CN105259285A - Rapid detection method of pyridine pesticides in plant extract - Google Patents
Rapid detection method of pyridine pesticides in plant extract Download PDFInfo
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Abstract
The invention discloses a rapid detection method of pyridine pesticides in a plant extract. The method specifically comprises steps as follows: firstly, the plant extract and a solvent are mixed for pretreatment, and a plant extract sample after extraction and concentration is obtained; then pyridine pesticide residues in the plant extract are detected with the high performance liquid chromatography-tandem mass spectrometry. According to the detection method, the pretreatment method is simple and convenient to operate, the solid phase extraction or gel permeation purification process in the traditional method is omitted, the sample pretreatment time is shortened by more than 2 times, only 1 hour is taken to detect one sample completely, the detection limit can reach 10 mu g/kg, the detection period is short, the detection cost is low, the detection limit is low, the repeatability is good, and the method is suitable for product quality detection by production enterprises and management departments.
Description
Technical field
The invention belongs to nuisance detection technique field, relate to the method for quick of pyridine farm chemical in a Plant Extracts.
Background technology
Pyridine farm chemical has the advantages that biologically active is high, toxicity is low, interior absorption is strong, selectivity is good, be by pyridine replace phenyl ring and obtain a class noval chemical compound.The features such as Acetamiprid and Imidacloprid belong to nicotinic insecticide, have desinsection wide spectrum, and activity is high, the duration is long, the pyridines herbicide that dithiopyr, fluridone, imazamox and thrizopyr wide spectrum, high activity and selectivity are strong; Boscalid is Novel tobacco acid amide fungicides, is mainly used in various rot, powdery mildew etc., has very strong rejection ability to the sprouting of spore, and with other germifuge without cross resistance.Due to pyridine farm chemical Be very effective in desinsection, sterilization and weeding, use in be everlasting plant and Chinese crude drug.
Plant extracts (PlantExtract, P.E) take plant as raw material, through the method extracting and developing of physics or chemistry, obtains a certain or plurality of active ingredients in plant, and do not change a kind of product of its effective constituent structure.Along with a large amount of outlets of Chinese Plants extract, the problems such as plant extracts Pesticide Residues, heavy metal, organic solvent, environmental contaminants also display, and require increasingly stringent in the world to its limitation, and plant extracts outlet is faced with strict quality requirements.
At present, the analytical approach of pyridine farm chemical mainly contains vapor-phase chromatography, high performance liquid chromatography, HPLC MS etc., but the sample pre-treatments of these methods all needs to adopt Solid-Phase Extraction or gel permeation chromatography purification, the problems such as process is complicated, cost is high, the cycle is long, can not realize the quick detection of 7 kinds of pyridine farm chemicals.
Summary of the invention
The object of this invention is to provide the method for quick of pyridine farm chemical in a Plant Extracts, the sample pre-treatments solving the existence of existing detection method all needs to adopt solid-phase extraction column or gel permeation chromatography purification, the problem that process is complicated, cost is high, the cycle is long.
The technical solution adopted in the present invention is, the method for quick of pyridine farm chemical in a Plant Extracts, specifically implements according to the following steps:
Step 1, pre-treatment is carried out to plant extracts:
Plant extracts is mixed with solvent, obtains and extract the plant extract matter sample after concentrating;
Step 2, the pyridine farm chemical detected in plant extracts remains:
Adopt high performance liquid chromatography-tandem mass method, be called for short TF-LC-MS/MS, the pyridine farm chemical detected in plant extracts remains.
Feature of the present invention is also,
Step 1 is specially: ultrasonic extraction 25 ~ 35min, centrifugal 4 ~ 10min under 4000 ~ 6000rpm after plant extracts and ammoniacal liquor, ethyl acetate vortex being mixed; Get supernatant 10 ~ 15mL, be concentrated into dry, redissolve with 1mL methyl alcohol-0.1% aqueous formic acid, vortex evenly filters afterwards, obtains extracting the plant extract matter sample after concentrating.
Mass volume ratio 1:0.2 ~ the 0.4g/mL of plant extracts and ammoniacal liquor, the mass volume ratio of plant extracts and ethyl acetate is 1:10 ~ 30g/mL.
