CN114088841A - QuEChERS-UPLC-MS/MS method for analyzing pesticide residues in rosa roxburghii - Google Patents
QuEChERS-UPLC-MS/MS method for analyzing pesticide residues in rosa roxburghii Download PDFInfo
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- CN114088841A CN114088841A CN202111395835.8A CN202111395835A CN114088841A CN 114088841 A CN114088841 A CN 114088841A CN 202111395835 A CN202111395835 A CN 202111395835A CN 114088841 A CN114088841 A CN 114088841A
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Classifications
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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
-
- 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
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
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Abstract
The invention discloses an economic, rapid, sensitive and accurate analysis method capable of simultaneously measuring 11 common pesticide residues in rosa roxburghii. After a sample is crushed, the sample is pretreated by an optimized QuEChERS method, acetonitrile is used as an extracting agent, N-propyl ethylenediamine and graphitized carbon black are used as purifying agents, and the analysis is carried out by combining ultra-high performance liquid chromatography-tandem mass spectrometry. The Agilent Eclipse Plus C is adopted18Separating with a column, taking 0.1% formic acid water-acetonitrile as a mobile phase, carrying out gradient elution, detecting in an electrospray positive ion multi-reaction monitoring mode, and quantifying by an external standard method. The method verifies that the detection limit of the 11 pesticides is between 1.31 and 8.56 mu g/kg, the quantitative limit is between 4.13 and 43.57 mu g/kg, and the linear correlation coefficient (R) is between 0.9912 and 0.9999. The method selects 3 concentration levels to carry out addition recovery rate experiments, the average standard addition recovery rate is 84.54-103.81%, and the relative standard deviation (n is 6) is 1.15-8.46%. Pretreatment in the methodThe method is rapid, sensitive and accurate, and can provide technical support for supervision of the pesticide in the roxburgh rose.
Description
Technical Field
The invention relates to the technical field of analytical chemistry and agricultural product safety, mainly relates to a determination technology of various pesticide residues in roxburgh roses, and particularly relates to a QuEChERS-UPLC-MS/MS method for analyzing the pesticide residues in roxburgh roses.
Background
Rosa roxburghii Tratt is a rare nutritional precious fruit with nourishing and body-building functions, and belongs to Rosa plants in Rosaceae, also called King mountain fruit, Rosa roxburghii fruit, Buddha fruit, arrowroot pear, Murraya koenigii, Elaeagnus davidiana, Acronychia sinensis, Rosa roxburghii, Jiupou, Xanthocerana cathayensis and punica granatum (Shaanxi). The method mainly uses the large distribution area and the large yield of Guizhou, Sichuan, Yunnan, Hubei and Hunan, wherein the wild roxburgh roses in Guizhou province are distributed most and are special advantageous resources of the Guizhou province. The roxburgh rose fruit is rich in various vitamins, amino acids, trace elements, carotene, organic acids, flavone, beta-sitosterol, superoxide dismutase (SOD) and the like, wherein every 100g of roxburgh rose pulp contains 2054-2725 mg of vitamin C, 5980-12895 mg of vitamin P and 32100U of SOD, which are far superior to fruits such as kiwi fruits, oranges, raspberries and the like, and is the 'King of vitamin C' and 'the fruit of three King' which are really true, and is also the crown of the third-generation fruits in the world at present.
In recent years, with the continuous expansion of the cultivation area of the roxburgh rose, the problems of various diseases such as powdery mildew, brown spot, sooty mold, stem rot, virus diseases and the like of the roxburgh rose, insect pests such as oriental fruit moth, fruit fly, aphid, whitefly, scale insect and the like, and weeds such as horse pond, creeping oxalis, goosegrass, green bristlegrass and purslane and other insect pests are gradually highlighted. Although no pesticide registered in the Chinese pesticide information network can be used in the production of rosa roxburghii, the research on the major production area of rosa roxburghii in Guizhou shows that pesticides, bactericides and herbicides such as difenoconazole, imidacloprid, pyraclostrobin, diuron, acetamiprid, carbendazim, myclobutanil, chlorantraniliprole, kresoxim-methyl, azoxystrobin, triadimefon and the like, are commonly used by fruit growers for the purpose of rapidly preventing and treating diseases and pests in order to ensure the yield. The maximum limit of the pesticide residue of rosa roxburghii tratt is not specified in the standard GB 2763-2021: "maximum limit of pesticide residue in food", so that the pesticide is applied for a long time on the production of rosa roxburghii tratt, and whether the pesticide residue exists, the amount of the pesticide residue and the quality safety of rosa roxburghii tratt cannot be influenced are needed to be researched. Therefore, a method for rapidly analyzing the common pesticides on the rosa roxburghii tratt is needed to be invented, and technical support is provided for the use and supervision of the pesticides on the rosa roxburghii tratt.
