CN114814027B - Method for determining residual quantity of tebufenpyrad and cyenopyrafen in plant-derived product by gas chromatography-triple quadrupole mass spectrometry - Google Patents
Method for determining residual quantity of tebufenpyrad and cyenopyrafen in plant-derived product by gas chromatography-triple quadrupole mass spectrometry Download PDFInfo
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Abstract
The invention discloses a method for determining residual quantity of cyenopyrafen and cyenopyrafen in a plant-derived product by gas chromatography-triple quadrupole mass spectrometry. Sample pretreatment and chromatographic conditions are optimized, residual tebufenpyrad and cyromazine in a plant-derived product are extracted by n-hexane-acetone (1, 2, V).
Description
Technical Field
The invention belongs to the technical field of measuring the residual quantity of the cyenopyrafen and the cyenopyrafen in plant-derived products, and particularly relates to a method for measuring the residual quantity of the cyenopyrafen and the cyenopyrafen in the plant-derived products by a gas chromatography-triple quadrupole mass spectrometry method.
Background
The cyenopyrafen is also called diafenthiuron. The foreign trade name Genite; genitol. In 1947, it was promoted by Allied Chemical Corporation as an acaricide, which is a non-systemic acaricide. Cyenopyrafen is also an acaricide and has little related information. The national food safety standard GB 2763-2021 maximum pesticide residue limit in food safety national standard food sets temporary limit (0.01 mg/kg) in vegetable products such as vegetables, fruits, grains, oil materials, tea leaves, seasonings, medicinal plants and the like for the geifer and the cyenopyrafen, but no quantitative detection method for the geifer and the cyenopyrafen in mature and available vegetable products exists at present, so that the establishment of the rapid, sensitive and reliable quantitative detection method for the geifer and the cyenopyrafen in the vegetable products has important significance for providing technical support for related research works such as monitoring the residues of the geifer and the cyenopyrafen in the vegetable products, risk assessment and the like. The residue detection methods of the tebufenpyrad and cyenopyrafen are rarely reported.
Disclosure of Invention
The invention aims to solve the existing problems and provides a method for determining the residual quantity of the cyenopyrafen and the cyenopyrafen in a plant-derived product by using a gas chromatography-triple quadrupole mass spectrometry method.
The invention is realized by the following technical scheme:
a method for determining the residual quantity of the cyenopyrafen and the cyenopyrafen in a plant-derived product by a gas chromatography-triple quadrupole mass spectrometry method comprises the following steps:
s1, sample pretreatment:
s101, chopping and homogenizing a vegetable and fruit sample, and fully and uniformly mixing crushed grains, tea leaves, oil materials, seasonings and medicinal plants;
s102, weighing 10g of vegetable and fruit samples into a 50mL plastic centrifuge tube;
s103, weighing 5g of cereal, tea, oil, seasoning and medicinal plant samples, putting the samples into a 50mL plastic centrifuge tube, and adding 10mL of saturated saline solution to soak for 30min;
s104, adding 4g of sodium chloride and 10mL of extraction solvent, homogenizing a ceramic proton, and performing vortex oscillation extraction for 10min; centrifuging at 4000r/min for 3min;
s105, accurately sucking 1.5mL of supernatant into a 2mL polypropylene centrifuge tube, mixing for 1min in a vortex mode, centrifuging for 3min at 14000r/min, and taking the supernatant to pass through a 0.22-micron organic filter membrane for determination;
s2, preparing a standard solution:
s201, accurately weighing a proper amount of the standard products of the cyenopyrafen and the cyenopyrafen, and preparing standard stock solutions with mass concentration of 1000mg/L by using acetone respectively;
s202, respectively sucking a proper amount of the standard stock solutions, and preparing a mixed standard intermediate solution of 10mg/L by using acetone;
s203, sucking the mixed standard intermediate solution, and diluting the mixed standard intermediate solution into mixed standard working solution with the mass concentration of 2.5 mu g/L, 10 mu g/L, 50 mu g/L, 100 mu g/L and 250 mu g/L by using acetone;
s3, researching matrix effect:
preparing a blank matrix solution according to the S1 pretreatment method, preparing a standard working solution according to the S2 method, performing on-machine detection on the matrix matching standard working solution, and evaluating the purified matrix effect: matrix effect (ME,%) = [ (matrix matching calibration curve slope/pure solvent standard curve rate) -1] × 100, | ME | <20% is weak matrix effect, negligible without taking compensation measures; medium substrate effect is achieved when the proportion of ME is more than or equal to 20% and less than or equal to 50%, strong substrate effect is achieved when the proportion of ME is more than or equal to 50%, and measures are needed to compensate the substrate effect;
s4, instrument conditions:
column box temperature program: maintaining at 100 deg.C for 0min, heating to 200 deg.C at 20 deg.C/min, and maintaining for 0min; heating to 270 deg.C at a rate of 10 deg.C/min, and maintaining for 1min; finally, heating to 310 ℃ at a speed of 30 ℃/min, and keeping for 1min;
carrier gas: helium with purity not less than 99.999%, and flow rate of 1.0mL/min in constant flow mode;
sample inlet temperature: 280 ℃;
sample introduction amount: 1 mu L of the solution;
and (3) sample introduction mode: no shunt sampling;
electron bombardment source: 70eV;
ion source temperature: 300 ℃;
transmission line temperature: 280 ℃;
solvent retardation: 4min;
detecting by adopting a multi-reaction monitoring mode;
s5, detecting an actual sample:
5 samples of Shanghai green, celery, cucumber, carrot, ginger, apple, orange, rice, corn, peanut, tea, cumin and pseudo-ginseng purchased in the market are respectively detected.
