CN105784894A - Pesticide residue detection method for traditional Chinese medicine - Google Patents
Pesticide residue detection method for traditional Chinese medicine Download PDFInfo
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- CN105784894A CN105784894A CN201410827302.6A CN201410827302A CN105784894A CN 105784894 A CN105784894 A CN 105784894A CN 201410827302 A CN201410827302 A CN 201410827302A CN 105784894 A CN105784894 A CN 105784894A
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- 239000003814 drug Substances 0.000 title claims abstract description 44
- 238000001514 detection method Methods 0.000 title claims abstract description 32
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 30
- 239000000523 sample Substances 0.000 claims description 24
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
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- 238000010792 warming Methods 0.000 claims description 8
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- 230000000694 effects Effects 0.000 claims description 7
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- 230000014759 maintenance of location Effects 0.000 claims description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
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- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002024 ethyl acetate extract Substances 0.000 claims description 2
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- 235000017168 chlorine Nutrition 0.000 abstract 1
- 125000001309 chloro group Chemical class Cl* 0.000 abstract 1
- 150000008056 dicarboxyimides Chemical class 0.000 abstract 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000003908 quality control method Methods 0.000 abstract 1
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- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to a pesticide residue detection method for modern traditional Chinese medicine preparations.According to the method, a GC-MS/MS method for detecting 103 types of pesticide residues including organic chlorines, organic phosphoruses, dicarboximides, pyrethroids and the like is established, ethyl acetate is adopted as extraction solvent in a test, amino columns are adopted for purification, and a solution marked with a traditional Chinese medicine matrix is adopted for measurement.By means of the method, an effective and accurate quality control method for safety of traditional Chinese medicine is provided.
Description
Technical field：
The present invention relates to the detection method in a kind of drug products about residues of pesticides, the detection method that the Multiple Pesticides in more particularly to a kind of modern Chinese herbal medicine preparation are remained.
Background technology：
Chinese native medicine security problem incident occurs again and again in recent years, and this brings great challenge to one to the Chinese medicine taken pride in for " safely, effectively ".In addition some media are to the excessive publicity and misleading about Chinese native medicine security problem incident, so that concern of the people to Chinese native medicine security has reached unprecedented degree, the viewpoint of " common people do not suspect the drug effect of Chinese medicine, but suspect the security of Chinese medicine " has become the bottleneck of restriction Development of Chinese Medicine.It is also the bottleneck for restricting internationalization of tcm.Its Pesticide Residues is to influence the key factor of Chinese native medicine security.
So-called residues of pesticides：Finger is influenceed by growing environment or in Chinese medicine plant, processing, storage using the agricultural chemicals parent after agricultural chemicals, remained in medicinal part and the special derivative for having toxicological significance, such as degraded or converted product, metabolin and industrial impurity.
Chinese medicine easily exposed to pesticides, and country is not perfect using resignation system to medicinal material Pesticides in plantation, production, process, therefore the residual material of medicinal material agriculture that may be present can not be determined；Thus make there is unknown trace amount pesticide residue in the compound Chinese medicinal preparation being made after Chinese medicine extraction.The a large amount of small-molecule substances contained in compound Chinese medicinal preparation matrix after refined, matrix is complicated, and the measure formation to the pesticide residue of trace is disturbed.The present invention on the basis of existing technology, finds a kind of detection method of the pesticide residue of trace in Chinese medicine.
The content of the invention：
The present invention provides a kind of middle medicinal herb grower residual assay method, and the present invention uses GC-MS/MS, i.e. triple quadrupole bar gas phase-mass spectrometry detection technique that the residues of pesticides in Chinese medicine are detected with its method comprises the following steps：
Step 1, the composition in Chinese medicine is extracted,
Step 2, extract solution is purified,
Step 3, the solution injection GC-MS/MS chromatographs after purification, obtain chromatogram,
Step 4, standard curve is made with matrix mark-on solution and eliminates matrix effect, the content for obtaining Chinese medicine Pesticide Residues is calculated according to chromatogram.
Extracted wherein described in step 1, step is as follows：Chinese medicine is taken, grinding and sieving takes the sample 1.0-3.0g after crushing, accurately weighed, addition 5-15mL ethyl acetate extracts 20-40min, centrifuges 2-4min, takes supernatant appropriate, volatilization is closely dry, dissolved with 1-3mL leacheates, to be clean.
