CN110554132A - Method for detecting residual amount of prothioconazole in citrus - Google Patents
Method for detecting residual amount of prothioconazole in citrus Download PDFInfo
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- G—PHYSICS
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- 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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- 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
- G01N30/12—Preparation by evaporation
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/047—Standards external
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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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
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
Abstract
The invention discloses a method for detecting prothioconazole residual quantity in citrus, which comprises the steps of weighing a proper amount of homogenized citrus sample, placing the citrus sample in a triangular flask, adding acetonitrile for oscillation extraction, carrying out suction filtration, salting out with NaCl, standing for layering, absorbing a half of organic phase supernatant, transferring the organic phase supernatant into the triangular flask, concentrating the organic phase to be nearly dry, transferring the organic phase supernatant into a centrifugal tube after constant volume, adding PSA adsorbent, carrying out vortex and centrifugation, taking the supernatant to pass through an organic filter membrane to obtain a sample solution to be detected, and carrying out HPLC-Ms/Ms detection and external standard method quantification. Under the conditions of sample extraction, purification and detection provided by the invention, the prothioconazole and impurities in a citrus matrix are well separated, the separation capability of a chromatograph and the qualitative function of a mass spectrum are combined by a liquid chromatogram tandem mass spectrometry method, so that more accurate quantitative and qualitative analysis of prothioconazole in citrus is realized, and a methodological verification test shows that the sensitivity, accuracy and precision of the established method all meet the technical requirements of pesticide residue determination.
Description
Technical Field
The invention relates to a pesticide residue detection method, and in particular relates to a method for detecting the residual amount of prothioconazole in citrus.
Background
Common english name of albendazole: albendazole, chemical name: 5- (propylsulfanyl) -1H-benzimidazol-2-yl]methyl carbamate, chemical formula: c12H15N3O2And S. Prothioconazole was a new compound developed in 1972 in the united states "SmithKline animal health laboratory" for bacterial and parasitic infections in animals. The Guizhou dao Yuan biotechnology Limited company integrates the joint attack of the national medical field and the first expert of the pesticide field, uses albendazole for agricultural fungal bactericide for the first time in the world, belongs to systemic albendazole new generation agricultural bactericide, is an agricultural bactericide with independent intellectual property rights in China, has the functions of prevention, protection, systemic treatment and permeation conduction, has a broad bactericidal spectrum, has a stronger action mode and complementarity of biological activity, is a high-efficiency, low-toxicity and true broad-spectrum systemic bactericide, and has the characteristics of high activity, long duration, strong systemic property and flexible pesticide application time. The albendazole has been officially registered on various crop diseases, and the currently registered crops comprise rice, tobacco, watermelon, banana, Chinese cabbage and the like.
when the albendazole is applied to different crops for sterilization, part of pesticide residues inevitably exist along with the increase of the using amount of the albendazole, and the research on the albendazole analysis technology in different crops such as citrus and the like is very necessary for ensuring the food safety and reducing the pesticide pollution. At present, no published report is found on a residual analysis method of the albendazole in the plant matrix at home and abroad.
Disclosure of Invention
the invention aims to provide a method for analyzing the residue of prothioconazole in citrus, which is mainly used for measuring the residue of prothioconazole in bases such as citrus pulp, whole citrus fruit and the like, has the characteristics of simplicity, accuracy, rapidness, reliability, low cost and easiness in mastering and popularization, and provides a rapid and reliable method for analyzing the residue of prothioconazole in citrus.