At present, the pesticide detection methods commonly used in fruits include gas chromatography, gas chromatography-tandem mass spectrometry, liquid chromatography, and liquid chromatography-tandem mass spectrometry. Common sample pretreatment technologies comprise a QuEChERS method, a solid phase microextraction method, a microwave extraction method and the like, wherein the QuEChERS method is used as a pretreatment method for pesticide residues in fruits and vegetables from the beginning of birth, and is gradually popularized to a larger detection range and a matrix due to the characteristics of rapidness, simplicity and convenience, so that the QuEChERS method becomes the first choice of the rapid pretreatment technology for the pesticide residues. The QuEChERS method is widely applied to the research of analyzing pesticide residues in fruits and vegetables by chromatography-tandem mass spectrometry. At present, the research of analyzing various organochlorine pesticide residues in rosa roxburghii tratt by a gas chromatography-tandem mass spectrometry method is reported in documents, but according to the actual research result, organochlorine pesticides are not commonly used in rosa roxburghii tratt production, and the gas chromatography is not easy to analyze some pesticides with strong polarity and poor thermal stability, so that a liquid chromatography-tandem mass spectrometry method with high reliability, good stability and wide detection range is urgently needed to be established. Meanwhile, the roxburgh rose sample has complex matrix, contains more vitamins, SOD, organic acid, roxburgh rose glycoside and flavonoid active substances, can interfere with the extraction of pesticide, has low extraction rate, can generate stronger matrix interference to influence the accuracy of a detection result, and causes more complex extraction and purification of pesticide residue in roxburgh rose, so that the conventional QuEChERS method cannot meet the requirement of pesticide residue detection in roxburgh rose. The invention aims to establish a multi-residue analysis method for simultaneously and rapidly detecting 11 pesticides in roxburgh rose by optimizing QuEChERS pretreatment method and determination conditions and combining ultra-high performance liquid chromatography-tandem mass spectrometry detection on the basis of fully investigating and researching the currently common pesticides used by roxburgh rose fruit growers.
Disclosure of Invention
The invention aims to provide a rapid, sensitive, accurate, simple, convenient, durable and low-cost method for analyzing pesticide residues in roxburgh roses, which is used for solving the problems that the existing detection mode has complicated steps, a limited detection range and a long detection period and cannot well meet the rapid detection requirements of the roxburgh roses and products thereof.
In order to achieve the purpose, the technical scheme of the invention is to provide a QuEChERS-UPLC-MS/MS method for analyzing pesticide residues in roxburgh rose, which comprises the following steps: the method comprises the following steps:
crushing a roxburgh rose sample to be analyzed, and performing sample pretreatment on the roxburgh rose sample to obtain a liquid to be detected;
crushing a roxburgh rose sample without pesticide residues, transferring a certain amount of ultrapure water, performing sample pretreatment on the sample, and filtering the ultrapure water by a membrane to obtain a matrix solution;
adding a pure organic solvent into a pesticide standard substance to obtain a pesticide standard substance mother liquor with a set concentration, respectively transferring the same amount of pesticide standard substance mother liquor into two volumetric flasks, and then fixing the volume by using the pure organic solvent to obtain a mixed intermediate liquor of two solvent standard substances;
diluting a solvent standard mixed intermediate solution into a plurality of solvent standard working solutions with concentration gradients by using a pure organic solvent;
diluting another solvent standard mixed intermediate solution into a plurality of concentration gradient matrix standard working solutions by using the matrix solution;
determining the solvent standard substance working solution and the matrix standard substance working solution by using ultra-high performance liquid chromatography-tandem mass spectrometry to obtain a solvent standard curve and a matrix standard curve;
and (3) determining the solution to be determined by using ultra performance liquid chromatography-tandem mass spectrometry, and substituting the determination result into a matrix standard curve to obtain the pesticide residue condition in the roxburgh rose to be analyzed.
