CN115047107B - Method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng - Google Patents
Method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng Download PDFInfo
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- 239000005782 Fluopicolide Substances 0.000 title claims abstract description 54
- GBOYJIHYACSLGN-UHFFFAOYSA-N fluopicolide Chemical compound ClC1=CC(C(F)(F)F)=CN=C1CNC(=O)C1=C(Cl)C=CC=C1Cl GBOYJIHYACSLGN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- YXKMMRDKEKCERS-UHFFFAOYSA-N cyazofamid Chemical compound CN(C)S(=O)(=O)N1C(C#N)=NC(Cl)=C1C1=CC=C(C)C=C1 YXKMMRDKEKCERS-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- G—PHYSICS
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- G01N30/14—Preparation by elimination of some components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G—PHYSICS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng. The method improves the QuEChERS pretreatment technology (samples are extracted by extracting solution (acetonitrile: water: acetic acid=79:20:1), PSA and C18 purification treatment are adopted), and a set of residual detection method for simultaneously detecting fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-nitrile in ginseng traditional Chinese medicinal materials is established by combining an ultra-high performance liquid chromatography-mass spectrometer. The method has the advantages of rapid and simple pretreatment process, good instrument analysis sensitivity and high accuracy, and can provide detection basis for developing risk assessment of fluopicolide, cyazofamid and metabolites thereof on ginseng and safety use research thereof.
Description
Technical Field
The invention relates to a method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng, belonging to the technical field of pesticide residue detection.
Background
Ginseng (Panax ginseng c.a. mey) is a perennial herb of the araliaceae family. In China, ginseng is regarded as the king of herbal, nourishing the upper-grade. The ginseng extract is prepared by extracting and refining roots, stems and leaves of ginseng of Araliaceae, is rich in eighteen ginsenosides, and is mainly suitable for coronary heart disease, angina pectoris, bradycardia or tachycardia, ventricular premature beat, blood pressure imbalance, neurasthenia, climacteric syndrome, overfatigue, post-illness, post-partum or post-operation physical weakness and other symptoms; it has effects in prolonging life, enhancing physical strength, treating immunity hypofunction caused by radiotherapy and chemotherapy, enhancing cell activity on human surface, and inhibiting aging. In recent years, export of ginseng extracts has been growing year by year, and countries such as europe and america have strict control over pesticide residue limits of imported ginseng extracts.
Fluopicolide, chemical name: 2, 6-dichloro-N- [ (3-chloro-5-trifluoromethyl-2-pyridyl) methyl ] benzamide is a pyrazole amide broad-spectrum bactericide, can be conducted from a plant leaf base to a leaf tip direction, has good protection performance and strong permeability, has higher biological activity on oomycete diseases, and the metabolic product is mainly 2, 6-dichlorobenzamide. Researches show that fluopicolide can be used for preventing and treating root rot, black spot and the like of ginseng.
Cyazofamid, chemical name: the 4-chloro-2-cyano-N, N-dimethyl-5-p-tolylimidazole-1-sulfonamide is a mitochondrial respiration inhibitor, has an inhibiting effect on all growth stages of oomycetes, has special effects on downy mildew, epidemic disease, clubroot, damping-off and the like, and the metabolic product is mainly 4-chloro-5- (4-tolyl) -1H-imidazole-2-nitrile, so that researches show that cyazofamid can prevent and treat ginseng epidemic diseases.