Leacheate therein is selected from following solution：
Dichloromethane: methanol=100: 1 (volume ratio)；
Acetonitrile：Toluene=3：1 (volume ratio)；
Toluene etc..
Wherein described extract is extracted or ultrasonic extraction selected from shaking.
Nearly dry separation of volatilizing is rotated to nearly dry or nitrogen from water-bath is blown near do.
It is preferred that extracting method be：Take Chinese medicine, No. 3 sieves are crossed after crushing, the sample 2.0g after crushing is taken, it is accurately weighed, in 50mL polypropylene plastics centrifuge tubes, 10mL ethyl acetate is added, 30min (135r/min), 5000r/min centrifugations 3min are extracted in shaking, supernatant 5mL is taken in 150ml hearts bottle, rotate near dry, dissolved with 2mL leacheates (V (dichloromethane): V (methanol)=100: 1) in 40 DEG C of water-baths, it is to be clean.
Purified wherein described in step 2, step is as follows：Before nh 2 column sample-adding, first with 2-4mL leacheate prewashing posts, when pre- washing lotion liquid level is reached at the top of column packing, sample solution is moved into post rapidly, and leacheate is received with boiling flask；With 2~4 washing heart bottles of 10-20ml leacheates altogether point, when last leacheate liquid level is close at the top of column packing, cleaning solution is equally transferred in pillar, collect all effluxes, spin concentration is done near in 35-45 DEG C of water-bath, 1-3ml acetone or acetonitrile are added, mixes, treats Gas Chromatography-Mass Spectrometry.
It is preferred that purification method be：Before nh 2 column sample-adding, first with 3mL leacheate prewashing posts, when pre- washing lotion liquid level is reached at the top of column packing, sample solution is moved into post rapidly, and leacheate is received with 150ml boiling flasks；3ml is used respectively, and 5ml, 3 washing heart bottles of 5ml leacheates when last leacheate liquid level is close at the top of column packing, cleaning solution are equally transferred in pillar, all effluxes are collected.Spin concentration adds 1ml acetone and mixed near dry in 40 DEG C of water-baths.
Wherein described leacheate is identical with leacheate in step 1.
The chromatographic condition of wherein step 3 is as follows：
Gas-chromatography：Chromatographic column is selected from：Rtx-5MS, HP-5MS or DB-5MS post.Initial temperature is in 50-70 DEG C, retention time 0-5min；First stage, heating rate scope was in 15-35 DEG C of min-1Between, it is warming up to 85-150 DEG C；Second stage heating rate scope is in 8-15 DEG C of min-1Between, maximum temperature is 300-350 DEG C, and the retention time is between 5-20min.It is preferred that post heating schedule：50 DEG C, 1min is kept, with 25 DEG C of min-1Speed is warming up to 125 DEG C, then with 10 DEG C of min-1300 DEG C are warming up to, 10min is kept；
Mass Spectrometry Conditions：Ionization mode：EI, ionizing energy：70eV；Ion source temperature：200 DEG C, transmission line temperature：250℃；Solvent delay：2.8min；Carrier gas：High-pure helium (purity：99.999%)；Column flow rate：1.69mL·min-1；Injector temperature：250 DEG C, Splitless injecting samples；Sample size：1μL.
Full scan pattern, quality of scanning scope 40~500 obtains each Compound Retention time in sample.
Select ion detection：According to peak sequence, each chemical parameters are obtained.
Wherein standard curve described in step 4, preparation method is as follows：
Take traditional Chinese medicine sample appropriate, operated by sample pre-treatments mode, prepare sample substrate solution；Mixing reference substance storing solution is taken, sample-adding product matrix solution is configured to the matrix hybrid standard working solution of various concentrations, for doing standard working curve.Prepare and contain each 2~500ngmL of agricultural chemicals-1Serial mixed standard solution, it is accurate respectively to draw 1 μ L, inject gas chromatography-mass spectrometry, determine, calculate.Using peak area as ordinate, mass concentration is abscissa, draws standard curve.
Wherein described matrix is：Traditional Chinese medicine sample is according to the solution obtained after step 1,2 progress extraction and cleanings.