Optionally, weighing a set amount of roxburgh rose sample to be analyzed in a first centrifuge tube, adding an extracting agent, adding a dehydration reagent, and then performing first centrifugation to obtain a first supernatant;
transferring the first supernatant into a second centrifugal tube, adding an adsorbent, performing vortex oscillation firstly, and then performing secondary centrifugation to obtain a second supernatant;
and filtering the second supernatant through a filter membrane to obtain a solution to be detected.
Optionally, the extractant is an acetonitrile solution.
Optionally, the dehydrating reagent is anhydrous magnesium sulfate.
Optionally, the adsorbent is a mixture of N-propyl ethylene diamine and graphitized carbon black.
Optionally, in the first centrifugation process, the centrifugation rotation speed is 4000r/min, and the centrifugation time duration is 5min, and in the second centrifugation process, the centrifugation rotation speed is 12000r/min, and the centrifugation time duration is 5 min.
Optionally, the rotation speed is 2000r/min and the time is 3min during the vortex oscillation.
Optionally, an ultra high performance liquid phaseThe chromatographic conditions adopted by the chromatographic-tandem mass spectrometry are as follows: and (3) chromatographic column: agilent Eclipse Plus C18A column; column temperature: 30 ℃; temperature of the sample chamber: room temperature; sample introduction amount: 5 mu L of the solution; flow rate: 0.4 mL/min; analysis time: 5 min; mobile phase A: 0.1% formic acid water; mobile phase B: acetonitrile, gradient elution.
Optionally, the mass spectrometry conditions adopted by the ultra performance liquid chromatography-tandem mass spectrometry method are as follows: sheath gas temperature and flow rate: 250 ℃ and 11.0L/min; nozzle voltage: 500V; capillary voltage: 4000V; atomizing gas pressure: 45 psi; drying gas temperature and flow rate: 300 ℃ and 5L/min; the scanning mode is as follows: and detecting in a multi-reaction monitoring mode.
Optionally, the pesticide standard solution comprises: difenoconazole, imidacloprid, pyraclostrobin, diuron, acetamiprid, carbendazim, myclobutanil, chlorantraniliprole, kresoxim-methyl, azoxystrobin and triadimefon.
Compared with the prior art, the invention has the following advantages:
the optimized QuEChERS method is effectively combined with UPLC-MS/MS, and the detection method for simultaneously determining 11 common pesticide residues in the rosa roxburghii tratt by the QuEChERS-UPLC-MS/MS method is established. Extracting 11 kinds of pesticide residues in the roxburgh rose by using acetonitrile, purifying by using PSA adsorbent, and then carrying out UPLC-MS/MS determination. The method not only effectively shortens the pretreatment time, but also has less waste and less environmental pollution, and simultaneously has less organic reagent dosage and is relatively safer for experimenters; through the optimization of the adsorbent, the matrix interference is reduced, and the purification efficiency is improved. Research results show that the method is rapid, sensitive and accurate, has the advantages of durability, simplicity and low cost, and is suitable for confirmation and quantitative determination of 11 common pesticide residues in the rosa roxburghii tratt.
Drawings
FIG. 1 is a quantitative ion diagram of a sample with 1mg/kg difenoconazole roxburgh rose added.
FIG. 2 is a quantitative ion diagram of a sample with 1mg/kg imidacloprid roxburgh rose added.
FIG. 3 is a quantitative ion diagram of a roxburgh rose sample added with 1mg/kg pyraclostrobin.
FIG. 4 is a quantitative ion graph of a diuron Roxburgh rose sample added with 1 mg/kg.
FIG. 5 is a quantitative ion diagram of a sample added with 1mg/kg acetamiprid roxburgh rose.
FIG. 6 is a quantitative ion diagram of a Rosa roxburghii sample added with 1mg/kg carbendazim.
FIG. 7 is a quantitative ion diagram of a sample of Rosa roxburghii added with 1mg/kg myclobutanil.
