CN108508130B - Method for splitting and measuring enantiomers of chiral pesticides metalaxyl and dimethomorph by ultra-high performance combined chromatography-tandem mass spectrometry technology - Google Patents
Method for splitting and measuring enantiomers of chiral pesticides metalaxyl and dimethomorph by ultra-high performance combined chromatography-tandem mass spectrometry technology Download PDFInfo
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Abstract
The invention belongs to the field of analytical chemistry and the technical field of pesticide residue detection, and particularly relates to ultra-high efficiencyA method for resolving and measuring chiral pesticides metalaxyl and dimethomorph enantiomers by a combined phase chromatography-tandem mass spectrometry technology relates to a method for resolving and quantifying racemes of various chiral pesticides. The method adopts a QuEChERS method to extract metalaxyl and dimethomorph in tobacco and dried fruits, and uses a combined phase chromatography chiral stationary phase and a triple quadrupole tandem mass spectrometry to synchronously detect enantiomers of 2 chiral pesticides of metalaxyl and dimethomorph. The invention adopts the combined phase chromatography to rapidly carry out chiral separation on metalaxyl and dimethomorph for the first time, and has high sensitivity. By supercritical CO2The organic solvent is a mobile phase, so that the use of a large amount of organic solvent is saved, and the environment is protected.
Description
Technical Field
The invention belongs to the field of analytical chemistry and the technical field of pesticide residue detection, in particular to a method for splitting and determining enantiomers of chiral pesticides metalaxyl and dimethomorph by an ultra-high performance combined chromatography-tandem mass spectrometry technology, and relates to a method for splitting and quantifying racemates of various chiral pesticides.
Background
25% of the currently used pesticides are chiral, the biological activity of the chiral pesticides has enantiomer difference, the activity of the chiral pesticides usually exists in one or a few enantiomers, and the resolution and tendency of the enantiomers of the chiral pesticides in the environment are also usually obviously different. Namely, the activity, toxicity, absorption, metabolism, degradation and the like of chiral pesticide enantiomers in natural environment and organisms can be greatly different.
The pesticide metalaxyl, chemical name D, L- (2, 6-dimethylphenyl) -N- (2' -methoxyethyl) methyl aminopropionate, is a high-efficiency bactericide which is easy to be absorbed by plants and conducts upwards. The pesticide is commercially available as its R, S racemate. However, pharmacological studies have shown that the main bactericidal effect of metalaxyl comes from the R-body. Hou nations et al [ analytical chemistry, 2003, 31(3),307-310 ] adopted a chiral chromatographic column to separate a group of enantiomers of metalaxyl by high performance liquid chromatography, but the chiral column of the method is complicated to synthesize and has long separation time. Dimethomorph usually has cis-isomer and trans-isomer (Z isomer and E isomer), and Z isomer has bactericidal function and belongs to effective components. Wherein the solubility of E isomer in water is twice of that of Z isomer, and besides different physical properties, the spectral effect and ionization efficiency are different [ Proc. in agro-pharmaceutical science, 2011, 13(2),169-173 ].
The structural formulas of the metalaxyl and the dimethomorph are shown as follows:
the two types of pesticides are also commonly used for preventing and treating the black shank of tobacco, and the detection rate in the tobacco is high, so that the establishment of a method for measuring the enantiomeric purity of metalaxyl and dimethomorph is necessary for developing and producing single products of R-type metalaxyl and Z-type dimethomorph and controlling the product quality of manufacturers.
Disclosure of Invention
The invention aims to provide a method for resolving and measuring enantiomers of chiral pesticides metalaxyl and dimethomorph by adopting a combined phase chromatography-tandem mass spectrometry technology, which can quickly and accurately separate a group of enantiomers of racemic metalaxyl and dimethomorph, can accurately quantify, has less matrix interference and is environment-friendly.
The purpose of the invention is realized by the following technical scheme:
a method for resolving and measuring enantiomers of chiral pesticides metalaxyl and dimethomorph by an ultra-high performance combined chromatography-tandem mass spectrometry technology comprises the following steps:
(1) pretreating a sample; the sample may be tobacco, grain or dried fruit.