At present, formal registration of fluopicolide for preventing and treating ginseng rot and black spot is underway in China, cyazofamid is being explored for preventing and treating ginseng epidemic diseases, and technical support for safe use of fluopicolide, cyazofamid and metabolites thereof on ginseng is urgently needed. The European Union prescribes that the MRL of fluopicolide in ginseng is 7mg/kg and the cyazofamid is 0.05mg/kg; the united states prescribes that the MRL of cyazofamid in ginseng is 0.3mg/kg, and there has been no report so far on a method for simultaneously detecting fluopicolide and the metabolite 2, 6-dichlorobenzamide, cyazofamid and the metabolite 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile in ginseng. The invention establishes the method for analyzing the residual quantity of fluopicolide and metabolite 2, 6-dichlorobenzamide, cyazofamid and metabolite 4-chloro-5- (4-tolyl) -1H-imidazole-2-nitrile thereof in ginseng for the first time, and provides detection basis for risk assessment and safe use research of the fluopicolide and the metabolite 4-chloro-5- (4-tolyl) -1H-imidazole-2-nitrile.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng. The method improves the QuEChERS pretreatment technology, combines an Ultra-high performance liquid chromatography-mass spectrometer (Ultra-high performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS), establishes a set of residual detection method for simultaneously detecting fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-nitrile in ginseng traditional Chinese medicinal materials, has the advantages of quick and simple pretreatment process, good instrument analysis sensitivity and high accuracy, and can provide detection basis for developing risk assessment and safe use research of fluopicolide, cyazofamid and metabolites thereof on ginseng.
The technical scheme of the invention is as follows: a method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng is characterized in that,
1) Pretreatment of
Adding dry ginseng into an extracting solution (acetonitrile: water: acetic acid=79:20:1), extracting, taking a supernatant, adding sodium citrate, sodium chloride, PSA and C18, performing dispersed solid phase extraction (QuEChERS), centrifuging at a high speed, taking the supernatant, adding water for dilution, and filtering to obtain a solution to be detected;
2) Detection of
ACQUITY UPLC BEH C18 is taken as a chromatographic column, and the residue of 4 target compounds of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile in ginseng is quantified by adopting an ultra-high performance liquid chromatography-mass spectrometer.
The chromatographic conditions of the ultra-high performance liquid chromatography are as follows: chromatographic column: ACQUITY UPLC BEH C18, 2.1X150 mm, i.d.1.7 μm; column temperature: 40 ℃; sample injection volume: 2.0 μl; mobile phase a: water (0.1% formic acid), mobile phase B: methanol (0.1% formic acid); flow rate: 0.3mL/min; gradient elution, elution procedure is as follows table 1.
The mass spectrum conditions of the ultra-high performance liquid chromatography-mass spectrometer are as follows: ion source: electrospray ionization source (ESI) + ) The method comprises the steps of carrying out a first treatment on the surface of the Drying Gas temperature (Gas Temp): 130 ℃; dry air Flow (Gas Flow): 11L/min; atomizer pressure (Nebulizer): 25psi; sheath air temperature (Sheath Gas Temp): 400 ℃; sheath air Flow (Sheath Gas Flow): 12L/min; capillary voltage (capillary): 3500V; nozzle Voltage (Nozzle Voltage): 500V (positive ion); scanning mode: scanning positive ions; monitoring mode: multiple Reaction Monitoring (MRM); qualitative ion pair (m/z) quantitative ion pair (m/z) and scan pattern are shown in table 2.
Preferably, the extraction and the dispersed solid phase extraction in the step 1) adopt a vortex oscillation mode.
Preferably, the pretreatment step of the step 1) is as follows: 1.0g of crushed dry ginseng is weighed into a plastic centrifuge tube, 10mL of extracting solution (acetonitrile: water: acetic acid=79:20:1) is added, vortex shaking is carried out for 5min, 5mL of supernatant is taken, 0.1g of sodium citrate and 2g,PSA 0.1g,C18 0.1g of sodium chloride are added, after vortex shaking is carried out for 5min, standing is carried out for 30min,4000r/min high-speed centrifugation is carried out for 5min, 1mL of supernatant is taken, 1mL of water is added, vortex shaking is carried out for 30s, and an organic filter membrane with the thickness of 0.22 mu m is arranged, and the mixture is put on a machine for standby.
Furthermore, the invention uses standard solution curve matched with matrix to quantify 4 target compounds.
The invention has the technical effects that:
1. experiments prove that the improved QuEChERS method (extraction of samples by extracting solution (acetonitrile: water: acetic acid=79:20:1, and purification treatment by adopting PSA and C18) is the optimal pretreatment method for detecting the residual quantity of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile in ginseng). Meanwhile, in order to reduce the solvent effect, adding 1 into the supernatant after the extraction: 1, a better peak shape can be obtained.