FIG. 8 is a quantitative ion diagram of a roxburgh rose sample added with 1mg/kg chlorantraniliprole.
FIG. 9 is a quantitative ion diagram of a sample with the addition of kresoxim-methyl at 1mg/kg of roxburgh rose.
FIG. 10 is a graph of the quantitative ionization of a sample with the addition of 1mg/kg azoxystrobin roxburgh rose.
FIG. 11 is a quantitative ionograph of a sample of Roxburgh rose with the addition of 1mg/kg triazolone.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment of the invention provides a method for rapidly analyzing pesticide residues in roxburgh roses, which comprises the following steps:
crushing a roxburgh rose sample to be analyzed, and performing sample pretreatment on the roxburgh rose sample to obtain a liquid to be detected.
Crushing a roxburgh rose sample without pesticide residues, transferring a certain amount of ultrapure water, performing sample pretreatment on the sample, and filtering the ultrapure water by a membrane to obtain a matrix solution;
adding a pure organic solvent into a pesticide standard substance, preparing a mother solution of a pesticide standard substance mother solution standard substance with a certain set concentration by using the pure organic solvent, transferring each pesticide standard substance mother solution with the same amount into two volumetric flasks respectively, and then fixing the volume by using the pure organic solvent to obtain a mixed intermediate solution of the two solvent standard substances;
diluting a solvent standard mixed intermediate solution into a plurality of solvent standard working solutions with concentration gradients by using a pure organic solvent;
diluting another solvent standard mixed intermediate solution into a plurality of concentration gradient matrix standard working solutions by using the matrix solution;
determining the solvent standard substance working solution and the matrix standard substance working solution by using ultra-high performance liquid chromatography-tandem mass spectrometry to obtain a solvent standard curve and a matrix standard curve;
and (3) determining the solution to be determined by using ultra performance liquid chromatography-tandem mass spectrometry, and substituting the determination result into a matrix standard curve to solve the pesticide residue condition in the rosa roxburghii tratt to be analyzed.
In one embodiment, the ultra performance liquid chromatography-tandem mass spectrometry adopts the following chromatographic conditions:
a chromatographic column: agilent Eclipse Plus C18Column (2.1 mm. times.50 mm, 1.8 μm particle size);
column temperature: 30 ℃; temperature of the sample chamber: room temperature; sample introduction amount: 5 mu L of the solution; flow rate: 0.4 mL/min; analysis time: 5 min; mobile phase A: 0.1% formic acid water; mobile phase B: acetonitrile, gradient elution.
In one embodiment, the mass spectrometry conditions adopted by the ultra performance liquid chromatography-tandem mass spectrometry are as follows:
sheath gas temperature and flow rate: 250 ℃ and 11.0L/min; nozzle voltage: 500V; capillary voltage: 4000V; atomizing gas pressure: 45 psi; drying gas temperature and flow rate: 300 ℃ and 5L/min; the scanning mode comprises the following steps: and (4) detecting in a multi-reaction monitoring mode.
In one embodiment, the pesticide standard solution comprises: difenoconazole, imidacloprid, pyraclostrobin, diuron, acetamiprid, carbendazim, myclobutanil, chlorantraniliprole, kresoxim-methyl, azoxystrobin and triadimefon.
The sample pretreatment specifically comprises the following steps:
weighing a set amount of roxburgh rose sample to be analyzed in a first centrifuge tube, adding an extracting agent, adding a dehydration reagent, and then carrying out first centrifugation to obtain a first supernatant;
transferring the first supernatant into a second centrifugal tube, adding an adsorbent, performing vortex oscillation firstly, and then performing secondary centrifugation to obtain a second supernatant;
and filtering the second supernatant through a filter membrane to obtain a solution to be detected.
In one embodiment, the extractant is an acetonitrile solution.
In one embodiment, the dehydrating reagent is anhydrous magnesium sulfate.
In one embodiment, the adsorbent is a mixture of N-propyl ethylene diamine and graphitized carbon black.
In one embodiment, the first centrifugation process has a centrifugation speed of 4000r/min and a centrifugation time of 5 min.
In one embodiment, the second centrifugation is performed at 12000r/min for 5 min.
In one embodiment, the vortex oscillation process has a rotation speed of 2000r/min and a time of 3 min.