The volume ratio of methyl alcohol and 0.1% formic acid water is 1:9.
Step 2 is specially:
2.1 arrange chromatographic condition and Mass Spectrometry Conditions;
2.2 production standard curves;
2.3 precision and recovery of standard addition are tested;
2.4 sample liquid detect.
Step 2.1 is specially:
Chromatographic condition is arranged, and comprises TF detected parameters and arranges and the setting of liquid phase detected parameters, be specially:
1) TF detected parameters is arranged:
TF decontaminating column: Cyclone
tM-P, 0.5mm × 50mm; Mobile phase: A is methyl alcohol; B is 0.1% formic acid water; The volume ratio of mobile phase A and Mobile phase B is 3:7;
2) liquid phase detected parameters is arranged:
HypersilGOLDaQC18, column length 50mm, column internal diameter 2.1mm, packing material size 3 μm; Mobile phase: A is methyl alcohol; B is 0.1% formic acid water; The volume ratio of mobile phase A and Mobile phase B is 1:9; Column temperature: room temperature 18 ~ 22 DEG C, sample size: 50 ~ 100 μ L;
Mass Spectrometry Conditions is arranged:
Scan mode: electron spray positive ion mode;
Detection mode: multiple-reaction monitoring MRM; Spray voltage: 3300V; Gasification temperature: 330 DEG C; Sheath air pressure N
2: 0.5L/min, assist gas pressure N
2: 4.5L/min; Ion transfer tube temperature: 300 DEG C; Collision gas Ar; Collision gas pressure 1.5mTorr.
Step 2.2 is specially:
Take pyridine farm chemical standard items appropriate, dissolve with methyl alcohol and be settled to 10mL, being mixed with the standard reserving solution of 1.0mg/mL; Get in pyridine farm chemical 100 μ L to 10.00mL volumetric flask, be mixed with the hybrid standard working fluid of 10 μ g/mL, with blank plant extracts sample solution for dilute solution; It is the mixed-matrix standard solution of 500ng/mL, 100ng/mL, 50ng/mL, 20ng/mL, 10ng/mL series by storing solution stepwise dilution, sample introduction measures, carry out linear regression with the mass concentration of the corresponding compound of the peak area of often kind of compound, obtain standard working curve.
Step 2.3 is specially:
Adopt and do not carry out recovery of standard addition experiment containing the plant extracts of pyridine farm chemical as blank sample, each sample be respectively 10 μ g/kg, 20 μ g/kg, 50 μ g/kg Pitch-based sphere the recovery experiment, each Pitch-based sphere does 6 parts of Duplicate Samples, measure, ask its average recovery rate and relative standard deviation.
Step 2.4 is specially: get the sample liquid handled well that step 1 obtains, and each sample all repeats sample introduction and gets its peak area mean value for 3 times and bring corresponding typical curve equation into, calculates the content of various pyridine farm chemical in sample liquid.
The invention has the beneficial effects as follows, in plant extracts of the present invention, the pre-treating method of the method for quick of pyridine farm chemical is easy and simple to handle, eliminate Solid-Phase Extraction or gel infiltration purification process in classic method, save time for sample pretreatment more than 2 times, this method complete detection sample only needs 1 hour, detection limit can reach 10 μ g/kg, and sense cycle is short, testing cost is low, detection limit is low, reproducible, is applicable to manufacturing enterprise and administrative authority carries out product quality detection.
Accompanying drawing explanation
Fig. 1 is the upper sample chromatograms of 7 kinds of pyridine farm chemicals at TF decontaminating column;
Fig. 2 is that 7 kinds of pyridine farm chemicals purify on-column sample reservation chromatogram at TF;
Fig. 3 be in embodiment 1 in wolfberry fruit extract 7 kinds of pyridine farm chemicals extraction standard chromatic graph;
Fig. 4 is embodiment 1 wolfberry fruit extract sample chromatogram figure;
The chromatogram of Fig. 5 to be wolfberry fruit extract sample mark-on level be 10 μ g/kg.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The invention provides the method for quick of pyridine farm chemical in a Plant Extracts, specifically implement according to the following steps:
Step 1, pre-treatment is carried out to plant extracts:
According to the mass volume ratio 1:0.2 ~ 0.4g/mL of plant extracts and ammoniacal liquor, the mass volume ratio of plant extracts and ethyl acetate is 1:10 ~ 30g/mL, take plant extracts, ammoniacal liquor and ethyl acetate respectively, ultrasonic extraction 25 ~ 35min, centrifugal 4 ~ 10min under 4000 ~ 6000rpm after vortex mixing; Get supernatant 10 ~ 15mL, be concentrated into dry, redissolve with 1mL methyl alcohol-0.1% aqueous formic acid, vortex evenly crosses 0.22 μm of organic miillpore filter afterwards, obtains extracting the plant extract matter sample after concentrating;
Wherein the volume ratio of methyl alcohol and 0.1% formic acid water is 1:9.