2. Experiments prove that the 4 target compounds have good peak shape and high sensitivity by adopting ACQUITY UPLC BEH C18 as a chromatographic column and water (0.1% formic acid) and methanol (0.1% formic acid) as mobile phases.
3. The test proves that: the recovery rate of fluopicolide in ginseng is 74-104%, and the relative standard deviation is 7.3-8.7%; the recovery rate of the 2, 6-dichlorobenzamide in ginseng is 86-119%, and the relative standard deviation is 1.7-8.0%; the recovery rate of cyazofamid in ginseng is 74-102%, and the relative standard deviation is 4.6-10.0%; the recovery rate of 4-chloro-5- (4-tolyl) -1H-imidazole-2 nitrile in ginseng is 74-106%, and the relative standard deviation is 8.4-10.8%; the recovery rate of RSD meets the precision requirement.
4. The method has the advantages of rapid and simple pretreatment process, good instrument analysis sensitivity and high accuracy, and can be used for detecting and analyzing fluopicolide, cyazofamid and metabolite residues thereof in ginseng traditional Chinese medicinal materials.
Drawings
FIG. 1 is a matrix standard curve of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile; wherein, a diagram: matrix standard curve of 2, 6-dichlorobenzamide; b, drawing: a matrix standard curve of fluopicolide; c, drawing: a matrix standard curve of cyazofamid; d, drawing: matrix standard curve of 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile;
FIG. 2 is a total ion chromatogram of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile; wherein a is: total quantitative ion chromatograms (B-E) (0.01 mg/L); b, drawing: quantitative ion peak chromatogram of 2, 6-dichlorobenzamide; c, drawing: quantitative ion peak chromatogram of 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile; d, drawing: quantitative ion peak chromatogram of fluopicolide; e, drawing: quantitative ion peak chromatogram of cyazofamid.
FIG. 3 shows the results of the adsorbent dose screening test, wherein series 1-5 are test groups 1-5 of Table 8, respectively.
Detailed Description
The effects thereof are described below with reference to the embodiments and drawings.
Example 1
1 materials and methods
1.1 materials and reagents
Methanol (chromatographic purity, feishier technologies, usa); water (purified water, a company of the ouha group, hangzhou); formic acid (chromatographic purity, a Sha Aisha (Tianjin) chemical company); sodium chloride (analytically pure, national pharmaceutical chemicals limited); acetonitrile (chromatographic purity, feishier technologies, usa); amine acetate (chromatographic purity, feishier technologies, usa). ethylenediamine-N-propylsilane (PSA, 40-60 μm,) Fillers (Tianjin bona Ai Jieer company); cleanertODS C18 solid phase extraction column (C18, 40-60 μm,) for the purification of the extract>) Fillers (Tianjin bona Ai Jieer company); speedTestTM activated carbon (GCB, 120-400 mesh) pack (beijing positive detection technologies limited); copure QuEChERS Clean-up Kit (900 mg MgSO) 4 +150mg PSA+15mg GCB) purifying tube (Shenzhen comma biotechnology Co., ltd.); WGlabs QuECHERS (900 mg MgSO) 4 +150mg PSA) purge tube (WG-LabS Co., U.S.; WGlabs QuECHERS (900 mg MgSO) 4 +150mg PSA+150mg C18) purge tube (WG-LabS, USA).
Fluopicolide, 2, 6-dichlorobenzamide, cyazofamid, 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile Standard were purchased from First Standard company (Tianjin, china). Fluopicolide, 2, 6-dichlorobenzamide, cyazofamid stock solution (1000 mg/L), 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile (0.1 g) were stored at-18 ℃.
1.2 instruments
Ultra-high performance liquid chromatography system: agilent 1290 info ii (Agilent); triple quadrupole tandem mass spectrometer: agilent 6470 (Agilent), with ESI source; multitube vortex mixer: TBOYS MULTI-TUBE VORTEXER STD V230; ultrasonic cleaner: KQ-500B (Kunshan ultrasonic instruments Co., ltd.); electronic balance (ten-thousandth): TP-A500 (Hua Zhi, fujian electronic technologies Co., ltd.); centrifuge: TDZ5-WS (Hunan Instrument centrifuger Co., ltd.); high-speed universal pulverizer: FW-100 (Beijing Yongguangming medical instruments Co., ltd.); YP097 (cerdolischen instruments, inc.); nitrogen blowing instrument: EFAA-DC type 24 (Shanghai Annotation laboratory science and technology Co., ltd.); microporous filter membrane (mixed membrane, 0.22 μm, PALL Co., U.S.A.).