The whole analysis process is described in the following by specific embodiments:
example 2
1. Experimental part
1.1 instruments and reagents
Ultra high performance liquid chromatography-tandem mass spectrometry (including Agilent 1290Infinity ii ultra high performance liquid chromatograph and Agilent 6470 triple quadrupole mass spectrometer) (Agilent corporation, usa); MS200 multi-tube vortex mixer (Hangzhou Ruichi Instrument Co., Ltd.); 1-16 small high speed centrifuge (Sigma, Germany); CK2000 high-throughput tissue milling apparatus (Beijing Tomo Morgan Biotech Co., Ltd.); BY-400B centrifuge (Beijing Baiyang medical devices, Inc.); AL104 analytical balance (mettler-toledo).
C18(40-60 μm), PSA (40-60 μm), Tianjin Bonne Aijiel technologies, Inc.; flori silica (100-; GCB, shanghai alatin biochemistry science and technology limited; anhydrous magnesium sulfate (analytically pure), Yongda chemical reagents, Inc., Tianjin; sodium chloride (analytical grade), methanol (analytical grade), chemical reagents ltd of kyou europe, tianjin; acetonitrile (analytical grade), shanghai alatin biochemical technology; acetonitrile (chromatographically pure), merck, germany; purified water, wa haha group ltd; 0.22 μm filter head, picui, guangzhou, piscine limited; 1mL syringe, Jiangxi Yikang medical instrument group Co., Ltd; 2mL sampleBottle, Agilent, usa.
And (3) standard substance: the purity of the standard, CAS number, manufacturer, etc. are shown in Table 1:
TABLE 1 Standard pesticide test
1.2 chromatographic conditions
A chromatographic column: agilent Eclipse Plus C18Column (2.1 mm. times.50 mm, 1.8 μm particle size); column temperature: 30 ℃; temperature of the sample chamber: room temperature; sample introduction amount: 5 mu L of the solution; flow rate: 0.4 mL/min; analysis time: 5 min; mobile phase A: 0.1% formic acid water; mobile phase B: acetonitrile, gradient elution, gradient conditions see table 2:
TABLE 2 gradient elution procedure
1.3 Mass Spectrometry conditions
Sheath gas temperature and flow rate: 250 ℃ and 11.0L/min; nozzle voltage: 500V; capillary voltage: 4000V; atomizing gas pressure: 45 psi; drying gas temperature and flow rate: 300 ℃ and 5L/min; the scanning mode is as follows: and (4) detecting in a multi-reaction monitoring mode.
1.4 sample pretreatment
Weighing 10.0g of the crushed roxburgh rose sample, placing the sample in a 50mL centrifuge tube, adding 15mL acetonitrile solution, shaking for extraction for 10min, then adding 1.0g of sodium chloride and 4.0g of anhydrous magnesium sulfate, shaking for 5min, and then centrifuging for 5min at 4000 r/min. 1.5mL of the supernatant was taken into a 2mL purification tube containing 150mg of anhydrous magnesium sulfate, 50mg of PSA and 5mg of GCB, vortexed at 2000r/min for 3min, centrifuged at 12000r/min for 5min, and the supernatant was drawn off with a 1mL syringe through a 0.22 μm filter for UPLC-MS/MS detection.
1.5 preparation of Standard solution
11 kinds of pesticide standard mother liquor (100 mu g/mL): 11 pesticide standard substances are accurately weighed (accurate to 0.001g) respectively, dissolved by acetonitrile, prepared into 100 mu g/mL standard mother liquor respectively, and refrigerated and stored in a refrigerator at 4 ℃.
Standard mix solution (1. mu.g/mL): accurately transferring 0.1mL of each of 11 pesticide standard mother solutions into a 10mL volumetric flask, diluting the volume to 10mL with acetonitrile, and refrigerating and storing the solution in a refrigerator at 4 ℃.
Solvent standard working curve: 1, 5, 10, 20 and 40 mu L of 1 mu g/mL mixed standard stock solution is respectively added into a 1mL volumetric flask, the volume is fixed to the scale by acetonitrile, and solvent standard mixed working solutions of 0.001, 0.005, 0.01, 0.02 and 0.04 mu g/mL are prepared and are ready to use.