Step 2, the pyridine farm chemical detected in plant extracts remains:
The pyridine farm chemical adopting high performance liquid chromatography-tandem mass method (TurboFlow-LC-MS/MS is called for short TF-LC-MS/MS (Thermofisher company)) to detect in plant extracts remains, and specifically implements according to following steps:
2.1 arrange chromatographic condition and Mass Spectrometry Conditions:
1) TF detected parameters:
TF decontaminating column: Cyclone
tM-P, 0.5mm × 50mm;
Mobile phase: A is methyl alcohol; B is 0.1% formic acid water;
Gradient elution program and flow velocity are in table 1.
2) liquid phase detected parameters:
HypersilGOLDaQC18 (column length 50mm, column internal diameter 2.1mm, packing material size 3 μm), or quite;
Mobile phase: A is methyl alcohol; B is 0.1% formic acid water;
Column temperature: room temperature 18 ~ 22 DEG C, sample size: 50 ~ 100 μ L; Gradient elution program and flow velocity are in table 1.
Table 1TF in-line purification gradient elution program
3) Mass Spectrometry Conditions:
Scan mode: electron spray positive ion mode (ESI+);
Detection mode: multiple-reaction monitoring (MRM); Spray voltage: 3300V; Gasification temperature: 330 DEG C; Sheath air pressure (N
2): 0.5L/min (35arb), assist gas pressure (N
2): 4.5L/min (arb); Ion transfer tube temperature: 300 DEG C; Collision gas (Ar): 1.5mTorr, mass spectrometry parameters is in table 2.
The mass spectrometry parameters of table 27 kind of pyridine farm chemical
2.2 production standard curves, specifically implement according to following steps:
2.2.1 respectively take 7 kinds of pyridine farm chemical standard items appropriate, dissolve with methyl alcohol and be settled to 10mL, being mixed with the standard reserving solution of 1.0mg/mL.
2.2.2 respectively get in 7 kinds of pyridine farm chemical 100 μ L to 10.00mL volumetric flasks, be mixed with the hybrid standard working fluid of 10 μ g/mL, with blank plant extracts sample solution for dilute solution, it is the mixed-matrix standard solution of 500ng/mL, 100ng/mL, 50ng/mL, 20ng/mL, 10ng/mL series by storing solution stepwise dilution, under above-mentioned chromatogram and Mass Spectrometry Conditions, sample introduction measures, carry out linear regression with the mass concentration of the corresponding compound of the peak area of often kind of compound, obtain standard working curve.
2.3 precision and recovery of standard addition are tested:
Adopt and do not carry out recovery of standard addition experiment containing the plant extracts of pyridine farm chemical as blank sample after measured, each sample be respectively 10 μ g/kg, 20 μ g/kg, 50 μ g/kg Pitch-based sphere the recovery experiment, each Pitch-based sphere does 6 parts of Duplicate Samples, measure, ask its average recovery rate and relative standard deviation.
2.4 sample liquid detect:
Get the sample liquid handled well that step 1 obtains, each sample all repeats sample introduction and gets its peak area mean value for 3 times and bring corresponding typical curve equation into, calculates the content of various agricultural chemicals in sample liquid.
7 kinds of pyridine farm chemicals retain chromatogram at the upper sample chromatogram of TF decontaminating column and sample, as depicted in figs. 1 and 2.Sample is retained preferably on TF pillar as can be seen from Figure 1, uses 30% methyl alcohol and 70% formic acid water can by complete for target compound wash-out as can be seen from Figure 2.
