodium chloride, performing vortex extraction for 5min, centrifuging for 5min at 4000rmp, and taking supernatant;
and (3) putting 1.5mL of the supernatant into a centrifuge tube which is added with 100mg of C18 in advance, uniformly mixing the supernatant in a vortex manner for 5min, centrifuging the mixture at 11000rmp for 3min, transferring the supernatant after centrifugation, and filtering the supernatant through a 0.22-micron filter membrane to obtain the tobacco sample extraction purification solution for measuring the residual dichloroquinacrine. Preparing a tobacco matrix standard working solution of quinclorac by taking the tobacco blank matrix extraction purification solution as a solvent;
in the tobacco substrate mixed standard working solution in the step (1), the concentration range of quinclorac is 1-1000 mug/L;
(2) determining the peak area of extracted ions of pesticide components in a matrix standard working solution of quinclorac by using an ultra-high performance liquid chromatography tandem mass spectrometry, and drawing a standard working curve of the quinclorac by taking the concentration as a horizontal coordinate and the peak area of the extracted ions as a vertical coordinate;
wherein the determination conditions are as follows: ionization source mode: ESI; ionization source polarity: positive; atomizing: nitrogen gas; sheath gas pressure: 276 kPa; ion transfer tube temperature: 320 ℃; temperature of the spray needle: 300 ℃; ion spray voltage: 3500V; column Hypersil GOLD C18(2.1 mm. times.100 mm1.9 μm), column temperature: 35 ℃; flow rate: 0.3 mL/min; sample introduction amount: 5 mu L of the solution; other specific mass spectrometry conditions are shown in table 1. The mobile phase B was methanol solution, the mobile phase C was 0.1% formic acid in water (v/v), and the gradient elution conditions are shown in Table 2 (the ratio of the two solvents in mobile phase B, C in Table 2 is volume ratio).
The tobacco matrix standard solution chromatogram mass spectrum of quinclorac is shown in figure 1.
(3) The method for detecting the residual amount of quinclorac in the tobacco sample comprises the following steps:
extracting a tobacco sample; weighing 3.00g of tobacco sample, adding 20mL of ultrapure water, 30mL of extracting solution (V formic acid: V acetonitrile: 0.5: 99.5), continuously adding 5g of sodium chloride, performing vortex extraction for 5min, centrifuging for 3min at 4000rmp, and taking supernatant;
purifying the tobacco sample extracting solution to be purified; putting 1.5mL of the supernatant into a centrifuge tube which is added with 100mg of C18 in advance, uniformly mixing for 5min in a vortex manner, centrifuging for 3min at 11000rmp, transferring the supernatant after centrifugation, and filtering the supernatant through a 0.22-micron filter membrane to obtain a tobacco sample extraction purification solution for measuring the residual dichloroquinacrinic acid;
(4) determining the residual amount of quinclorac in the tobacco sample extraction purification solution by using an ultra-high performance liquid chromatography-tandem mass spectrometry method, recording the peak area of a chromatogram, and quantifying by using a matrix external standard method to obtain the determined value of quinclorac in the tobacco sample extraction purification solution; then bringing the measured value into a quantitative calculation formula to finally obtain the residual amount of quinclorac to be measured in the tobacco sample;
quantitative calculation formula: r ═ C × V1 × V3)/m × V2, where: r is the residual quantity (mg/kg) of the pesticide in the sample; c, obtaining sample injection concentration (mg/L) through standard curve or single-point quantitative calculation according to the peak area of the sample; m is a weighed amount (g); v1 is extract volume (mL); v2 is the volume of the aliquot (mL); v3 constant volume (mL);
wherein the chromatographic conditions of the quinclorac in the tobacco sample extraction purification solution are the same as the chromatographic conditions of the quinclorac in the step (2).
The chromatogram mass spectrum of quinclorac in the tobacco sample is shown in figure 2.
(5) According to the measured value of quinclorac, the concentration of quinclorac in the tobacco sample is determined to be 0.64mg/kg according to a quantitative formula.
The substrate standard working curve and quantitative range of quinclorac, the limit of detection (LOQ) of the method are shown in Table 3.