Furthermore, the weight of the vegetables and fruits in step S102 and the weight of the cereals, tea leaves, oil materials, seasonings and medicinal plants in step S103 are all accurately measured to be 0.01g.
Further, step S104 further includes:
s1041, selecting an extraction solvent:
selecting n-hexane-acetone, n-hexane, ethyl acetate and acetonitrile with a volume ratio of 1.
Further, the polypropylene centrifuge tube described in step S105 is filled with a purification reagent and an adsorbent.
Further, the method also comprises the selection of purifying reagents and the optimization of the dosage of the adsorbent.
Further, the mixed standard working solution described in step S203 is ready for use.
Further, the standard solutions obtained in step S2 were stored at a temperature below-18 ℃.
Further, step S4 further includes:
s401, selection of mass spectrum conditions:
selecting 10.0mg/L of tebufenpyrad and cyenopyrafen acetone solution, and carrying out full scanning on the tebufenpyrad and the cyenopyrafen within the mass number range of 50-400; selecting fragment ions with larger mass number and higher response to carry out secondary fragmentation, and optimizing collision voltage by adopting Auto SRM (sequence-related resonance) software of the instrument;
s402, selecting a chromatographic column:
the separation effect of two columns, TG-5SILMS with a specification of 30m 0.25mm 0.25 μm and TG-1701MS with a specification of 30m 0.25mm 0.25 μm, on the cyenopyrafen and cyenopyrafen was compared.
Further, the multiple reaction monitoring mode described in step S4: the method comprises the following steps that a quantitative ion pair and two qualitative ion pairs are respectively selected for the cyenopyrafen and the cyenopyrafen, the retention time of the cyenopyrafen is 10.43min, the quantitative ion pair 141.0>77.0, the collision energy is 10eV, the qualitative ion pair 141.0>51.0 and the collision energy is 30eV; the qualitative ion pair 302.0 is more than 76.9, and the collision energy is 20eV; the retention time of cyromazine is 11.12min, the quantitative ion pair 86.8 >; the qualitative ion pair 86.8 is greater than 41.0, and the collision energy is 20eV.
Further, step S4 further includes:
s403, determining a linear range, a correlation coefficient and a method detection limit:
preparing a series of standard working solution of the gefarnate and the cyenopyrafen with the concentration of 2.5 mug/L, 10 mug/L, 50 mug/L, 100 mug/L and 250 mug/L by using acetone, detecting according to the instrument condition, drawing a standard working curve by taking the mass concentration of the gefarnate and the cyenopyrafen as a horizontal coordinate and taking the peak area Y of the gefarnate and the cyenopyrafen as a vertical coordinate, and obtaining a linear equation and a correlation coefficient; adding a proper amount of standard solution into the blank sample solution, and performing on a machine for measurement, wherein the quantitative limit is determined according to S/N = 10;
s404, determination of recovery rate and precision:
the blank samples of green vegetables, celery, cucumbers, tomatoes, carrots, gingers, apples, oranges, brown rice, corns, peanuts, tea leaves, cumin and pseudo-ginseng are subjected to standard addition recovery experiments with different concentrations, and each addition level is measured for 6 times and is parallel.