In order to achieve the purpose of the invention, the invention provides a method for detecting the residual quantity of prothioconazole in citrus, which comprises the following steps:
a: uniformly cutting the collected citrus sample into 4 sections along a central axis, taking out non-adjacent 2 sections, uniformly mixing, and then carrying out homogenate by a homogenate machine and filling in a clean sealed plastic bag to obtain a citrus sample to be detected;
b: accurately weighing 10g of the citrus sample to be detected pretreated in the step a, placing the citrus sample into a 250mL triangular flask with a plug, adding 40mL-60mL of acetonitrile, carrying out oscillation extraction at 25 ℃ for 30min-60min, then carrying out vacuum filtration through a Buchner funnel, salting out with 2g of NaCl, standing for layering, sucking a half of organic phase supernatant, transferring the organic phase supernatant into a 250mL triangular flask with a ground opening, concentrating the organic phase supernatant to be nearly dry at 50 ℃ on a rotary evaporator, and carrying out volume fixing to 5.0mL by using chromatographic methanol to obtain an extracting solution;
c: transferring the extract into a 5.0mL centrifuge tube, adding 0.10g PSA adsorbent, vortexing on a vortex mixer for 1min, centrifuging on a centrifuge at 6000r/min for 3min, and filtering the supernatant with 0.22 μm organic filter membrane to obtain citrus sample detection solution to be detected;
And d, selecting a 1290 II ultra-performance liquid chromatography-G6470A triple quadrupole mass spectrometer produced by Agilent of America as an HPLC-MS/MS, and setting the chromatographic conditions: the chromatographic column is ZORBAX Eclipse Plus C18 column, 3.0mm × 100mm, 1.8 μm; column temperature: 25 ℃; sample introduction amount: 5 mu L of the solution; flow rate: 0.3m L/min; mobile phase composition: formic acid water solution with mass concentration of 0.1% and acetonitrile; mobile phase composition: formic acid water solution with mass concentration of 0.1% and acetonitrile; the conditions for gradient elution were: eluting with 90% formic acid water solution for 0.5min, then eluting with 10% formic acid water solution for 2.5min, and finally eluting with 90% formic acid water solution for 1.5min at flow rate of 0.30 mL/min; temperature of the drying gas: 350 ℃; flow rate of drying gas: 3L/min; temperature of sheath gas: 350 ℃; the flow rate of the sheath gas: 12L/min, and the sheath gas is nitrogen; the Fragmentmentor taper hole voltage is 97eV, the qualitative ion pair of the albendazole is 266.1/191, the energy of the collision gas is 32, and the quantitative ion pair is 266.1/234.1; the energy of the collision gas is 16, and under the condition, the retention time of the albendazole is 1.613 min;
e: accurately weighing standard prothioconazole, dissolving the standard prothioconazole with chromatographic methanol to prepare standard mother liquor, then respectively preparing the standard mother liquor of prothioconazole into standard working solution by adopting a gradient dilution method, so that the mass concentrations of prothioconazole are respectively 0.001, 0.005, 0.01, 0.05, 0.10, 0.50 and 1.00mg/L,And respectively injecting the mixture into the HPLC-MS/MS selected in the step d for determination, and respectively drawing a standard working curve of the albendazole by taking the mass concentration x of the albendazole as a horizontal coordinate and the corresponding chromatographic peak area y as a vertical coordinate, so as to obtain a standard curve equation of the albendazole: y 200000x +1834.8, correlation coefficient R2＝0.999；
f: and (e) injecting the citrus sample detection solution to be detected prepared in the step c into HPLC-MS/MS, detecting according to the chromatographic conditions in the step d, and substituting the measured chromatographic peak area into the standard curve equation of the prothioconazole in the step e to obtain the mass concentration of the prothioconazole in the citrus sample.
the invention has the beneficial effects that:
The invention researches and establishes a liquid chromatography-mass spectrometer combined analysis and detection method for the residual amount of the albendazole in the citrus, so as to provide scientific basis for dietary risk assessment of the albendazole and residual monitoring of the albendazole in agricultural products.
the method uses an external standard method for quantification, has good linearity of a standard curve and good reproducibility, obtains high-efficiency separation, and effectively detects the residual quantity of the albendazole in the citrus.
the standard working solution of the albendazole is added into a blank citrus sample, so that the mass concentrations of the albendazole in the citrus pulp and the whole citrus fruit are respectively 0.01, 0.10 and 1.00mg/kg, each concentration is repeated for 5 times, and the established method is used for sample preparation and analysis determination to find that the average recovery rate of the albendazole in the citrus pulp and the whole citrus fruit is 70.7-117.3%, and the relative standard deviation is 2-4%, so that the sensitivity, accuracy and precision of the method meet the requirements of pesticide residue detection, and the method is suitable for accurate and rapid analysis of the residual amount of the albendazole in the citrus.
the method can effectively extract the albendazole from the citrus, effectively purifies the influence of other impurities in the citrus on subsequent detection, and combines the separating capacity of a chromatogram with the qualitative function of a mass spectrum by using the liquid chromatogram tandem mass spectrometry to realize more accurate quantitative and qualitative analysis of the albendazole in the citrus.