The plant extract matter sample that step 1 obtains is detected, obtain the chromatogram of plant extract matter sample, chromatographic peak is had to occur if the mass spectrogram of sample goes out peak position in standard solution chromatogram, signal to noise ratio (S/N ratio) is greater than 5, and abundance of ions is than the requirement meeting table 3, this can remain containing pyridine farm chemical in judgement sample, otherwise, chromatographic peak is not had to occur if the mass spectrogram of sample goes out peak position in standard solution chromatogram, then do not detect pyridine farm chemical in sample to remain, if or the mass spectrogram of sample goes out peak position in standard solution chromatogram and has chromatographic peak to occur, but abundance of ions is than the requirement not meeting table 3, then can be judged as false positive sample, do not detect pyridine farm chemical in sample to remain.
Table 3 qualitative confirmation time relative abundance of ions maximum allowable offset
| Relative ion abundance (%) | ＞50 | > 20 to 50 | > 10 to 20 | ≤10 |
| The relative deviation (%) allowed | ±20 | ±25 | ±30 | ±50 |
Embodiment 1
Take wolfberry fruit extract 0.5g (being accurate to 0.01g) in 50mL glass centrifuge tube, add the mixed mark of 10ng standard items, add 10mL ethyl acetate, 0.2mL ammoniacal liquor, vortex mixes, the centrifugal 10min of ultrasonic extraction 20min, 4000r/min.Get supernatant 8mL, concentrate near dry, add 1mL methyl alcohol-0.1% formic acid water (1+9) constant volume, cross 0.22 μm of organic miillpore filter, obtain extracting the plant extract matter sample after concentrating, treat sample introduction.
The pyridine farm chemical adopting TF-LC-MS/MS method to detect in plant extracts remains, TF detected parameters: TF decontaminating column: Cyclone
tM-P:0.5 × 50mm; Mobile phase: A is methyl alcohol, and B is 0.1% formic acid water; Gradient elution program and flow velocity are in table 3.Liquid phase detected parameters: HypersilGOLDaQC18 (column length 50mm, column internal diameter 2.1mm, packing material size 3 μm), or quite; Mobile phase: A is methyl alcohol, and B is 0.1% formic acid water, gradient elution program and flow velocity in table 4, column temperature room temperature 18 DEG C, sample size 100 μ L.7 kinds of pyridine farm chemicals in mark-on sample, appearance time is identical with the appearance time of 7 kinds of agricultural chemicals in extraction standard, 7 kinds of pyridine farm chemical appearance times, between 3.5 ~ 5.5min, utilize calibration curve method to calculate the recovery of 7 kinds of agricultural chemicals in sample solution between 65% ~ 93%.In wolfberry fruit extract 7 kinds of pyridine farm chemicals extraction standard chromatic graph, wolfberry fruit extract sample chromatogram figure, respectively as shown in Figure 3, Figure 4.
Table 4 in-line purification gradient elution program
Example 2
Take wolfberry fruit extract 1g (being accurate to 0.01g) in 50mL glass centrifuge tube, add the mixed mark of 20ng standard items, add 30mL ethyl acetate, 0.3mL ammoniacal liquor, vortex mixes, the centrifugal 6min of ultrasonic extraction 25min, 5000r/min.Get supernatant 10mL, concentrate near dry, add 1mL methyl alcohol-0.1% formic acid water (1+9) constant volume, cross 0.22 μm of organic miillpore filter, obtain extracting the plant extract matter sample after concentrating, treat sample introduction.
The pyridine farm chemical adopting TF-LC-MS/MS method to detect in plant extracts remains, TF detected parameters: TF decontaminating column: Cyclone
tM-P:0.5 × 50mm; Mobile phase: A is methyl alcohol, and B is 0.1% formic acid water; Gradient elution program and flow velocity are in table 4.Liquid phase detected parameters: HypersilGOLDaQC18 (column length 50mm, column internal diameter 2.1mm, packing material size 3 μm), or quite; Mobile phase: A is methyl alcohol, and B is 0.1% formic acid water, gradient elution program and flow velocity in table 5, column temperature room temperature 20 DEG C, sample size 80 μ L.7 kinds of pyridine farm chemicals in mark-on sample, appearance time is identical with the appearance time of 7 kinds of agricultural chemicals in extraction standard, 7 kinds of pyridine farm chemical appearance times, between 3 ~ 4.5min, utilize calibration curve method to calculate the recovery of 7 kinds of agricultural chemicals in sample solution between 75% ~ 105%.