Compared with the prior art, the invention has the following advantages:
1. according to the method, the residual tebufenpyrad and cyromazine in the plant-derived product are extracted by n-hexane-acetone (1, 2, V: V), the extracting solution is subjected to dispersive solid-phase extraction and purification, and in combination with the national food safety standard on the residual limit requirements of the tebufenpyrad and the cyromazine, a gas chromatography-triple quadrupole mass spectrometer is adopted to establish the detection method of the tebufenpyrad and the cyromazine in the plant-derived product, and the established method is simple and convenient to operate and can meet the detection requirements of the residual tebufenpyrad and the cyromazine in the plant-derived product.
2. The application establishes a detection method for simultaneously determining the residual quantity of the cyenopyrafen and the cyenopyrafen in the plant-derived products by using a gas chromatography-triple quadrupole mass spectrometry method, and the method has good detection sensitivity and accuracy. The method is simple to operate, high in sensitivity, good in recovery rate and high in accuracy, can meet the detection requirements and relevant regulatory requirements of the residual cyenopyrafen and cyenopyrafen in the plant-derived products, and can provide effective technical support for risk monitoring of the residual cyenopyrafen and cyenopyrafen in the plant-derived products.
Drawings
FIG. 1 is a graph of ion chromatograms of extracted gramicidin and cyenopyrafen;
FIG. 2 is a graph showing the effect of different extraction solvents on the geifer and cyenopyrafen;
FIG. 3 is a graph of the effect of different adsorbent combinations on extraction recovery of spiked blank samples;
FIG. 4 shows the matrix effect of the cyenopyrafen and cyenopyrafen in different samples;
FIG. 5 is a second order mass spectrum of the cyenopyrafen and cyenopyrafen;
FIG. 6 is ion chromatograms of extracted green vegetable blank sample and labeled sample;
FIG. 7 is an ion chromatogram extracted from a blank sample and a labeled sample of celery;
FIG. 8 is ion chromatograms of cucumber blank sample and labeled sample;
FIG. 9 is ion chromatograms of tomato blank and spiked samples;
FIG. 10 is ion chromatograms of carrot blank sample and labeled sample;
FIG. 11 is ion chromatograms of extracted ginger blank sample and labeled sample;
FIG. 12 is an ion chromatogram for the extraction of apple blank and spiked samples;
FIG. 13 is an ion chromatogram for extraction of orange blank sample and spiked sample;
FIG. 14 is ion chromatograms of brown rice blank sample and labeled sample;
FIG. 15 is ion chromatograms of extracted corn blank and spiked samples;
FIG. 16 is ion chromatograms of extracted peanut blank samples and spiked samples;
FIG. 17 is ion chromatograms of extracted blank samples and labeled samples of tea leaves;
FIG. 18 shows ion chromatograms of extracted cumin blank sample and labeled sample;
FIG. 19 is an ion chromatogram of extracted Notoginseng radix blank sample and labeled sample.
Detailed Description
For further explanation of the present invention, reference will now be made to the following specific examples.
A method for determining the residual quantity of the cyenopyrafen and the cyenopyrafen in a plant-derived product by a gas chromatography-triple quadrupole mass spectrometry method comprises the following steps:
s1, sample pretreatment:
s101, chopping and homogenizing a vegetable and fruit sample, and fully and uniformly mixing crushed grains, tea leaves, oil materials, seasonings and medicinal plants;
s102, weighing 10g of vegetable and fruit (accurate to 0.01 g) sample in a 50mL plastic centrifuge tube;
s103, weighing 5g of grains, tea leaves, oil plants, seasonings and medicinal plants (accurate to 0.01 g) into a 50mL plastic centrifuge tube, and adding 10mL of saturated salt water to soak for 30min;
s104, adding 4g of sodium chloride and 10mL of extraction solvent, homogenizing a ceramic proton, and performing vortex oscillation extraction for 10min; centrifuging at 4000r/min for 3min;
s1041, selection of extraction solvent:
selecting n-hexane-acetone, n-hexane, ethyl acetate and acetonitrile with a volume ratio of 1.