Matrix standard working curve: adding 1, 5, 10, 20 and 40 mu L of 1 mu g/mL mixed standard stock solution into a 1mL volumetric flask respectively, using a blank sample extracting solution to fix the volume to a scale, and preparing into 0.001, 0.005, 0.01, 0.02 and 0.04 mu g/mL solvent standard mixed working solution which is prepared for use.
2 results and discussion
2.1 optimization of Mass Spectrometry conditions
Optimizing the settings of instrument conditions such as fragmentation voltage, collision energy, residence time, accelerating voltage and the like, screening mass spectrum conditions capable of generating high-response and specific ion pairs, and completing the detection of all target objects by one injection in the modes of positive ion scanning and multi-reaction monitoring. The specific results are shown in Table 3.
Mass Spectrometry parameters for the 311 pesticides in Table
2.2 selection and optimization of sample Pre-treatment conditions
2.2.1 extraction
TABLE 4 Total recovery of 11 pesticides from different extraction methods
First, acetonitrile, methanol, ethyl acetate and dichloromethane were used as extractants, and the extraction efficiency of these 4 extractants was examined by adding and recovering them. The specific process is as follows: weighing 10.0g of a homogenized blank roxburgh rose sample, placing the sample in a 50mL centrifuge tube (each processing 3 parallel), adding a standard substance, standing for 30min, adding 15mL of an extractant solution, shaking for 10min, then adding 1.0g of sodium chloride and 4.0g of anhydrous magnesium sulfate, shaking for 5min, then centrifuging for 5min at 4000r/min, taking the supernatant, detecting by 0.22 mu m, and inspecting the extraction effect by calculating the recovery rate of 11 pesticides.
By examining the extraction efficiency of the 4 extracting agents, the result shows that the extraction efficiency of acetonitrile is better than that of other extracting agents, and the average value of the overall recovery rate can reach 99 percent (Table 4). Then, 0.1% formic acid-acetonitrile, 1% formic acid-acetonitrile, 0.1% glacial acetic acid-acetonitrile, 1% ammonia water-acetonitrile are used as extracting agents, the influence of common buffers on the extraction rate of pesticides is examined, and the experimental steps are the same as the above. As can be seen from table 4, the overall recovery rate of 11 pesticides after the addition of the buffer is between 63% and 74%, which indicates that the addition of some buffers such as formic acid, glacial acetic acid, ammonia water and the like to the extractant cannot improve the extraction rate of acetonitrile, and therefore the extractant is finally determined to be acetonitrile.
2.2.2 purification
TABLE 5 Total recovery of 11 pesticides purified with different purifiers
A commonly used purification material for the QuEChERS method is C18PSA, Florisil and GCB. C18The PSA can be used for removing fat, organic acid, pigment, sugar and fatty acid of various fruits and vegetables, and the GCB can be used for removing steroid, chlorophyll and other pigments, but has strong adsorption effect on compounds containing benzene functional groups, and the recovery rate is reduced. Thus, this study investigates C18Influence of the four purification materials of PSA, Florisil and GCB on recovery of the analyte by using alone and in combination. The method comprises the following specific steps: under the optimized extraction condition in section 2.2.1, centrifuging after extraction is finished, taking 1.5mL of supernatant into a 2mL centrifuge tube filled with 150mg of anhydrous magnesium sulfate and different purification materials, firstly whirling at 2000r/min for 3min, then centrifuging at 12000r/min for 5min, and extracting with a 1mL syringeAfter the clear liquid is detected by 0.22 mu m, the adsorption condition of different purifying materials on the pesticide is investigated by calculating the recovery rate of 11 pesticides, and the result shows that except PSA, other purifying agents have certain adsorption on a few pesticides, especially the purifying agent containing GCB has the largest influence, so that the recovery rate of individual pesticides is low (Table 5). As can also be seen from Table 5, by combining the highest recovery PSA with different GCB qualities, it was found that the recovery increased with decreasing GCB mass, with the most desirable recovery being 86% for a 5mg GCB mass, and the supernatant was cleaner than the supernatant with PSA alone. Although the recovery rate (86%) of the 50mg PSA and 5mg GCB combined purification is not as high as that (97%) of the PSA alone purification, the sample without the GCB purifying agent contains more pigments, so that the risk of pollution of a chromatographic column and a detector is increased, and the experiment finally selects 50mg PSA +5mg GCB as the purifying agent by comprehensive consideration.