(2) Detection conditions are as follows: performing combined chromatography-tandem mass spectrometry detection on a sample to be detected, separating each elution peak according to the retention time of the elution peak, the quantitative ion pair and the qualitative ion pair of the target compound to obtain each chiral pesticide enantiomer,
a. the detection conditions of the synthetic phase chromatography are as follows: a chromatographic column: ACQUITY UPC with specification of 150 mm multiplied by 3.0 mm and 2.5 mu m2A Trefoil CEL1 column; mobile phase: supercritical CO2Ethanol, flow rate: 2 mL/min; gradient elution; column temperature: 40 ℃; back pressure: 1600 psi; sample introduction amount: 2 muL;
b. the gradient elution mode is as follows: initial to 2 minute CO2The volume ratio of the alcohol to the CO is changed from 99 percent to 1 percent to 92 percent to 8 percent, and the CO is added from the 2 nd minute to the 3.5 th minute2The volume ratio of the alcohol to the CO is changed from 92 percent to 8 percent to 88 percent to 12 percent, and the CO is added from the 3.5 th minute to the 4 th minute2The volume ratio of the alcohol to the CO is changed from 88 percent to 12 percent to 70 percent to 30 percent, and the CO is added from the 4 th minute to the 5.5 th minute2The volume ratio of the alcohol to the CO is changed from 77 percent to 30 percent to 99 percent to 1 percent, and the CO is added from 5.5 minutes to 8 minutes2The volume ratio of the alcohol to the ethanol is 99 percent to 1 percent;
c. the method for separating each elution peak according to the retention time of the elution peak and the mass-to-charge ratio characteristics of the parent ion/daughter ion is as follows:
the retention time is 3.05 minutes, the elution peak with the quantitative ion pair of 280.1/192.1 and the qualitative ion pair of 280.1/220.1 is S-metalaxyl;
the elution peak with the retention time of 3.16 minutes, the quantitative ion pair of 280.1/192.1 and the qualitative ion pair of 280.1/220.1 is R-metalaxyl;
the retention time is 7.56 minutes, the elution peak with the quantitative ion pair of 388.1/165.0 and the qualitative ion pair of 388.1/300.9 is the E-dimethomorph;
the retention time is 7.70 minutes, the elution peak with the quantitative ion pair of 388.1/165.0 and the qualitative ion pair of 388.1/300.9 is the Z-dimethomorph;
(3) the detection method comprises the following steps: preparing a matrix mixed standard working solution of R-metalaxyl and E-dimethomorph, separating according to the chromatographic and mass spectrum conditions provided in the step (2), recording the peak area corresponding to each enantiomer, and obtaining a unitary linear regression equation of the R-metalaxyl and the E-dimethomorph by taking the concentration value of each enantiomer as an independent variable and the corresponding peak area as a dependent variable;
separating a sample to be detected according to the method, and recording the peak area corresponding to each enantiomer; substituting the peak area corresponding to each enantiomer into the unitary linear regression equation to obtain the concentration of each enantiomer in the sample to be detected.
In the present invention, the sample pretreatment process in step (1) is specifically as follows: accurately weighing 2 g of ground powder sample into a 50 mL centrifuge tube with a cover, adding 10mL of water, adding 10mL of acetonitrile after foaming, then placing the centrifuge tube on a vortex mixing and oscillating instrument, and oscillating for 5min at the speed of 2000 rpm; then adding 5g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5 g of disodium hydrogen citrate into the centrifuge tube, immediately oscillating for 5min at the speed of 2000rpm on a vortex mixing and oscillating instrument, and then centrifuging for 3 min at the speed of 6000 rpm; transferring 1.0 mL of the supernatant into a 1.5 mL centrifuge tube, adding 50 mg of C18 and 50 mg of neutral alumina, shaking for 2min at 2000rpm on a vortex mixing and shaking instrument, and centrifuging for 3 min at 6000 rpm; and (4) absorbing the supernatant, filtering the supernatant by using a 0.45-micron organic phase filter membrane, and diluting the filtrate by 2 times by using acetonitrile to obtain the sample solution to be detected.
In the mass spectrum condition in the step (2), the ion source is an electrospray ion source (ESI); the scanning mode is positive ion scanning; the capillary voltage is 2.6 KV; the ion source temperature is 150 ℃; the temperature of desolventizing gas is 350 ℃; the flow rate of the desolventizing gas is 800L/h; the flow rate of the gas in the taper hole is 50L/h; compensating a 0.1% methanoic acid solution of a solvent at a flow rate of 0.2 mL/min;
the declustering voltage and collision energy for each pesticide were as follows:
the declustering voltage of the metalaxyl quantitative ion pair and the declustering voltage of the qualitative ion pair are both 26V, and the collision energy is respectively 17V and 13V;
the declustering voltage of the dimethomorph quantitative ion pair and the declustering voltage of the dimethomorph qualitative ion pair are both 41V, and the collision energy is respectively 30V and 20V.