1.3 preparation of Standard solution
Fluopicolide standard curve working solution: transferring a proper amount of standard solution into a 10mL volumetric flask by using a scale pipette, and dissolving and diluting the standard solution into 100mg/L stock solution by using acetonitrile; the 100mg/L stock solution is sequentially and gradiently prepared into 10mg/L intermediate solution and 1mg/L intermediate solution, and the intermediate solution is sequentially and gradiently prepared into standard working solutions with different concentrations.
2, 6-dichlorobenzamide standard curve working solution: transferring a proper amount of standard solution into a 10mL volumetric flask by using a scale pipette, and dissolving and diluting into 100mg/L stock solution by using methanol; the 100mg/L stock solution is sequentially and gradiently prepared into 10mg/L intermediate solution and 1mg/L intermediate solution, and the intermediate solution is sequentially and gradiently prepared into standard working solutions with different concentrations.
Cyazofamid standard curve working solution: transferring a proper amount of standard solution into a 10mL volumetric flask by using a scale pipette, and dissolving and diluting the standard solution into 100mg/L stock solution by using acetonitrile; the 100mg/L stock solution is sequentially and gradiently prepared into 10mg/L intermediate solution and 1mg/L intermediate solution, and the intermediate solution is sequentially and gradiently prepared into standard working solutions with different concentrations.
Standard curve working solution of 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile: accurately weighing 0.01g (accurate to 0.0001) of 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile standard powder into a small 50mL beaker, dissolving with acetonitrile, transferring into a 10mL volumetric flask, and diluting with acetonitrile to prepare 1000.00mg/L, 100.00mg/L and 10.00mg/L stock solution; the 100mg/L stock solution is sequentially and gradiently prepared into 10mg/L intermediate solution and 1mg/L intermediate solution, and the intermediate solution is sequentially and gradiently prepared into standard working solutions with different concentrations.
2 detection step
2.1 pretreatment step
2.1.1 extraction and purification of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile from Ginseng radix
1.0g of crushed dry ginseng is weighed into a50 mL plastic centrifuge tube, 10mL of extracting solution (acetonitrile: water: acetic acid=79:20:1) is added, and vortex shaking is carried out for 5min. Taking 5mL of supernatant, adding 0.1g of sodium citrate, 2g of sodium chloride, 0.1g of PSA (pressure sensitive adhesive) and 0.1g of C18, carrying out vortex oscillation for 5min, standing for 30min, and carrying out high-speed centrifugation for 5min at 4000 r/min. Taking 1mL of supernatant, adding 1mL of water, carrying out vortex oscillation for 30s, and passing through an organic filter membrane with the thickness of 0.22 mu m to obtain the liquid to be detected, and loading the liquid to be detected on a machine for standby.
2.2 conditions for liquid chromatography measurements
Chromatographic column: ACQUITY UPLC BEH C18, 2.1X105 mm, i.d.1.7 μm;
column temperature: 40 ℃;
sample injection volume: 2.0 μl;
mobile phase a: water (0.1% formic acid), mobile phase B: methanol (0.1% formic acid); flow rate: 0.3mL/min; gradient elution, elution procedure is as follows table 1.