2.3 evaluation of method
2.3.1 Linear Range, detection Limit, quantification Limit results
TABLE 611 linear equations, determination coefficients, ion suppression rates, detection limits and quantitation limits for pesticides
Under the condition of the chromatographic mass spectrometry, a series of target pesticides with mass concentration are added into a blank sample, a series of matrix standard solutions of the target pesticides are prepared (a standard curve comprises a matrix blank and at least one horizontal state near a detection limit), and after the standard solution is measured by UPLC-MS/MS, a standard curve is drawn by taking the mass concentration of the target pesticides as an x (mu g/mL) abscissa and the peak area of mass spectrometry quantitative ions as a y ordinate.
11 kinds of pesticides were added to the blank sample, and the detection limit and the quantification limit were calculated with the signal-to-noise ratio of 3 and 10, respectively. The experimental result shows that the detection limit is between 1.31 and 8.56 mu g/kg, the quantification limit is between 4.13 and 43.57 mu g/kg, and the specific result is shown in Table 6. After the quantitative limit of each target pesticide is determined, preparing the mixed target pesticide storage solution with high quality and concentration according to a certain proportion. And adding a series of mixed target pesticide storage solutions with mass concentrations into the blank sample extracting solution, repeating the adding level for 6 times, calculating a linear range, and drawing a standard curve. Experimental results show that the linear correlation coefficient (R) of the target pesticide is 0.9912-0.9999, the basic requirements of quantitative analysis can be met, and specific results are shown in Table 6.
2.3.2 matrix Effect
The matrix effect is to be avoided as much as possible by using LC-MS/MS to detect residues. According to the literature report, the ion inhibition rate calculation formula is as follows:
wherein KmMatch the slope of the standard curve for the substrate, KsThe slope of the standard curve for pure solvent. When the ion suppression ratio is 0, no matrix effect is shown; when the ion inhibition rate is more than 0, the matrix enhancement effect of the sample matrix on the determination of the target compound is shown; when the ion inhibition ratio is less than 0, it indicates that the matrix inhibition effect exists in the determination of the target compound by the sample matrix. By comparing the ion inhibition rates of 11 pesticides in the roxburgh rose matrix, the experimental results show that: the roxburgh rose sample matrix has a remarkable matrix inhibition effect on all pesticides except imidacloprid (see table 6), so matrix standard curves are needed to be corrected to eliminate the influence caused by the matrix effect.
2.3.3 accuracy and precision of the method
11 target pesticide mixed standard solutions with proper volumes are added into a roxburgh rose sample, and the adding levels are respectively 0.1mg/kg, 1mg/kg and 5 mg/kg. As can be seen from table 7, the average spiked recovery rate of the 11 pesticides was between 84.54% and 103.81%, and the relative standard deviation (n ═ 6) was between 1.15% and 8.46%, and the method had better recovery rate and repeatability.
TABLE 711 Standard recovery and relative standard deviation of pesticides
3 conclusion
The invention establishes a UPLC-MS/MS method for simultaneously detecting 11 common pesticide residues in roxburgh rose. The method has high sensitivity and good reproducibility, and through the verification of a series of methodologies, the LOD of 11 common pesticides is between 1.31 and 8.56 mu g/kg, the LOQ is between 4.13 and 43.57 mu g/kg, and the linear correlation coefficient (R) is between 0.9912 and 0.9999; the average recovery rate of the added standard is 84.54-103.81%, and the relative standard deviation (n is 6) is 1.15-8.46%. The method is accurate, simple to operate, good in purification effect, quick, has important practical significance and social benefit for promoting government regulatory authorities to enforce law, improving detection efficiency, reducing detection cost, promoting third party detection market overall technical progress and the like, and can be applied to the use and safety monitoring work of the roxburgh rose pesticide.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundary of the appended claims, or the equivalents of such scope and boundary.