The unary linear regression equation of each pesticide in the step (3) is as follows:
r-metalaxyl: y =329X +879, linear range 25ng/mL-500ng/mL, linear correlation coefficient 0.9998;
e-dimethomorph: y =932X +4854, linear range 25ng/mL-500ng/mL, linear correlation coefficient 0.9996.
In the step (3), the specific method for preparing the matrix mixed standard working solution is as follows: respectively weighing 10 mg of R-metalaxyl and E-dimethomorph standard substances into a 10mL volumetric flask, dissolving the R-metalaxyl and the E-dimethomorph standard substances with acetonitrile, and fixing the volume to a scale to prepare a single standard stock solution of each pesticide; transferring a certain amount of single standard stock solution of each pesticide into a 100 mL volumetric flask, and performing constant volume to scale with acetonitrile to obtain a mixed standard stock solution; respectively transferring 25 muL, 50 muL, 100 muL, 250 muL, 500 muL and 1000 muL of the mixed standard stock solution into 6 10mL volumetric flasks, and performing constant volume by using acetonitrile to prepare a standard working solution; then respectively transferring 500 mu L of the standard working solution and 500 mu L of blank sample matrix solution to be mixed to prepare matrix mixed standard working solution.
The preparation method of the blank sample matrix solution in the step (3) comprises the following steps: accurately weighing 2 g of ground blank sample into a 50 mL centrifuge tube with a cover, adding 10mL of water, adding 10mL of acetonitrile after foaming, then placing the centrifuge tube on a vortex mixing and oscillating instrument, and oscillating for 5min at the speed of 2000 rpm. Then adding 5g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5 g of disodium hydrogen citrate into the centrifuge tube, immediately oscillating for 5min at the speed of 2000rpm on a vortex mixing and oscillating instrument, and then centrifuging for 3 min at the speed of 6000 rpm; transferring 1.0 mL of the supernatant into a 1.5 mL centrifuge tube, adding 50 mg of C18 and 50 mg of neutral alumina, shaking for 2min at 2000rpm on a vortex mixing and shaking instrument, and centrifuging for 3 min at 6000 rpm; the supernatant is sucked and filtered by a 0.45 mu m organic phase filter membrane, and the filtrate is reserved.
The invention realizes the separation and analysis of 2 chiral pesticides of metalaxyl and dimethomorph for the first time by combining the combination of the synthetic phase chromatography and the tandem mass spectrum. The method employs polysaccharidesThe chromatographic column of the chiral stationary phase splits the chiral pesticide enantiomer on a combined phase chromatographic system, inspects the influence of different mobile phase compositions, system backpressure and the like on the splitting, and optimizes the separation conditions. And then, the mass spectrum parameters of each pesticide are optimized, and an analysis method for synchronously separating the enantiomers of the metalaxyl and dimethomorph chiral pesticides is established. Finally, the enantiomer resolution method is adopted, after a sample is extracted by taking acetonitrile as an extraction solvent, an extracting solution is purified and then UPC is carried out2MS/MS analysis, good separation and determination of metalaxyl and dimethomorph enantiomers were obtained. In the method, the minimum detection limits of metalaxyl and dimethomorph are 0.0015 and 0.0018mg/kg respectively. The invention adopts supercritical CO2The organic solvent is a mobile phase, so that the use of a large amount of organic solvent is saved, and the environment is protected. The method uses the combined phase chromatography for rapid analysis, is beneficial to the separation of isomers, reduces the false positive results, has high analysis speed, takes only 8 minutes and has high sensitivity.
Drawings
FIG. 1: UPC of metalaxyl and dimethomorph standard solutions2MS/MS selective ion chromatograms (the figure is taken as abstract figure).
Detailed Description
The invention is further described below with reference to examples, but without limiting the invention.
Example 1:
1. instruments and reagents:
acetonitrile, methanol and ethanol are chromatographic grade reagents, and sodium citrate and sodium chloride are analytically pure reagents; distilled water, which meets the requirements of first-grade water in GB/T6682.
Waters TQD quadrupole tandem mass spectrometers; a water bath constant temperature oscillator; mettler AE 163 Switzerland electronic balance (sensory: 0.0001 g).