As can be seen from fig. 2: when n-hexane and ethyl acetate are used as extraction solvents, the extraction recovery rates of the cyenopyrafen and the cyenopyrafen in the matrixes of the green vegetables, the apples and the peanuts are lower than 70 percent, and the requirements of a detection method cannot be met; when acetonitrile is used as an extraction solvent, the extraction recovery rate of the cyenopyrafen and the cyenopyrafen in the peanut matrix is lower than 70 percent, and the requirement of a detection method cannot be met; when n-hexane-acetone (1, 2, v).
S105, accurately sucking 1.5mL of supernatant into a 2mL polypropylene centrifuge tube (filled with a purification reagent and an adsorbent), mixing by vortex for 1min, centrifuging for 3min at 14000r/min, and filtering the supernatant with a 0.22-micron organic filter membrane for determination;
s1051, selecting a purifying reagent;
common QuEChERS purifiers are GCB and C 18 PSA and NH 2 Adsorbents, etc., of which PSA and NH 2 The adsorption action mechanism of the adsorbent is similar, both the adsorbent and the adsorbent have weak anion exchange capacity, and organic acid, polar pigment, fatty acid, saccharide and other components capable of forming hydrogen bonds in a sample can be effectively removed through the action of the hydrogen bonds and the compound; c 18 Can remove nonpolar compounds such as volatile oil, terpenes, and lipids, and GCB can remove pigment and carotenoidInterference of steroid and plane structure impurity, anhydrous magnesium sulfate can remove water in sample liquid, and C is examined 18 GCB, PSA and MgSO 4 The recovery rate of the four purifying reagents after adsorbing the mixed standard solution of the cyenopyrafen and the cyenopyrafen of 0.2mg/L is shown by experimental results, and the average adsorption recovery rate of the four purifying reagents to the cyenopyrafen and the cyenopyrafen is between 90 and 110 percent, so that the four purifying reagents can meet the requirement of an analysis method;
s2052, optimizing the dosage of the adsorbent:
the plant source samples are various in types and the matrixes are relatively complex, so that two or more adsorption purifiers need to be considered when dispersed solid phase extraction purification is used, and impurities which interfere with the analysis of an instrument, such as pigments, lipids and the like in the samples, can be removed well. Experiment is compounded with three groups of adsorbent combinations with different contents (I: 5mg PSA +5mg GCB +5mg C 18 +50mg MgSO 4 ，Ⅱ：20mg PSA+20mg GCB+20mg C 18 +50mg MgSO 4 ，Ⅲ：50mg PSA+50mg GCB+50mg C 18 +50mg MgSO 4 ) Purifying 0.099mg/kg of a blank sample of vegetables, fruits, grains, oil, tea leaves, seasonings and medicinal plants, namely green vegetables, apples, brown rice, peanuts, tea leaves, cumin and pseudo-ginseng blank samples, and adding 1.5mL of a standard sample extracting solution; the extraction and purification experiment step is carried out according to the step 1, and the purification effect and the addition recovery rate of different combined adsorbents are inspected; the result is shown in fig. 3, along with the gradual increase of the dosage of the adsorbent, the recovery rates of the cyenopyrafen and the cyenopyrafen are changed to a certain extent, compared with the situation that the substrate is not purified, the recovery rates of the cyenopyrafen and the cyenopyrafen in the substrate with higher partial recovery rates are reasonably restored, and the average recovery rates of the cyenopyrafen and the cyenopyrafen after the purification by using the combinations II and III can meet the requirement of GB/T27404-2008 'laboratory quality control standard product physicochemical detection' on the recovery rate (70% -120%); comprehensively considering the purification effect, cost, convenience, and time-base line interference of instrument analysis, 20mg PSA +20mg GCB +20mg C is selected 18 +50mg MgSO 4 Purifying the sample by combining;
s2, preparing a standard solution:
s201, accurately weighing a proper amount of the standard products of the cyenopyrafen and the cyenopyrafen, and preparing standard stock solutions with mass concentration of 1000mg/L by using acetone respectively;
s202, respectively sucking a proper amount of the standard stock solutions, and preparing a mixed standard intermediate solution of 10mg/L by using acetone;
s203, sucking the mixed standard intermediate solution, and diluting the mixed standard intermediate solution into mixed standard working solution with the mass concentration of 2.5 mu g/L, 10 mu g/L, 50 mu g/L, 100 mu g/L and 250 mu g/L by using acetone;
s3, exploring matrix effect:
preparing a blank matrix solution according to an S1 pretreatment method, preparing a standard working solution according to an S2 method, performing on-machine detection on the standard working solution matched with the matrix, and evaluating the matrix effect after purification: matrix effect (ME,%) = [ (matrix matching calibration curve slope/pure solvent standard curve rate) -1] × 100, | ME | <20% is weak matrix effect, negligible without taking compensation measures; medium-level matrix effect is achieved when the absolute value of ME is more than or equal to 20% and less than or equal to 50%, strong matrix effect is achieved when the absolute value of ME is more than or equal to 50%, and measures are required to compensate the matrix effect; the matrix effect of the cyenopyrafen and cyenopyrafen is shown in figure 4, wherein the matrix effect (ME value is 5-18%) of the cyenopyrafen in 14 kinds of matrixes; the cyenopyrafen has a matrix effect (ME value is 3-18%) in 14 kinds of matrixes, and the matrix effects of the cyenopyrafen and the cyenopyrafen after purification are both weak matrix effects and can be compensated without taking measures;
s4, instrument conditions:
column box temperature program: maintaining at 100 deg.C for 0min, heating to 200 deg.C at 20 deg.C/min, and maintaining for 0min; heating to 270 deg.C at a rate of 10 deg.C/min, and maintaining for 1min; finally, heating to 310 ℃ at a speed of 30 ℃/min, and keeping for 1min;
carrier gas: helium with purity not less than 99.999%, and flow rate of 1.0mL/min in constant flow mode;
sample inlet temperature: 280 ℃;
sample injection amount: 1 mu L of the solution;
and (3) sample introduction mode: no-shunt sample introduction;
electron bombardment source: 70eV;
ion source temperature: 300 ℃;
transmission line temperature: 280 ℃;
solvent retardation: 4min;
detecting by adopting a multi-reaction monitoring mode;
s401, selection of mass spectrum conditions:
selecting 10.0mg/L of the cyenopyrafen and cyenopyrafen acetone solution, and carrying out full scanning on the cyenopyrafen and the cyenopyrafen within the mass number range of 50-400; selecting fragment ions with larger mass number and higher response to carry out secondary fragmentation, and optimizing collision voltage by adopting Auto SRM (sequence-related resonance) software of the instrument;
the quantitative ion pair, the qualitative ion pair and the collision energy of the cyenopyrafen and the cyenopyrafen are shown in table 1, the secondary mass chromatogram of the cyenopyrafen and the cyenopyrafen is shown in figure 5, and the extraction ion chromatogram of the cyenopyrafen and the cyenopyrafen in the 0.1mg/L mixed standard solution is shown in figure 1;
TABLE 1 retention time, quantitative ion-pair, qualitative ion-pair and collision energy for the gemanfen and cyenopyrafen
S402, selecting a chromatographic column:
comparing the separation effect of two chromatographic columns of TG-5SILMS with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m and TG-1701MS with the specification of 30m multiplied by 0.25mm multiplied by 0.25 mu m on the cyenopyrafen and the cyenopyrafen, the result shows that the cyenopyrafen and the cyenopyrafen can be effectively retained and separated on the two chromatographic columns, and both have good peak patterns, but the peak area when the TG-5SILMS chromatographic column is adopted is higher than that of the TG-1701MS chromatographic column, and finally the TG-5SILMS chromatographic column is selected as the chromatographic column of the method;
s403, determining a linear range, a correlation coefficient and a method detection limit:
preparing a series of standard working solution of the gefarnate and the cyenopyrafen with the concentration of 2.5 mug/L, 10 mug/L, 50 mug/L, 100 mug/L and 250 mug/L by using acetone, detecting according to the instrument condition, drawing a standard working curve by using the mass concentration (X, mug/L) of the gefarnate and the cyenopyrafen as a horizontal coordinate and using the peak area Y of the gefarnate and the cyenopyrafen as a vertical coordinate to obtain a linear equation and a correlation coefficient; adding an appropriate amount of standard solution to the blank sample solution, and performing on-machine measurement to determine a limit of quantitation (LOQ) with S/N = 10;
TABLE 2 regression equations, correlation coefficients, linear ranges and quantitative limits for the gramcast and cyenopyrafen
S404, determination of recovery rate and precision:
the green vegetable, celery, cucumber, tomato, carrot, ginger, apple, orange, brown rice, corn, peanut, tea, cumin and pseudo-ginseng blank samples are subjected to standard addition recovery experiments with different concentrations, each addition level is measured for 6 times, and the experimental data of the addition concentrations and the average recovery rates of the cyenopyrafen and the cyenopyrafen in the plant source samples are shown in table 3.