Drawings
FIG. 1 is a standard graph of example 1, wherein the regression equation: y 200000x +1834.8 (R)2＝0.999)；
FIG. 2 is a Multiple Reaction Monitoring (MRM) chromatogram corresponding to prothioconazole (0.5mg/L) of example 1.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1:
(1) Sample pretreatment
The collected whole citrus fruit sample is evenly cut into 4 sections along the central axis, 2 sections which are not adjacent are taken, and after being evenly mixed, the whole citrus fruit sample is evenly mixed by a pulp homogenizing machine and is contained in a clean sealed plastic bag. Citrus pulp sample: peeling the collected citrus sample, uniformly peeling the citrus sample into 4 parts, taking out non-adjacent 2 sections, uniformly mixing, homogenizing by a homogenizer, filling in a clean sealed plastic bag, and adhering a label.
(2) Preparation of sample solution to be tested
Extraction of alphos
Accurately weighing 10g of pretreated citrus sample (pulp and whole fruit), placing the orange sample into a 250mL triangular flask with a plug, adding 40mL of acetonitrile, carrying out oscillation extraction at 25 ℃ for 1h, then carrying out vacuum filtration through a Buchner funnel, then salting out with 2g of NaCl, standing for layering, absorbing 20mL of organic phase supernatant, transferring the organic phase supernatant into a 250mL triangular flask with a ground opening, concentrating the organic phase supernatant to be nearly dry on a rotary evaporator (50 ℃), using chromatographic methanol to fix the volume to 5.0mL, and carrying out solid phase extraction and purification after PSA dispersion.
b purification of the extract
The extraction concentrated solution of the sample needs to be purified by dispersed solid phase extraction by using PSA adsorbent: and (3) carrying out constant volume on the extract concentrated solution of the citrus sample to 5.0mL by using chromatographic methanol, transferring the extract concentrated solution into a 5.0mL centrifuge tube, adding 0.10g of PSA adsorbent, carrying out vortex on a vortex mixer for 1min, then centrifuging on a centrifuge at 6000r/min for 3min, taking the supernatant, filtering the supernatant through a 0.22 mu m organic system filter membrane, and carrying out HPLC-MS/MS detection.
(3) Preparation of Standard solutions
Accurately weighing 0.1010g (accurate to 0.0001g) of a standard prothioconazole (with the purity of 99.9 percent), transferring the standard prothioconazole into a 100mL brown volumetric flask, dissolving the standard prothioconazole with chromatographic methanol, and preparing a standard mother solution with the mass concentration of the prothioconazole of 1000 mg/L; then, the standard mother liquor of the albendazole is respectively taken by adopting a gradient dilution method to prepare standard working solution, so that the mass concentration of the albendazole is 0.001, 0.005, 0.01, 0.05, 0.10, 0.50 and 1.00 mg/L.
(4) Instrument detection condition for measuring albendazole by liquid chromatography-mass spectrometer
The instrument comprises the following steps: 1290 II ultra high performance liquid chromatography-G6470A triple quadrupole mass spectrometer (Agilent, USA);
a chromatographic column: ZORBAX Eclipse Plus C18Columns (3.0 mm. times.100 mm, 1.8 μm); column temperature: 25 ℃; sample introduction amount: 5 mu L of the solution; flow rate: 0.3m L/min; the gradient elution table is given in table 1 below.
TABLE 1 elution time program
An ion source: ESI; the detection mode is as follows: monitoring multiple reactions; positive ion spray voltage: 3000 v; atomizing gas pressure: 45 psi; temperature of the drying gas: 350 ℃; flow rate of drying gas: 3L/min; temperature of sheath gas: 350 ℃; the flow rate of the sheath gas: 12L/min, and the sheath gas is nitrogen. The detected ion pairs, collision gas energy and cone hole voltage are shown in table 2 below:
TABLE 2 Collection parameters of Prothioconazole (MRM model)
(5) Drawing of standard curve
And (4) injecting the standard series solution configured in the step (3) into a liquid chromatography-mass spectrometer, and measuring under the HPLC-MS/MS detection condition selected in the step (4). And drawing a standard working curve of the albendazole by taking the mass concentration (x, mg/L) of the albendazole as an abscissa and taking a corresponding response value (y) as an ordinate.