The compound method of reference substance storing solution is mixed, it is accurately weighed to take each reference substance 10.00mg respectively, it is placed in 1000mL measuring bottles, plus acetone solution and scale is settled to, it is configured to 10.0mgL- 1Standard reserving solution, at -20 DEG C preserve.
The compound method of matrix mark-on solution：The matrix solution being made with traditional Chinese medicine sample, step by step dilution series mixed standard solution.
Wherein prepare and contain each 2~500ngmL of agricultural chemicals-1Serial mixed standard solution, compound method is as follows：Mixing reference substance storing solution 0.5mL is taken to be placed in 10mL measuring bottles, plus matrix solution dissolves and is settled to scale and obtains concentration for 500ngmL-1Mixed standard solution, dilute the standard liquid of a upper concentration point step by step respectively with matrix solution, obtain concentration for 200,100,50,20,5,2ngmL-1Serial mixed standard solution.
Chromatographic condition is identical with step 3.
Chinese medicine of the present invention, refers to the Chinese medicine preparation prepared after processing is extracted.
The measure of the rate of recovery, precision and quantitative limit：
Add 0.01,0.05,0.1mgkg in the sample respectively-1Determined after the mixed reference substance solution of 3 levels, extraction and cleaning, each horizontal parallel is determined 5 times, calculate the rate of recovery and method repeatability.Instrument precision is according to 50ngmL-1The meter of mixed reference substance solution continuous sample introduction No. 6 times, the equal ＜ 3% of precision of each test substance.Quantitative limit：Precision weighs traditional Chinese medicine sample powder 2.0g, and the certain density reference substance mixed solution of addition is a certain amount of, carries out quantitative limit experiment, and spiked levels are 3 levels, respectively 0.001,0.002,0.005mgkg-1, each horizontal parallel determines 3 times, and the selection rate of recovery meets between 60-120%, and RSD is less than 20%, and the signal to noise ratio that addition standard liquid mass concentration is obtained is not less than 10：1 minimum pitch-based sphere, as the quantitative limit of the material, the results are shown in Table 1.Chromatogram is shown in Fig. 1.
Quantitative manner：
For single test substance, it can be quantified using calibration curve method or one point external standard method, for the residual test substance of similar agriculture (such as Permethrin includes Permethrin -1, Permethrin -2) containing isomer, the material total amount can be calculated using the standard curve of Permethrin.
Method of the present invention sensitivity is high, the degree of accuracy is good, can effectively carry out multi-pesticide residue in Chinese medicine preparation and detect, its operating method is obtained by screening, and screening process is as follows：
Extracting method：
Contain substantial amounts of small-molecule substance in Chinese medicine matrix, using traditional 1. water infiltration, acetonitrile is extracted and salting out method, and impurity is extracted altogether too much, when further purifying, easily blocks solid phase extraction column or gel chromatographic columnses；2. acetonitrile directly extracts that rear impurity is more, and single purification can not meet detection demand, needs SPE combination GPC series connection purifications；3. acetone direct extraction method, is used alone Solid phase extraction, matrix interference is serious when low concentration is added, and method Sensitivity is slightly worse.
The present invention, as Extraction solvent, the interference of water-soluble and alcohol-soluble small molecule composition can be eliminated to greatest extent using ethyl acetate.The purification of the step of nh 2 column one can meet sensitivity 0.01mgkg after extraction- 1, the requirement of the methodology such as degree of accuracy 70-110% (low concentration is based on 60-120%).
Effect：103 kinds of test substances, in pitch-based sphere 0.001-0.01mgkg- 1Between can quantify detect.Extracts reagent ethyl acetate is more friendly for environment, has saved the reagent and time cost of further purification.
Influence of the matrix effect to method：
In Pesticide Residues detection, because its matrix is relatively simple, disturb smaller；Chinese medicine is complicated compared with food many；And the Chinese medicine preparation being refined by herbal mixture material, its matrix effect is more notable.Complicated matrix, meeting interference measurement result, causes false positive or false negative.
This method establishes the GC-MS/MS methods of multichannel, mass spectrography is used to detect that agriculture is residual, it can be very good to exclude false positive results, for each determinand, this method sets one group of quota ion, two groups of qualitative ions (including above-mentioned quota ion), for excluding the interference that complex matrices are caused.And all reference substance solutions use bare substrate mark-on, it is to avoid mass spectrometer matrix effect causes the inaccurate of result when quantitative.The measure of method quantitative limit, using addition sample, upper machine analysis after extracted purification is selected to meet the least concentration of the degree of accuracy and repeatability as detection limit, and is different from traditional reference substance solution that uses and carries out signal to noise ratio as method detection degree.The ability that the detection limit reflects extracting method, instrumental sensitivity two parts are detected to test substance.