Table 3 mean spiked recovery and relative standard deviation of the gahnite and cyenopyrafen at three levels in different samples (n = 6)
S5, detecting an actual sample:
5 samples of vegetables, celery, cucumber, tomato, carrot, ginger, apple, orange, brown rice, corn, peanut, tea, cumin and pseudo-ginseng purchased in the market are respectively detected. Extracted ion chromatograms of blank samples and labeled samples of green vegetables, celery, cucumber, tomato, carrot, ginger, apple, orange, brown rice, corn, peanut, tea, cumin and pseudo-ginseng are shown in fig. 6-19.
The application establishes a detection method for simultaneously determining the residual quantity of the tebufenpyrad and the cyenopyrafen in the plant-derived products by using a gas chromatography-triple quadrupole mass spectrometry method, and the method has good detection sensitivity and accuracy. The method is simple to operate, high in sensitivity, good in recovery rate and high in accuracy, can meet the detection requirements and relevant regulatory requirements of the residual cyenopyrafen and cyenopyrafen in the plant-derived products, and can provide effective technical support for risk monitoring of the residual cyenopyrafen and cyenopyrafen in the plant-derived products.
Claims (5)
1. A method for determining the residual quantity of the cyenopyrafen and the cyenopyrafen in a plant-derived product by a gas chromatography-triple quadrupole mass spectrometry method is characterized by comprising the following steps of:
s1, sample pretreatment:
s101, respectively chopping and homogenizing green vegetables, celery, cucumbers, tomatoes, carrots, gingers, apples and oranges, respectively crushing brown rice, corns, peanuts, tea leaves, cumin and pseudo-ginseng samples, and fully mixing;
s102, respectively weighing 10g of green vegetables, celery, cucumbers, tomatoes, carrots, gingers, apples and oranges in a 50mL plastic centrifuge tube;
s103, weighing 5g of brown rice, corn, peanut, tea, cumin and pseudo-ginseng samples respectively, putting the brown rice, corn, peanut, tea, cumin and pseudo-ginseng samples into a 50mL plastic centrifuge tube, and adding 10mL of saturated saline solution to soak for 30min;
s104, adding 4g of sodium chloride and 10mL of extraction solvent, homogenizing a ceramic proton, and performing vortex oscillation extraction for 10min; centrifuging at 4000r/min for 3min;
wherein the extraction solvent is n-hexane-acetone with a volume ratio of 1;
s105, accurately sucking 1.5mL of supernatant into a 2mL polypropylene centrifuge tube, carrying out vortex mixing for 1min, carrying out centrifugation for 3min at 14000r/min, and taking the supernatant to pass through a 0.22-micron organic filter membrane for determination;
the polypropylene centrifugal tube in the step S105 is filled with a purification reagent;
wherein the purification reagent is 20mgPSA +20mgGCB +20mgC 18 +50mgMgSO 4 Composition is carried out;
s2, preparing a standard solution:
s201, accurately weighing a proper amount of the standard products of the cyenopyrafen and the cyenopyrafen, and preparing standard stock solutions with mass concentration of 1000mg/L by using acetone respectively;
s202, respectively sucking a proper amount of the standard stock solutions, and preparing a mixed standard intermediate solution of 10mg/L by using acetone;
s203, sucking the mixed standard intermediate solution, and diluting the mixed standard intermediate solution into mixed standard working solution with the mass concentration of 2.5 mu g/L, 10 mu g/L, 50 mu g/L, 100 mu g/L and 250 mu g/L by using acetone;
s3, researching matrix effect:
preparing a blank matrix solution according to the S1 pretreatment method, preparing a standard working solution according to the S2 method, performing on-machine detection on the matrix matching standard working solution, and evaluating the purified matrix effect: matrix effect (ME,%) = [ (matrix matching calibration curve slope/pure solvent standard curve rate) -1] × 100, | ME | <20% is weak matrix effect, negligible without taking compensation measures; medium-level matrix effect is achieved when the absolute value of ME is more than or equal to 20% and less than or equal to 50%, strong matrix effect is achieved when the absolute value of ME is more than or equal to 50%, and measures are required to compensate the matrix effect;
s4, instrument conditions:
a chromatographic column: a TG-5SILMS column of specification 30m × 0.25mm × 0.25 μm;