TABLE 1 gradient elution procedure
| Time (min) | A(％) | B(％) | Flow rate (mL/min) |
| 0.00 | 90 | 10 | 0.300 |
| 1.00 | 90 | 10 | 0.300 |
| 3.50 | 10 | 90 | 0.300 |
| 4.00 | 10 | 90 | 0.300 |
| 5.00 | 90 | 10 | 0.300 |
2.3 Mass Spectrometry conditions
Ion source: electrospray ionization source (ESI) + )；
Drying Gas temperature (Gas Temp): 130 ℃;
dry air Flow (Gas Flow): 11L/min;
atomizer pressure (Nebulizer): 25psi;
sheath air temperature (Sheath Gas Temp): 400 ℃;
sheath air Flow (Sheath Gas Flow): 12L/min;
capillary voltage (capillary): 3500V;
nozzle Voltage (Nozzle Voltage): 500V (positive ion);
scanning mode: scanning positive ions;
monitoring mode: multiple Reaction Monitoring (MRM);
other mass spectrometry conditions were as follows:
table 2 mass spectrometry conditions
4 confirmation of the detection method
4.1 recovery of additives and precision test
According to the requirement of agricultural industry standard "pesticide residue test criterion in crops" (NY/T788-2018), three addition levels are designed for the test. The ginseng blank substrate was subjected to recovery by adding fluopicolide at a concentration of 0.01mg/kg, 0.1mg/kg and 7.0mg/kg, recovery by adding 2, 6-dichlorobenzamide at a concentration of 0.01mg/kg, 0.1mg/kg and 7.0mg/kg, recovery by adding cyazofamid at a concentration of 0.01mg/kg, 0.05mg/kg and 1.0mg/kg, recovery by adding 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile at a concentration of 0.01mg/kg, recovery by adding 0.05mg/kg and recovery by a concentration of 1.0mg/kg, and repeated 5 times for each stage, and the recovery was analyzed and determined by the above-mentioned detection steps, and the results are shown in tables 3 to 6.
TABLE 3 recovery of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid, 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile from Ginseng radix
The test result shows that the recovery rate of fluopicolide in ginseng is 74-104%, and the relative standard deviation is 7.3-8.7%; the recovery rate of the 2, 6-dichlorobenzamide in ginseng is 86-119%, and the relative standard deviation is 1.7-8.0%; the recovery rate of cyazofamid in ginseng is 74-102%, and the relative standard deviation is 4.6-10.0%; the recovery rate of 4-chloro-5- (4-tolyl) -1H-imidazole-2 nitrile in ginseng is 74-106%, and the relative standard deviation is 8.4-10.8%; the recovery rate of RSD meets the precision requirement.
4.2 Standard Curve
The standard solutions of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile are respectively diluted by a ginseng blank matrix solution and a solvent to prepare a series of standard working solutions of 0.001mg/L, 0.01mg/L, 0.05mg/L, 0.1 mg/L, 0.5mg/L and 1.0mg/L, the standard solutions of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile are respectively measured under the conditions of liquid chromatography/mass spectrometry, the concentrations and quantitative monitoring ion peak areas of the standard solutions are used as standard curves, the test results are shown in a table 4 and a figure 1, the linear correlation coefficients are all larger than 0.999, the linear range is 0.001-1 mg/L, and the quantitative limit is 0.0001-0.001 mg/kg (the quantitative limit is obtained according to the signal to noise ratio S/N of the self-contained software).
Linear equation, linear range, quantitative limit and matrix effect of the compounds of Table 4 in ginseng
4.3 matrix Effect
Matrix effects caused by matrix components of the sample are common and difficult to avoid in detection procedures using UPLC-MS/MS. The presence of matrix components may enhance or inhibit the response of the analyte during ionization and thus may interfere with quantification, producing erroneous results. In this study, the matrix effect (Me) was calculated as follows, with matrix enhancing effect when Me >0, and matrix attenuating effect otherwise.
Wherein: sm is the slope of a matrix matching standard solution curve; ss is the slope of the solvent standard solution curve.
Fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile all exhibited matrix weakening effects in ginseng (Table 7), to reduce the effect of matrix effects on the accuracy of the process, matrix matching standard curve quantification was used to eliminate the effects caused by matrix effects.
5 results and discussion
5.1 optimization of sample pretreatment methods
The invention adopts extracting solution 1 (acetonitrile: water=2:1), extracting solution 2 (acetonitrile: water: formic acid=79:20:1) and extracting solution 3 (acetonitrile: water: acetic acid=79:20:1) for extraction respectively.