Table 5 in-line purification gradient elution program
Example 3
Take wolfberry fruit extract 2g (being accurate to 0.01g) in 50mL glass centrifuge tube, add the mixed mark of 40ng standard items, add 20mL ethyl acetate, 0.4mL ammoniacal liquor, vortex mixes, the centrifugal 4min of ultrasonic extraction 30min, 6000r/min.Get supernatant 15mL, concentrate near dry, add 1mL methyl alcohol-0.1% formic acid water (1+9) constant volume, cross 0.22 μm of organic miillpore filter, obtain extracting the plant extract matter sample after concentrating, treat sample introduction.
The pyridine farm chemical adopting TF-LC-MS/MS method to detect in plant extracts remains, TF detected parameters: TF decontaminating column: Cyclone
tM-P:0.5 × 50mm; Mobile phase: A is methyl alcohol, and B is 0.1% formic acid water; Gradient elution program and flow velocity are in table 5.Liquid phase detected parameters: HypersilGOLDaQC18 (column length 50mm, column internal diameter 2.1mm, packing material size 3 μm), or quite; Mobile phase: A is methyl alcohol, and B is 0.1% formic acid water, gradient elution program and flow velocity in table 6, column temperature room temperature 22 DEG C, sample size 50 μ L.7 kinds of pyridine farm chemicals in mark-on sample, appearance time is identical with the appearance time of 7 kinds of agricultural chemicals in extraction standard, 7 kinds of pyridine farm chemical appearance times, between 2.5 ~ 3.5min, utilize calibration curve method to calculate the recovery of 7 kinds of agricultural chemicals in sample solution between 68% ~ 96%.
Table 6 in-line purification gradient elution program
From principle aspect, the present invention will be described below:
The optimization that TF selects:
In view of 7 kinds of pyridine compounds and theirs belong to middle polarity compound, in experiment, compare polymer-type Modified with Polar Monomer in-line purification post (Cyclone
tM-P) and reverse silica gel in-line purification post (C18), experiment shows: though C18 decontaminating column 7 kinds of pyridine farm chemicals are withed a hook at the end, peak exists conditions of streaking; 7 kinds of pyridine farm chemicals are at Cyclone
tM-P retains better.When comparing water and 0.1% formic acid water in experiment as load solution, target compound is at Cyclone
tMreservation situation on-P post.Experiment shows: when adopting water as load solution, about have 40% target compound to be retained, but when adopting 0.1% formic acid water as sample solution, about has the target compound of 90% to be retained.Therefore select Cyclone
tM-P post is as decontaminating column, and 0.1% formic acid water is mobile phase.
TF post elution requirement is optimized:
0.1% formic acid-the meoh eluate having investigated different proportion to the elute effect of each target compound, found that methanol ratio lower than 30% time, part of compounds elute effect is poor; Can by the target compound wash-out of 90% when 30%.Can solvent effect be caused when methanol ratio increases, occur solvent peak.Therefore this experimental selection 0.1% formic acid-methyl alcohol (7+3) is as eluent.
Optimize chromatography condition:
Investigated 0.1% formic acid-methyl alcohol, 0.1% formic acid-acetonitrile as separating effect during mobile phase, when finding 0.1% formic acid-acetonitrile as mobile phase, dithiopyr and imazamox respond lower; And 0.1% formic acid-methyl alcohol as mobile phase time, 7 kinds of target compound responses are high compared with 0.1% formic acid-acetonitrile.Select 0.1% formic acid-methyl alcohol as mobile phase, on gradient optimizing, after considering that in-line purification stream and liquid chromatography separation flow path merge, organic phase and watr-proportion change retain the impact of situation on target compound, make target compound retention time go out peak at 3 ~ 5min, the high aqueous phase 0.1% formic acid-methyl alcohol (9+1) of final selection is as initial flow phase.