column box temperature program: maintaining at 100 deg.C for 0min, heating to 200 deg.C at 20 deg.C/min, and maintaining for 0min; heating to 270 deg.C at a rate of 10 deg.C/min, and maintaining for 1min; finally, heating to 310 ℃ at a speed of 30 ℃/min, and keeping for 1min;
carrier gas: helium with purity not less than 99.999%, and flow rate of 1.0mL/min in constant flow mode;
sample inlet temperature: 280 ℃;
sample introduction amount: 1 mu L of the solution;
and (3) sample introduction mode: no shunt sampling;
electron bombardment source: 70eV;
ion source temperature: 300 ℃;
transmission line temperature: 280 ℃;
solvent retardation: 4min;
detecting by adopting a multi-reaction monitoring mode;
in step S4, the multiple reaction monitoring mode: the method comprises the following steps that a quantitative ion pair and two qualitative ion pairs are respectively selected for the cyenopyrafen and the cyenopyrafen, the retention time of the cyenopyrafen is 10.43min, the quantitative ion pair 141.0> < 77.0 >, the collision energy is 10eV, the qualitative ion pair 141.0> < 51.0 > and the collision energy is 30eV; the qualitative ion pair 302.0 is more than 76.9, and the collision energy is 20eV; the retention time of cyromazine is 11.12min, the quantitative ion pair 86.8 is 45.0, the collision energy is 10eV, and the qualitative ion pair 86.8 is 43.0, the collision energy is 10eV; the qualitative ion pair 86.8 is more than 41.0, and the collision energy is 20eV;
s5, detecting an actual sample:
5 samples of vegetables, celery, cucumber, tomato, carrot, ginger, apple, orange, brown rice, corn, peanut, tea, cumin and pseudo-ginseng purchased in the market are respectively detected.
2. The method for determining the residual quantity of the tebufenpyrad and the cyenopyrafen in the plant-derived product by using the gas chromatography-triple quadrupole mass spectrometry as claimed in claim 1, wherein the weight of the green vegetables, celery, cucumbers, tomatoes, carrots, gingers, apples and oranges in step S102 and the weight of the brown rice, the corns, the peanuts, the tea leaves, the cumin and the pseudo-ginseng in step S103 are accurately measured to be 0.01g.
3. The method for determining the residual quantity of the tebufenpyrad and the cyenopyrafen in the plant-derived product by using the gas chromatography-triple quadrupole mass spectrometry as claimed in claim 1, wherein the mixed standard working solution in the step S203 is prepared as it is.
4. The method for determining the residual quantity of the cyenopyrafen and the cyenopyrafen in the plant-derived product by using the gas chromatography-triple quadrupole mass spectrometry as claimed in claim 1, wherein the standard solutions obtained in the step S2 are all stored at a temperature below-18 ℃.
5. The method for determining the residual quantity of the tebufenpyrad and the cyenopyrafen in the plant-derived product by using the gas chromatography-triple quadrupole mass spectrometry as claimed in claim 1, wherein the step S4 further comprises the following steps:
s401, determination of a linear range, a correlation coefficient and a method detection limit:
preparing a series of 2.5 mu g/L, 10 mu g/L, 50 mu g/L, 100 mu g/L and 250 mu g/L mixed standard working solution of the tebufenpyrad and the cyenopyrafen by using acetone, detecting according to instrument conditions, drawing a standard working curve by taking the mass concentration of the tebufenpyrad and the cyenopyrafen as a horizontal coordinate and taking the peak area Y of the tebufenpyrad and the cyenopyrafen as a vertical coordinate, and obtaining a linear equation and a correlation coefficient; adding a proper amount of standard solution into the blank sample solution, and performing on-machine measurement, wherein the quantitative limit is determined according to S/N = 10;
s402, determination of recovery rate and precision:
the blank samples of green vegetables, celery, cucumbers, tomatoes, carrots, gingers, apples, oranges, brown rice, corns, peanuts, tea leaves, cumin and pseudo-ginseng are subjected to standard addition recovery experiments with different concentrations, and each addition level is measured for 6 times and is parallel.
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| CN114295761A (en) * | 2022-01-19 | 2022-04-08 | 广东省中鼎检测技术有限公司 | Method for detecting cyenopyrafen |
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| CN114295761A (en) * | 2022-01-19 | 2022-04-08 | 广东省中鼎检测技术有限公司 | Method for detecting cyenopyrafen |
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