2. Sample treatment:
accurately weighing 2 g of the ground grain sample in a 50 mL centrifuge tube with a cover, adding 10mL of water, adding 10mL of acetonitrile after foaming, then placing the centrifuge tube on a vortex mixing and oscillating instrument, and oscillating for 5min at the speed of 2000 rpm. Then 5g of anhydrous magnesium sulfate and 1g of chloride were added to the centrifuge tubeAdding sodium, 1g of sodium citrate and 0.5 g of disodium hydrogen citrate into a centrifuge tube, immediately placing on a vortex mixing and shaking instrument, shaking at the speed of 2000rpm for 5min, and then centrifuging at the speed of 6000rpm for 3 min; 1.0 mL of the supernatant was removed in a 1.5 mL centrifuge tube and 50 mg of C18 and 50 mg of neutral alumina were added and shaken on a vortex mixer shaker at 2000rpm for 2min and centrifuged at 6000rpm for 3 min. The supernatant was aspirated and filtered through a 0.45 μm organic phase filter and diluted 2-fold with acetonitrile. Advanced ultra-high performance phase-coherent chromatography tandem mass spectrometry (UPC)2-MS/MS) detection; the sample to be tested is preferably tobacco and cereal.
3. Detection conditions are as follows: the detection conditions of the synthetic phase chromatography are as follows: a chromatographic column: ACQUITY UPC with specification of 150 mm multiplied by 3.0 mm and 2.5 mu m2A Trefoil CEL1 column; mobile phase: supercritical CO2Ethanol, flow rate: 2 mL/min; gradient elution; column temperature: 40 ℃; back pressure: 1600 psi; sample introduction amount: 2 muL; the gradient elution mode was as follows: initial to 2 minute CO2The volume ratio of the alcohol to the CO is changed from 99 percent to 1 percent to 92 percent to 8 percent, and the CO is added from the 2 nd minute to the 3.5 th minute2The volume ratio of the alcohol to the CO is changed from 92 percent to 8 percent to 88 percent to 12 percent, and the CO is added from the 3.5 th minute to the 4 th minute2The volume ratio of the alcohol to the CO is changed from 88 percent to 12 percent to 70 percent to 30 percent, and the CO is added from the 4 th minute to the 5.5 th minute2The volume ratio of the alcohol to the CO is changed from 77 percent to 30 percent to 99 percent to 1 percent, and the CO is added from 5.5 minutes to 8 minutes2The volume ratio of the alcohol to the ethanol is 99 percent to 1 percent;
mass spectrum conditions: the ion source is an electrospray ion source (ESI); the scanning mode is positive ion scanning; the capillary voltage is 2.6 KV; the ion source temperature is 150 ℃; the temperature of desolventizing gas is 350 ℃; the flow rate of the desolventizing gas is 800L/h; the flow rate of the gas in the taper hole is 50L/h; compensating a 0.1% methanoic acid solution of a solvent at a flow rate of 0.2 mL/min; the quantitative ion pair of metalaxyl is 388.1/165.0, the qualitative ion pair is 388.1/300.9, the cluster removing voltage of the quantitative ion pair and the qualitative ion pair is 26V, and the collision energy is 17V and 13V respectively; the quantitative ion pair of dimethomorph is 280.1/192.1, the qualitative ion pair is 280.1/220.1, the declustering voltage of the quantitative ion pair and the qualitative ion pair is 41V, and the collision energy is 30V and 20V respectively;
4. the determination method comprises the steps of mixing R-metalaxyl with known concentration and E-dimethomorph standard solution, diluting by 2 times with blank sample matrix, separating according to the provided chromatographic and mass spectrometric methods, recording the peak area corresponding to each enantiomer, and obtaining a unitary linear regression equation by taking the concentration value of each enantiomer as an independent variable and the corresponding peak area as a dependent variable.
Separating a sample to be detected according to the method provided by the previous step, and recording the peak area corresponding to each enantiomer; substituting the peak areas corresponding to each enantiomer into a unitary linear regression equation to obtain the concentrations of the E-dimethomorph and the Z-dimethomorph in the sample to be detected, which are respectively 1.22 mg/kg and 0.45 mg/kg.
For judging the accuracy of the method, 1.0 microgram of E-dimethomorph standard solution is added into the sample, the sample is pretreated, and UPC is adopted2And (4) measuring the area of the selected ion peak of the analyte by MS/MS, substituting the area into a standard curve to obtain that the content of the E-dimethomorph in the sample at the moment is 2.18 mg/kg, namely the standard recovery rate of the target substance is 98.2%, and indicating that the method is accurate.