The standard curve equation y of the prothioconazole is 200000x +1834.8 (R)20.999), and then propylthiozole is obtainedthe peak areas of (A) are shown in Table 3, and the standard graph is shown in FIG. 1.
TABLE 3 Standard Curve for prothioconazole
As can be seen from Table 3, the peak area of prothioconazole in a certain linear range has a good linear relation with the mass concentration, and the correlation coefficient is 0.999.
(6) Method verification
adding standard working solution of prothioconazole into blank control samples of whole citrus fruit and pulp respectively to make the mass concentration of prothioconazole in whole citrus fruit or pulp respectively be 0.01, 0.10 and 1.00mg/kg, repeating each concentration for 5 times, measuring by using the selected analysis and detection method, and calculating the recovery rate. The results are shown in Table 4.
Table 4 spiked recovery of prothioconazole and its relative standard deviation (n ═ 5) in whole citrus fruit and pulp
Under the selected HPLC-MS/MS detection condition, the limit of the detection of the albendazole is 0.001mg/kg, and the limit of the quantification of the albendazole in the whole citrus fruit and the whole citrus pulp is 0.01 mg/kg; the lowest detection limit indicates that the method can detect substances with lower content. Therefore, the method can be used for accurately analyzing the sample and has higher sensitivity.
The invention establishes an HPLC-MS/MS method for detecting prothioconazole in citrus, the standard curve equation is that y is 200000x +1834.8, and the correlation coefficient R2The method has the advantages that the correlation is good, the limit of detection of the albendazole is 0.001mg/kg, the limit of quantification is 0.01mg/kg, the recovery rate of the citrus is 70.7-117.3%, the relative standard deviation is 2-4%, and the sensitivity, accuracy and precision of the method meet the requirements of pesticide residue detection.
(7) Calculation of measurement result of residual amount of sample solution
and (3) carrying out HPLC-MS/MS measurement on the to-be-measured solution of the citrus sample under the selected chromatographic conditions, measuring the chromatographic peak area of the albendazole in the citrus sample solution, and substituting the chromatographic peak area into the following formula to obtain the residual amount (mass concentration) of the albendazole in the sample solution.
The calculation formula of the prothioconazole in the citrus sample is as follows:
Wherein: x is the residual amount of the albendazole in the citrus sample, mg/kg; c, calculating the sample concentration of the citrus sample according to the peak area of the citrus sample through a standard curve: mg/L; m represents the sample weight and g represents the total weight of the sample; v- - -constant volume, mL.
(8) Determination of actual samples
Applying 20% albendazole suspending agent to east coast village of hibiscus region collected from Changsha city, Hunan province in 2018, adding water for dilution according to the active ingredient dosage of 133.3mg/kg (the dosage of the preparation is 1500 times liquid) and the mature period of oranges, and applying the pesticide by adopting a whole plant spraying method; the medicines are respectively applied for 3 times at intervals of 7d, the sampling time and the last application time are respectively 0d (2 h after the last application), 7d, 14d, 21d, 28d and 35 d. And detecting the residual quantity of the prothioconazole in the test paper. Some results are shown in tables 5-6.
TABLE 5 residual amount of prothioconazole in citrus pulp
TABLE 6 residual amount of prothioconazole in whole citrus fruit
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the present invention in any way, and the skilled in the art should cover within the scope of the present invention the modifications and equivalents of the embodiments within the technical scope of the present invention.