Table 3: relevant parameters such as substrate standard working curve of quinclorac
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (3)
1. An ultra-high performance liquid chromatography tandem mass spectrometry method for detecting the residual amount of quinclorac in tobacco is characterized in that: the method comprises the following steps:
(1) preparation of standard working solution:
accurately weighing quinclorac standard substance, ultrasonically dissolving the quinclorac standard substance by using methanol, and fixing the volume to 50mL to obtain 1000mg/L mother liquor, and preparing series of standard solutions with different concentrations by using methanol;
weighing 3.00g of blank tobacco sample which is determined not to contain quinclorac, adding 20mL of ultrapure water and 30mL of extracting solution (V formic acid: V acetonitrile is 0.5: 99.5), mixing uniformly, adding 5g of sodium chloride, performing vortex extraction for 5min, centrifuging for 5min at 4000rmp, and taking supernatant;
taking 1.5mL of the supernatant, putting the supernatant into a centrifuge tube which is added with 100mg of octadecyl bonded silica gel (C18) in advance, mixing the supernatant evenly, centrifuging the mixture for 3min at 11000rmp, and transferring the supernatant into a test tube after centrifugation. Filtering with 0.22 μm filter membrane to obtain blank matrix extraction purified solution; preparing a tobacco matrix standard working solution of quinclorac by taking the blank matrix extraction purification solution as a solvent;
(2) determining the peak area of extracted ions of pesticide components in a matrix standard working solution of quinclorac by using an ultra-high performance liquid chromatography tandem mass spectrometry, and drawing a standard working curve of the quinclorac by taking the concentration as a horizontal coordinate and the peak area of the extracted ions as a vertical coordinate;
(3) the method for detecting the residual amount of quinclorac in the tobacco sample comprises the following steps:
extracting a tobacco sample; weighing 3.00g of tobacco sample, adding 20mL of ultrapure water, 30mL of extracting solution (V formic acid: V acetonitrile: 0.5: 99.5), continuously adding 5g of sodium chloride, performing vortex extraction for 5min, centrifuging for 3min at 4000rmp, and taking supernatant;
purifying the tobacco sample extracting solution to be purified; putting 1.5mL of the supernatant into a centrifuge tube which is added with 100mgC18 in advance, uniformly mixing for 5min in a vortex manner, centrifuging for 3min at 11000rmp, transferring the supernatant after centrifugation, and filtering the supernatant through a 0.22 mu m filter membrane to obtain a tobacco sample extraction purification solution for measuring the residual dichloroquinacrinic acid;
(4) determining the residual amount of quinclorac in the tobacco sample extraction purification solution by using a high performance liquid chromatography-tandem mass spectrometry method, recording the peak area of an extracted ion chromatogram, and quantifying by using a matrix external standard method to obtain the determined value of the quinclorac in the tobacco sample extraction purification solution; then bringing the measured value into a quantitative calculation formula to finally obtain the residual amount of quinclorac to be measured in the tobacco sample;
quantitative calculation formula: r ═ C × V1×V3)/m×V2In the formula: r is the residual quantity (mg/kg) of the pesticide in the sample; c, obtaining sample injection concentration (mg/L) through standard curve or single-point quantitative calculation according to the peak area of the sample; m is a weighed amount (g); v1 is extract volume (mL); v2 is the volume of the aliquot (mL); v3 constant volume (mL);
in steps (2) and (4), the mass spectrometry conditions involved are shown in table 1;
TABLE 1 Mass Spectrometry conditions for Quinclorac
2. The method of claim 1, wherein: in steps (2) and (4), the measurement conditions involved are: ionization source mode: ESI; ionization source polarity: positive; atomizing: nitrogen gas; sheath gas pressure: 276 kPa; ion transfer tube temperature: 320 ℃; temperature of the spray needle: 300 ℃; ion spray voltage: 3500V; column Hypersil GOLD C18(2.1 mm. times.100 mm1.9 μm), column temperature: 35 ℃; flow rate: 0.3 mL/min; sample introduction amount: 5 mu L of the solution; the mobile phase B was methanol solution, the mobile phase C was 0.1% formic acid in water (v/v), and the gradient elution conditions are shown in Table 2 (the ratio of the two solvents in mobile phase B, C in Table 2 is volume ratio).
TABLE 2 gradient elution conditions
3. The method according to claim 2, wherein the concentration of quinclorac in the tobacco substrate mixed standard working solution of step (1) is in the range of 1-1000 μ g/L.
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