Example 2:
another tobacco sample was selected as described in example 1, with S-metalaxyl and R-metalaxyl contents of 1.42 and 0.88mg/kg, respectively.
Claims (7)
1. A method for resolving and measuring enantiomers of chiral pesticides metalaxyl and dimethomorph by an ultra-high performance combined chromatography-tandem mass spectrometry technology is characterized by comprising the following steps:
(1) pretreating a sample;
(2) detection conditions are as follows: performing combined chromatography-tandem mass spectrometry detection on a sample to be detected, confirming each elution peak according to the retention time of the elution peak, the quantitative ion pair and the qualitative ion pair of the target compound to obtain each chiral pesticide enantiomer,
the detection conditions of the synthetic phase chromatography are as follows: a chromatographic column: ACQUITY UPC with specification of 150 mm multiplied by 3.0 mm and 2.5 mu m2A Trefoil CEL1 column; mobile phase: supercritical CO2Ethanol, flow rate: 2 mL/min; gradient elution; column temperature: 40 ℃; back pressure: 1600 psi; sample introduction amount: 2 muL;
the gradient elution mode is as follows: from the beginning to the end2min CO2The volume ratio of the alcohol to the CO is changed from 99 percent to 1 percent to 92 percent to 8 percent, and the CO is added from the 2 nd minute to the 3.5 th minute2The volume ratio of the alcohol to the CO is changed from 92 percent to 8 percent to 88 percent to 12 percent, and the CO is added from 3.5 minutes to 4 minutes2The volume ratio of the alcohol to the CO is changed from 88 percent to 12 percent to 70 percent to 30 percent, and the CO is added from the 4 th minute to the 5.5 th minute2The volume ratio of the alcohol to the CO is changed from 70 percent to 30 percent to 99 percent to 1 percent, and the CO is added from 5.5 minutes to 8 minutes2The volume ratio of the alcohol to the ethanol is 99 percent to 1 percent;
the method for confirming each elution peak according to the retention time of the elution peak, the quantitative ion pair and the qualitative ion pair of the target compound is as follows:
the retention time is 3.05 minutes, the elution peak with the quantitative ion pair of 280.1/192.1 and the qualitative ion pair of 280.1/220.1 is S-metalaxyl;
the elution peak with the retention time of 3.16 minutes, the quantitative ion pair of 280.1/192.1 and the qualitative ion pair of 280.1/220.1 is R-metalaxyl;
the retention time is 7.56 minutes, the elution peak with the quantitative ion pair of 388.1/165.0 and the qualitative ion pair of 388.1/300.9 is the E-dimethomorph;
the retention time is 7.70 minutes, the elution peak with the quantitative ion pair of 388.1/165.0 and the qualitative ion pair of 388.1/300.9 is the Z-dimethomorph;
(3) the detection method comprises the following steps: preparing a matrix mixed standard working solution of R-metalaxyl and E-dimethomorph, separating according to the chromatographic conditions provided in the step (2), recording the peak area corresponding to each enantiomer, and obtaining a unitary linear regression equation of the R-metalaxyl and the E-dimethomorph by taking the concentration value of each enantiomer as an independent variable and the corresponding peak area as a dependent variable;
separating a sample to be detected according to the method, and recording the peak area corresponding to each enantiomer; substituting the peak area corresponding to each enantiomer into the unitary linear regression equation to obtain the concentration of each enantiomer of dimethomorph and metalaxyl in the sample to be detected.
2. The method for resolving and determining enantiomers of chiral pesticides metalaxyl and dimethomorph according to claim 1, characterized in that: the sample pretreatment process in the step (1) is specifically as follows: accurately weighing 2 g of ground powder sample into a 50 mL centrifuge tube with a cover, adding 10mL of water, adding 10mL of acetonitrile after foaming, then placing the centrifuge tube on a vortex mixing and oscillating instrument, and oscillating for 5min at the speed of 2000 rpm; then adding 5g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5 g of disodium hydrogen citrate into the centrifuge tube, immediately oscillating for 5min at the speed of 2000rpm on a vortex mixing and oscillating instrument, and then centrifuging for 3 min at the speed of 6000 rpm; transferring 1.0 mL of the supernatant into a 1.5 mL centrifuge tube, adding 50 mgC18 and 50 mg of neutral alumina, shaking for 2min at 2000rpm on a vortex mixing and shaking instrument, and centrifuging for 3 min at 6000 rpm; and (4) absorbing the supernatant, filtering the supernatant by using a 0.45-micron organic phase filter membrane, and diluting the filtrate by 2 times by using acetonitrile to obtain the sample solution to be detected.