The technical problem to be solved in the present invention is, in the prior art, the problem of Chinese medicine preparation multi-pesticide residue analytical technology is present is simple to operate there is provided a kind of high sensitivity, high stability, the cost-effective detection method for many residues of pesticides of traditional Chinese medicine sample.
At present, not yet there is the multiple types pesticide residue detection method carried out for Chinese medical extract preparation, the present invention develops pre-treating method simple and easy to apply, can be applied to the detection of Chinese medicine preparation Pesticide Residues material, or be used as the control device of the residual class safety indexes of Chinese medicine preparation agriculture.103 kinds of residual materials of agriculture are determined simultaneously, time cost, labour cost is saved, and method is quick, accurate, can more fully control the quality of the pharmaceutical preparations.
Brief description of the drawings：
Fig. 1 is the gas chromatography combined with mass spectrometry chromatogram of 103 kinds of residual materials of agriculture
Embodiment
The present invention is further illustrated by the following examples：
The detection citing of the Liuwei Dihuang Wan multi-pesticide residue of embodiment 1
The present embodiment selects certain commercially available brand Liuwei Dihuang Wan, carries out the detection of residues of pesticides.Specific method is as follows：
(1) sample pre-treatments：
Extract：
Take Liuwei Dihuang Wan sample, No. 3 sieves are crossed after crushing, the sample 2.0g after crushing is taken, it is accurately weighed, in 50mL polypropylene plastics centrifuge tubes, 10mL ethyl acetate is added, 30min (135r/min), 5000r/min centrifugations 3min are extracted in shaking, supernatant 5mL is taken in 150ml hearts bottle, rotate near dry, dissolved with 2mL leacheates (V (dichloromethane): V (methanol)=100: 1) in 40 DEG C of water-baths, it is to be clean.
Purification：
Before nh 2 column sample-adding, first with 3mL leacheate prewashing posts, when pre- washing lotion liquid level is reached at the top of column packing, sample solution is moved into post rapidly, and leacheate is received with 150ml boiling flasks；3ml is used respectively, and 5ml, 5ml leacheates washing heart bottle when last leacheate liquid level is close at the top of column packing, cleaning solution is equally transferred in pillar, all effluxes are collected.Spin concentration adds 1ml acetone near dry in 40 DEG C of water-baths, mixes, treats Gas Chromatography-Mass Spectrometry.
(2) by the good sample GC-MS/MS quantitative analyses of step (1) pre-treatment, make standard curve according to above-mentioned matrix mark-on solution and eliminate matrix effect, obtain the content of many residues of pesticides in sample.
Chromatographic condition：
Instrument is used：Triple level Four bar gas chromatograph-mass spectrometers (Shimadzu GCMS-TQ803)；Rtx-5MS (30m × 0.24mm, 0.25um)；Capillary column；Post heating schedule：50 DEG C, 1min is kept, with 25 DEG C of min-1Speed is warming up to 125 DEG C, then with 10 DEG C of min-1300 DEG C are warming up to, 10min is kept；Ionization mode：EI, ionizing energy：70eV；Ion source temperature：200 DEG C, transmission line temperature：250℃；Solvent delay：2.8min；Carrier gas：High-pure helium (purity:99.999%)；Column flow rate：1.69mL·min-1；Injector temperature：250 DEG C, Splitless injecting samples；Sample size：1μL；Select ion detection.
Full scan pattern, quality of scanning scope 40~500 obtains each Compound Retention time in sample.
Select ion detection：According to peak sequence, each chemical parameters are obtained.
According to peak sequence, the parameter of each compound is as follows：
The sweep time of 2103 kinds of agricultural chemicals of table, scan mode, quantitative and qualitative ion
Claims (11)
1. a kind of pesticide residue detection method for Chinese medicine, it is characterised in that the residues of pesticides in Chinese medicine are detected using gas phase-mass spectrometry detection technique, be the described method comprises the following steps：
Step 1, the composition in Chinese medicine is extracted,
Step 2, extract solution is purified,
Step 3, the solution injection GC-MS/MS chromatographs after purification, obtain chromatogram,
Step 4, standard curve is made with matrix mark-on solution and eliminates matrix effect, the content for obtaining Chinese medicine Pesticide Residues is calculated according to chromatogram.