Because ginseng is dry powder, it is necessary to add a proper amount of water for soaking, then acetonitrile is used for extraction, and four compounds are simultaneously extracted by this method, the recovery rate of cyazofamid and its metabolites is found to be low (less than 70%), which is probably that cyazofamid and its metabolites are more easily dissolved in an acidic solution; the recovery rate of fluopicolide and its metabolites is low (35% of fluopicolide, 42% of 2, 6-dichlorobenzamide) by extraction with extract 1, which may be more easily soluble in acidic solutions; the recovery rate of fluopicolide and its metabolites is increased by extracting with the extracting solution 2 (55% fluopicolide, 64% 2, 6-dichlorobenzamide), but the requirements (70% -120%) are still not met, which may be unstable in acidic solutions with higher concentrations; the extraction solution 3 is adopted, and a small amount of sodium citrate is added, so that the recovery rate of four target compounds can meet the requirement (70% -110%), and the sodium citrate is used as a buffering agent, thereby being beneficial to the extraction of fluopicolide and 2, 6-dichlorobenzamide. Experiments prove that: the improved QuEChERS method is the optimal pretreatment method for detecting the residual quantity of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile in ginseng. Meanwhile, in order to reduce the solvent effect, adding 1 into the supernatant after the extraction: 1, a better peak shape can be obtained.
In the research of sample pretreatment, quEChERS extraction method is generally selected for samples with different matrixes, and the recovery rates of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2 nitrile in ginseng extracted by a comparative vortex oscillation method, an ultrasonic method and a homogenization method are found, wherein the recovery rates of the fluopicolide, the 2, 6-dichlorobenzamide, the cyazofamid and the 4-chloro-5- (4-tolyl) -1H-imidazole-2 nitrile are about 90%, but the operation process is complex due to the need of repeatedly cleaning a tool bit in the homogenization process, and cross contamination is easy to generate. Ultrasonic vibration and vortex vibration do not have the problem of cross contamination, but the time required by ultrasonic vibration is longer. Comprehensively considering, finally extracting for 5min by adopting a vortex oscillation method.
Because the ginseng matrix contains various components such as saponin and volatile oil, if the ginseng matrix is directly measured after extraction, serious interference is generated to the detection of target compounds, so that the extracting solution needs to be purified. The effect of ethylenediamine-N-propylsilane filler (PSA), octadecylsilyl silica gel (C18) on the purification of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile, respectively, was examined. The PSA is mainly used for removing impurities such as saccharides, organic acid, fatty acid and the like in a sample, the C18 has good adsorption effect on cholesterol, sterol and fat in the sample, and experiments show that the C18 and the PSA have no obvious adsorption on fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2 nitrile, and can effectively remove the impurities; by the adsorbent dose screening test (experimental design is shown in table 5, screening results are shown in fig. 3), the results found: when the dosage of C18 and PSA is 20mg per milliliter of extracting solution, the interference impurities in ginseng can be well removed, and a good purifying effect is obtained.
TABLE 5 design of scavenger experiments
3.2 optimization of conditions for high-Performance liquid chromatography
Comparing 5 mobile phase combinations of a.methanol-pure water (0.1% formic acid), b.methanol (0.1% formic acid) -pure water (0.1% formic acid), c.methanol-pure water (0.1% formic acid+2 mmol/L ammonium acetate), d.acetonitrile-pure water (0.1% formic acid+2 mmol/L ammonium acetate), e.acetonitrile-pure water (0.1% formic acid), and the like, when the organic phase is methanol, peak shapes of fluopicolide, cyazofamid and other compounds are symmetrical, and no tail is removed; the peak shape is sharp, 0.1% formic acid is added into methanol, the sensitivity of the four target compounds is obviously improved, when the aqueous phase is 0.1% formic acid, the peak area response value of the four target compounds is obviously larger than that when the aqueous phase is other, and finally, the mobile phase b.methanol (0.1% formic acid) -pure water (0.1% formic acid) is adopted, as shown in fig. 2.
The invention establishes a UPLC-MS/MS method for rapidly extracting and measuring fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-nitrile in ginseng. The method is simple, convenient and quick, has high sensitivity, good repeatability and high qualitative and quantitative accuracy, and the detection limit and the quantitative limit are greatly lower than the MRL of fluopicolide in ginseng, which is specified by European Union standards, and are 7mg/kg; cyazofamid is 0.05mg/kg; the United states specifies that the MRL of cyazofamid in ginseng is 0.3mg/kg. The method of the invention provides basis for the establishment of Chinese limit standards.