3. The method for resolving and determining enantiomers of chiral pesticides metalaxyl and dimethomorph according to claim 1, characterized in that: in the mass spectrum condition in the step (2), the ion source is an electrospray ion source (ESI); the scanning mode is positive ion scanning; the capillary voltage is 2.6 KV; the ion source temperature is 150 ℃; the temperature of desolventizing gas is 350 ℃; the flow rate of the desolventizing gas is 800L/h; the flow rate of the gas in the taper hole is 50L/h; compensating a 0.1% methanoic acid solution of a solvent at a flow rate of 0.2 mL/min;
the declustering voltage and collision energy for each pesticide were as follows:
the declustering voltage of the metalaxyl quantitative ion pair and the declustering voltage of the qualitative ion pair are both 26V, and the collision energy is respectively 17V and 13V;
the declustering voltage of the dimethomorph quantitative ion pair and the declustering voltage of the dimethomorph qualitative ion pair are both 41V, and the collision energy is respectively 30V and 20V.
4. The method for resolving and determining enantiomers of chiral pesticides metalaxyl and dimethomorph according to claim 1, characterized in that: the unary linear regression equation of the two pesticides in the step (3) is as follows:
r-metalaxyl: y =329X +879, linear range 25ng/mL-500ng/mL, linear correlation coefficient 0.9998;
e-dimethomorph: y =932X +4854, linear range 25ng/mL-500ng/mL, linear correlation coefficient 0.9996.
5. The method for resolving and determining enantiomers of chiral pesticides metalaxyl and dimethomorph according to claim 1, characterized in that: the specific method for preparing the matrix mixed standard working solution in the step (3) is as follows: respectively weighing 10 mg of R-metalaxyl and E-dimethomorph standard substances into a 10mL volumetric flask, dissolving the R-metalaxyl and the E-dimethomorph standard substances with acetonitrile, and fixing the volume to a scale to prepare a single standard stock solution of each pesticide; transferring a certain amount of single standard stock solution of each pesticide into a 100 mL volumetric flask, and performing constant volume to scale with acetonitrile to obtain a mixed standard stock solution; respectively transferring 25 muL, 50 muL, 100 muL, 250 muL, 500 muL and 1000 muL of the mixed standard stock solution into 6 10mL volumetric flasks, and performing constant volume by using acetonitrile to prepare a standard working solution; then respectively transferring 500 mu L of the standard working solution and 500 mu L of blank sample matrix solution to be mixed to prepare matrix mixed standard working solution.
6. The method for resolving and determining enantiomers of chiral pesticides metalaxyl and dimethomorph according to claim 5, characterized in that: the preparation method of the blank sample matrix solution comprises the following steps: accurately weighing 2 g of ground blank sample into a 50 mL centrifuge tube with a cover, adding 10mL of water, adding 10mL of acetonitrile after foaming, then placing the centrifuge tube on a vortex mixing and oscillating instrument, and oscillating for 5min at the speed of 2000 rpm; then adding 5g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5 g of disodium hydrogen citrate into the centrifuge tube, immediately oscillating for 5min at the speed of 2000rpm on a vortex mixing and oscillating instrument, and then centrifuging for 3 min at the speed of 6000 rpm; transferring 1.0 mL of the supernatant into a 1.5 mL centrifuge tube, adding 50 mgC18 and 50 mg of neutral alumina, shaking for 2min at 2000rpm on a vortex mixing and shaking instrument, and centrifuging for 3 min at 6000 rpm; the supernatant is sucked and filtered by a 0.45 mu m organic phase filter membrane, and the filtrate is reserved.
7. The method for resolving and determining enantiomers of chiral pesticides metalaxyl and dimethomorph according to claim 1, characterized in that: the sample is tobacco, grain or dried fruit.
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| CN106226432A (en) * | 2016-08-09 | 2016-12-14 | 中国水稻研究所 | A kind of edible rice safe mass stage division |
| CN107478737B (en) * | 2017-07-18 | 2021-05-04 | 贵州茅台酒股份有限公司 | Method for detecting residual quantity of 80 pesticides in white spirit |
| CN107721945B (en) * | 2017-09-08 | 2020-10-13 | 南京农业大学 | Chiral complementary alkyl oxazinone compound and application thereof as bactericide |
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