Claims (1)
1. A method for detecting the residual amount of prothioconazole in citrus is characterized by comprising the following steps:
a: uniformly cutting the collected citrus sample into 4 sections along a central axis, taking out non-adjacent 2 sections, uniformly mixing, and then carrying out homogenate by a homogenate machine and filling in a clean sealed plastic bag to obtain a citrus sample to be detected;
b: accurately weighing 10g of the citrus sample to be detected pretreated in the step a, placing the citrus sample into a 250mL triangular flask with a plug, adding 40mL-60mL of acetonitrile, carrying out oscillation extraction at 25 ℃ for 30min-60min, then carrying out vacuum filtration through a Buchner funnel, salting out with 2g of NaCl, standing for layering, sucking a half of organic phase supernatant, transferring the organic phase supernatant into a 250mL triangular flask with a ground opening, concentrating the organic phase supernatant to be nearly dry at 50 ℃ on a rotary evaporator, and carrying out volume fixing to 5.0mL by using chromatographic methanol to obtain an extracting solution;
c: transferring the extract into a 5.0mL centrifuge tube, adding 0.10g PSA adsorbent, vortexing on a vortex mixer for 1min, centrifuging on a centrifuge at 6000r/min for 3min, and filtering the supernatant with 0.22 μm organic filter membrane to obtain citrus sample detection solution to be detected;
And d, selecting a 1290 II ultra-performance liquid chromatography-G6470A triple quadrupole mass spectrometer produced by Agilent of America as an HPLC-MS/MS, and setting the chromatographic conditions: the chromatographic column is ZORBAX Eclipse Plus C18 column, 3.0mm × 100mm, 1.8 μm; column temperature: 25 ℃; sample introduction amount: 5 mu L of the solution; flow rate: 0.3m L/min; mobile phase composition: formic acid water solution with mass concentration of 0.1% and acetonitrile; mobile phase composition: formic acid water solution with mass concentration of 0.1% and acetonitrile; the conditions for gradient elution were: eluting with 90% formic acid water solution for 0.5min, then eluting with 10% formic acid water solution for 2.5min, and finally eluting with 90% formic acid water solution for 1.5min at flow rate of 0.30 mL/min; temperature of the drying gas: 350 ℃; flow rate of drying gas: 3L/min; temperature of sheath gas: 350 ℃; the flow rate of the sheath gas: 12L/min, and the sheath gas is nitrogen; the Fragmentmentor taper hole voltage is 97eV, the qualitative ion pair of the albendazole is 266.1/191, the energy of the collision gas is 32, and the quantitative ion pair is 266.1/234.1; the energy of the collision gas is 16, and under the condition, the retention time of the albendazole is 1.613 min;
e: accurately weighing standard prothioconazole and usingDissolving chromatographic methanol to prepare standard mother liquor, then respectively preparing the standard mother liquor of the albendazole into standard working solution by adopting a gradient dilution method, enabling the mass concentration of the albendazole to be 0.001, 0.005, 0.01, 0.05, 0.10, 0.50 and 1.00mg/L, respectively injecting the standard working solution into the HPLC-MS/MS selected in the step d for determination, respectively drawing a standard working curve of the albendazole by taking the mass concentration x of the albendazole as a horizontal coordinate and taking the corresponding chromatographic peak area y as a vertical coordinate, and further obtaining a standard curve equation of the albendazole: y 200000x +1834.8, correlation coefficient R2＝0.999；
f: and (e) injecting the citrus sample detection solution to be detected prepared in the step c into HPLC-MS/MS, detecting according to the chromatographic conditions in the step d, and substituting the measured chromatographic peak area into the standard curve equation of the prothioconazole in the step e to obtain the mass concentration of the prothioconazole in the citrus sample.
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| CN112083116A (en) * | 2020-09-29 | 2020-12-15 | 合肥海关技术中心 | Method for measuring residual quantity of prothioconazole and metabolite thioneazole thereof in apples |
| CN113396920A (en) * | 2021-05-07 | 2021-09-17 | 广东省农业科学院果树研究所 | Application of albendazole in preparation of pesticide bactericide for preventing and treating postharvest chloromycete of citrus |
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Cited By (2)
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| CN112083116A (en) * | 2020-09-29 | 2020-12-15 | 合肥海关技术中心 | Method for measuring residual quantity of prothioconazole and metabolite thioneazole thereof in apples |
| CN113396920A (en) * | 2021-05-07 | 2021-09-17 | 广东省农业科学院果树研究所 | Application of albendazole in preparation of pesticide bactericide for preventing and treating postharvest chloromycete of citrus |
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