Example 2: actual sample detection
According to the optimized analysis and detection method, 5 ginseng samples collected from Shandong Jinan were detected respectively, and the detection method is as follows:
1) Extraction and purification
Weighing 1.0g of crushed dry ginseng, adding 10mL of extracting solution (acetonitrile: water: acetic acid=79:20:1) into a50 mL plastic centrifuge tube, vortex shaking for 5min, taking 5mL of supernatant, adding 0.1g of sodium citrate, 2g of sodium chloride, 0.1g of PSA (pressure swing), C18.1 g, standing for 30min after vortex shaking for 5min, centrifuging at a high speed for 5min, taking 1mL of supernatant, adding 1mL of water, vortex shaking for 30s, passing through an organic filter membrane of 0.22 mu m, and obtaining the liquid to be detected for standby.
2) And detecting the obtained liquid to be detected by adopting an ultra-high performance liquid chromatography-mass spectrometer under the chromatographic conditions of 2.2 and 2.3 of the embodiment 1 and the mass spectrometry conditions to obtain quantitative monitoring ion peak areas of 4 target compounds, obtaining the concentration of the 4 target compounds in the sample solution according to a standard curve, and further calculating the pesticide residue in the sample.
The detection result shows that 4 pesticide residues in 5 Chinese medicinal material samples are not detected.
Claims (4)
1. A method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng is characterized in that,
1) Pretreatment of
Weighing 1.0 and g crushed dry ginseng, adding 10mL of an extracting solution into a plastic centrifuge tube, carrying out vortex oscillation for 5min, taking 5mL of supernatant, adding 0.1g of sodium citrate, carrying out dispersion solid-phase extraction on the supernatant by using 2g,PSA 0.1g,C18 0.1g of sodium chloride, carrying out vortex oscillation for 5min, standing for 30min, carrying out high-speed centrifugation at 4000r/min for 5min, taking 1mL of supernatant, adding 1mL of water, carrying out vortex oscillation for 30s, and passing through an organic filter membrane of 0.22 mu m to obtain a liquid to be detected; the components of the extracting solution are, according to the volume ratio, acetonitrile: water: acetic acid=79: 20:1, a step of;
2) Detection of
Using ACQUITY UPLC BEH C as a chromatographic column, and quantifying residues of 4 target compounds of fluopicolide, 2, 6-dichlorobenzamide, cyazofamid and 4-chloro-5- (4-tolyl) -1H-imidazole-2-carbonitrile in ginseng by adopting an ultra-high performance liquid chromatography-mass spectrometer;
the chromatographic conditions of the ultra-high performance liquid chromatography are as follows: chromatographic column: ACQUITY UPLC BEH C18, 2.1X150 mm, i.d.1.7 μm; column temperature: 40 ℃; sample injection volume: 2.0 μl; mobile phase a: water containing 0.1% formic acid, mobile phase B: methanol containing 0.1% formic acid; flow rate: gradient elution was performed at 0.3 mL/min.
2. The method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng according to claim 1, wherein the elution procedure is as follows:
。
3. the method for detecting residues of fluopicolide, cyazofamid and metabolites thereof on ginseng according to claim 1, wherein the mass spectrometry conditions of the ultra-high performance liquid chromatography-mass spectrometer are as follows: ion source: electrospray ionization source ESI + The method comprises the steps of carrying out a first treatment on the surface of the Drying gas temperature: 130 ℃; dry air flow: 11L/min; atomizer pressure: 25psi; sheath temperature: 400 ℃; sheath air flow: 12L/min; capillary voltage: 3500V; nozzle voltage: positive ions 500V; scanning mode: scanning positive ions; monitoring mode: multiple reactions monitor MRM.
4. A method for detecting the residue of fluopicolide, cyazofamid and metabolites thereof on ginseng according to any one of claims 1-3, wherein the 4 target compounds are quantified by using a standard solution curve matched with a matrix.
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