Investigated the C18 chromatographic column of different size, find HypersilGOLDaQC18 (column length 50mm, column internal diameter 2.1mm, packing material size 3 μm) chromatographic column to target compound retain and separating effect best.Therefore select HypersilGOLDaQC18 chromatographic column as analytical column.
Extract the selection of solution:
The present invention is according to the feature of the dissolubility of target compound and plant extract matter sample, acetonitrile, ethyl acetate, 0.1% trichloroacetic acid-acetonitrile and ammoniacal liquor-ethyl acetate 4 kinds of Extraction solvent are investigated, because in plant extracts, impurity is more, these matrix interference to be removed in testing process, find in leaching process, it is comparatively dark that acetonitrile and 0.1% trichloroacetic acid-acetonitrile extracts color, seriously polluted to decontaminating column, affects the life-span of decontaminating column; And the comparatively ethyl acetate peak type of ammoniacal liquor-ethyl acetate is good, and the recovery that ammoniacal liquor-ethyl acetate extracts is between 60 ~ 120%, can reach requirement.Compare the impact of different pH value 7,9,12 on target compound, when finding that PH is 7, when the recovery is 12 lower than 50%, pH, Imidacloprid peak type is fat, sensitivity decrease; When pH is 9, peak shape is sharp-pointed, highly sensitive.
Linear relationship:
Get the hybrid standard working fluid of 10 μ g/mL, with blank wolfberry fruit extract sample solution for dilute solution, it is the mixed-matrix standard solution of 500.0ng/mL, 100ng/mL, 50ng/mL, 20ng/mL, 10ng/mL series by storing solution stepwise dilution, under above-mentioned chromatogram and Mass Spectrometry Conditions, sample introduction measures, carry out linear regression with the mass concentration of the corresponding compound of the peak area of often kind of compound, obtain standard working curve.In table 6.
Recovery of standard addition and Precision Experiment in wolfberry fruit extract:
Adopt and do not carry out recovery of standard addition experiment containing the plant extracts of pyridine farm chemical as blank sample after measured, each sample be respectively 10 μ g/kg, 20 μ g/kg, 50 μ g/kg Pitch-based sphere the recovery experiment, each Pitch-based sphere does 6 parts of Duplicate Samples, measure, ask its average recovery rate and relative standard deviation (RSD), as shown in table 7.Wolfberry fruit extract sample mark-on level be the chromatogram of 10 μ g/kg as shown in Figure 5.
Recovery of standard addition, precision, linear equation and related coefficient in table 7 wolfberry fruit extract
Recovery of standard addition test in the plant extracts such as sea-tangle, nettle, leaves of Hawthorn, the Radix Astragali, the root of herbaceous peony: by the detection method determined, not contain the extract of 7 kinds of pyridine farm chemicals for tested object, carry out recovery of standard addition experiment, to investigate the applicability of method to this several extract.Mark-on is carried out by minimum mark-on level 10 μ g/kg, sample weighting amount is 1.0g, add 10ng mixed standard solution, each sample all repeats 3 times, Thallus Laminariae (Thallus Eckloniae) extract sample recovery rate is between 67.2% ~ 103.0%, and nettle extract sample recovery rate is between 70.5% ~ 123.8%, and hawthorne leaf P.E sample recovery rate is between 66.5% ~ 118.3%, Astragalus Root P.E sample recovery rate is between 68.0% ~ 101.0%, and radix paeoniae alba extraction sample recovery rate is between 72.0% ~ 97.5%.The recovery is good, can meet testing requirement.
Claims (9)
1. the method for quick of pyridine farm chemical in a Plant Extracts, is characterized in that, specifically implements according to the following steps:
Step 1, pre-treatment is carried out to plant extracts:
Plant extracts is mixed with solvent, obtains and extract the plant extract matter sample after concentrating;
Step 2, the pyridine farm chemical detected in plant extracts remains:
Adopt high performance liquid chromatography-tandem mass method, be called for short TF-LC-MS/MS, the pyridine farm chemical detected in plant extracts remains.
2. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 1, it is characterized in that, described step 1 is specially: ultrasonic extraction 25 ~ 35min, centrifugal 4 ~ 10min under 4000 ~ 6000rpm after plant extracts and ammoniacal liquor, ethyl acetate vortex being mixed; Get supernatant 10 ~ 15mL, be concentrated into dry, redissolve with 1mL methyl alcohol-0.1% aqueous formic acid, vortex evenly filters afterwards, obtains extracting the plant extract matter sample after concentrating.
3. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 2, it is characterized in that, mass volume ratio 1:0.2 ~ the 0.4g/mL of plant extracts and ammoniacal liquor, the mass volume ratio of plant extracts and ethyl acetate is 1:10 ~ 30g/mL.
4. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 2, it is characterized in that, the volume ratio of described methyl alcohol and 0.1% formic acid water is 1:9.
5. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 1, it is characterized in that, described step 2 is specially:
2.1 arrange chromatographic condition and Mass Spectrometry Conditions;
2.2 production standard curves;
2.3 precision and recovery of standard addition are tested;
2.4 sample liquid detect.
6. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 5, it is characterized in that, described step 2.1 is specially:
Chromatographic condition is arranged, and comprises TF detected parameters and arranges and the setting of liquid phase detected parameters, be specially:
1) TF detected parameters is arranged:
TF decontaminating column: Cyclone
tM-P, 0.5mm × 50mm; Mobile phase: A is methyl alcohol; B is 0.1% formic acid water; The volume ratio of mobile phase A and Mobile phase B is 3:7;
2) liquid phase detected parameters is arranged:
HypersilGOLDaQC18, column length 50mm, column internal diameter 2.1mm, packing material size 3 μm; Mobile phase: A is methyl alcohol; B is 0.1% formic acid water; The volume ratio of mobile phase A and Mobile phase B is 1:9; Column temperature: room temperature 18 ~ 22 DEG C, sample size: 50 ~ 100 μ L;
Mass Spectrometry Conditions is arranged:
Scan mode: electron spray positive ion mode;
Detection mode: multiple-reaction monitoring MRM; Spray voltage: 3300V; Gasification temperature: 330 DEG C; Sheath air pressure N
2: 0.5L/min, assist gas pressure N
2: 4.5L/min; Ion transfer tube temperature: 300 DEG C; Collision gas Ar; Collision gas pressure 1.5mTorr.
7. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 5, it is characterized in that, described step 2.2 is specially:
Take pyridine farm chemical standard items appropriate, dissolve with methyl alcohol and be settled to 10mL, being mixed with the standard reserving solution of 1.0mg/mL; Get in pyridine farm chemical 100 μ L to 10.00mL volumetric flask, be mixed with the hybrid standard working fluid of 10 μ g/mL, with blank plant extracts sample solution for dilute solution; It is the mixed-matrix standard solution of 500ng/mL, 100ng/mL, 50ng/mL, 20ng/mL, 10ng/mL series by storing solution stepwise dilution, sample introduction measures, carry out linear regression with the mass concentration of the corresponding compound of the peak area of often kind of compound, obtain standard working curve.
8. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 5, it is characterized in that, described step 2.3 is specially:
Adopt and do not carry out recovery of standard addition experiment containing the plant extracts of pyridine farm chemical as blank sample, each sample be respectively 10 μ g/kg, 20 μ g/kg, 50 μ g/kg Pitch-based sphere the recovery experiment, each Pitch-based sphere does 6 parts of Duplicate Samples, measure, ask its average recovery rate and relative standard deviation.
9. the method for quick of pyridine farm chemical in a Plant Extracts according to claim 5, it is characterized in that, step 2.4 is specially: get the sample liquid handled well that step 1 obtains, each sample all repeats sample introduction and gets its peak area mean value for 3 times and bring corresponding typical curve equation into, calculates the content of various pyridine farm chemical in sample liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109239221A (en) * | 2018-10-02 | 2019-01-18 | 丁立平 | The gas chromatography-mass spectrometry of three kinds of trace imidazolinone herbicides in a kind of measurement bean powder |
| CN110455937A (en) * | 2019-06-13 | 2019-11-15 | 中国水产科学研究院长江水产研究所 | Imidacloprid is metabolized object detecting method in a kind of aquatic products |
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| CN110455937A (en) * | 2019-06-13 | 2019-11-15 | 中国水产科学研究院长江水产研究所 | Imidacloprid is metabolized object detecting method in a kind of aquatic products |
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