Claims (10)
1. A QuEChERS-UPLC-MS/MS method for analyzing pesticide residues in roxburgh rose, which is characterized by comprising the following steps:
crushing a roxburgh rose sample to be analyzed, and performing sample pretreatment on the roxburgh rose sample to obtain a liquid to be detected;
crushing a roxburgh rose sample without pesticide residues, transferring a certain amount of ultrapure water, performing sample pretreatment on the sample, and filtering the ultrapure water by a membrane to obtain a matrix solution;
adding a pure organic solvent into a pesticide standard substance to obtain a pesticide standard substance mother liquor with a set concentration, respectively transferring the same amount of pesticide standard substance mother liquor into two volumetric flasks, and then fixing the volume by using the pure organic solvent to obtain a mixed intermediate liquor of two solvent standard substances; diluting a solvent standard mixed intermediate solution into a plurality of solvent standard working solutions with concentration gradients by using a pure organic solvent; diluting another solvent standard mixed intermediate solution into a plurality of concentration gradient matrix standard working solutions by using the matrix solution;
determining the solvent standard substance working solution and the matrix standard substance working solution by using ultra-high performance liquid chromatography-tandem mass spectrometry to obtain a solvent standard curve and a matrix standard curve;
and (3) determining the solution to be determined by using ultra performance liquid chromatography-tandem mass spectrometry, and substituting the determination result into a matrix standard curve to obtain the pesticide residue condition in the roxburgh rose to be analyzed.
2. The method according to claim 1, wherein the sample pre-treatment specifically comprises:
weighing a set amount of roxburgh rose sample to be analyzed in a first centrifuge tube, adding an extracting agent, adding a dehydration reagent, and then carrying out first centrifugation to obtain a first supernatant;
transferring the first supernatant into a second centrifugal tube, adding an adsorbent, performing vortex oscillation firstly, and then performing secondary centrifugation to obtain a second supernatant;
and filtering the second supernatant through a filter membrane to obtain a solution to be detected.
3. The method of claim 2, wherein the extractant is an acetonitrile solution.
4. The method of claim 2, wherein the dehydrating reagent is anhydrous magnesium sulfate.
5. The method of claim 2, wherein the adsorbent is a mixture of N-propyl ethylene diamine and graphitized carbon black.
6. The method according to claim 2, wherein the first centrifugation is performed at a speed of 4000r/min for a period of 5min, and the second centrifugation is performed at a speed of 12000r/min for a period of 5 min.
7. The method of claim 2, wherein the rotational speed is 2000r/min and the time is 3min during the vortex oscillation.
8. The method of claim 1, wherein the ultra performance liquid chromatography-tandem mass spectrometry employs chromatographic conditions that are: and (3) chromatographic column: agilent Eclipse Plus C18A column; column temperature: 30 ℃; temperature of the sample chamber: room temperature; sample injection amount: 5 mu L of the solution; flow rate: 0.4 mL/min; analysis time: 5 min; a mobile phase A: 0.1% formic acid water; mobile phase B: acetonitrile, gradient elution.
9. The method of claim 1, wherein the mass spectrometry conditions adopted by the ultra performance liquid chromatography-tandem mass spectrometry are as follows: sheath gas temperature and flow rate: 250 ℃ and 11.0L/min; nozzle voltage: 500V; capillary voltage: 4000V; atomizing gas pressure: 45 psi; drying gas temperature and flow rate: 300 ℃ and 5L/min; the scanning mode is as follows: and (4) detecting in a multi-reaction monitoring mode.
10. The method of claim 1, wherein the pesticide standard solution comprises: difenoconazole, imidacloprid, pyraclostrobin, diuron, acetamiprid, carbendazim, myclobutanil, chlorantraniliprole, kresoxim-methyl, azoxystrobin and triadimefon.
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| CHRIS SACK等: "Collaborative Validation of the QuEChERS Procedure for the Determination of Pesticides in Food by LC MS/MS", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
| RESHMA PATIL等: "Comprehensive multiresidue determination of pesticides and plant growth regulators in grapevine leaves using liquid- and gas chromatography with tandem mass spectrometry", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 张建莹等: "QuEChERS/超高效液相色谱-串联质谱法测定果蔬中122种香港规例农药残留", 《分析测试学报》 * |
| 陈溪等: "QuEChERS-液相色谱-质谱法快速筛查和确证大米中205种农药残留", 《色谱》 * |
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