2. detection method according to claim 1, it is characterised in that extracted wherein described in step 1, step is as follows：Chinese medicine is taken, grinding and sieving takes the sample 1.0-3.0g after crushing, accurately weighed, addition 5-15mL ethyl acetate extracts 20-40min, centrifuges 2-4min, takes supernatant appropriate, volatilization is closely dry, dissolved with 1-3mL leacheates, to be clean.
3. detection method according to claim 2, it is characterised in that wherein described extract is extracted or ultrasonic extraction selected from shaking；The nearly dry separation of volatilization is rotated to nearly dry or nitrogen from water-bath is blown near do.
4. detection method according to claim 2, it is characterised in that extracting method is：Chinese medicine is taken, No. 3 sieves are crossed after crushing, the sample 2.0g after crushing is taken, accurately weighed, addition 10mL ethyl acetate, shaking extracts 30min, 5000r/min centrifugation 3min, takes supernatant 5mL, rotate near and do in 40 DEG C of water-baths, dissolved with 2mL leacheates, to be clean.
5. detection method according to claim 1, it is characterised in that purified wherein described in step 2, step is as follows：Before nh 2 column sample-adding, first with 2-4mL leacheate prewashing posts, when pre- washing lotion liquid level is reached at the top of column packing, sample solution is moved into post, leacheate is received；With 2-4 washing heart bottle of 10-20ml leacheates altogether point, when last leacheate liquid level is close at the top of column packing, cleaning solution is equally transferred in pillar, collect all effluxes, spin concentration is done near in 35-45 DEG C of water-bath, 1-3ml acetone or acetonitrile are added, mixes, treats Gas Chromatography-Mass Spectrometry.
6. detection method according to claim 5, it is characterised in that purification method is：Before nh 2 column sample-adding, first with 3mL leacheate prewashing posts, when pre- washing lotion liquid level is reached at the top of column packing, sample solution is moved into post rapidly, leacheate is received；3ml is used respectively, and 5ml, 5ml leacheates washing heart bottle when last leacheate liquid level is close at the top of column packing, cleaning solution is equally transferred in pillar, all effluxes are collected, spin concentration adds 1ml acetone and mixed near dry in 40 DEG C of water-baths.
7. according to any described detection method of claim 2,4,5,6, it is characterised in that leacheate therein is selected from following solution：The dichloromethane that volume ratio is 100: 1: methanol mixed solution；Volume ratio is 3：1 acetonitrile：Toluene mixed solution；Toluene.
8. detection method according to claim 7, it is characterised in that leacheate is selected from the dichloromethane: methanol mixed solution that volume ratio is 100: 1.
9. detection method according to claim 1, it is characterised in that the chromatographic condition of wherein step 3 is as follows：
Gas-chromatography：Chromatographic column is selected from：Rtx-5MS, HP-5MS or DB-5MS post, initial temperature is in 50-70 DEG C, retention time 0-5min；First stage, heating rate scope was in 15-35 DEG C of min-1Between, it is warming up to 85-150 DEG C；Second stage heating rate scope is in 8-15 DEG C of min-1Between, maximum temperature is 300-350 DEG C, and the retention time is between 5-20min；
Mass Spectrometry Conditions：Ionization mode：EI, ionizing energy：70eV；Ion source temperature：200 DEG C, transmission line temperature：250℃；Solvent delay：2.8min；Carrier gas：Purity：99.999% high-pure helium；Column flow rate：1.69mL·min-1；Injector temperature：250 DEG C, Splitless injecting samples；Sample size：1μL.
10. detection method according to claim 1, it is characterised in that gas-chromatography：Post heating schedule：50 DEG C, 1min is kept, with 25 DEG C of min-1Speed is warming up to 125 DEG C, then with 10 DEG C of min-1300 DEG C are warming up to, 10min is kept.
11. according to any described detection methods of claim 1-10, it is characterised in that the Chinese medicine, refer to the Chinese medicine preparation prepared after extraction.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290692A (en) * | 2016-11-02 | 2017-01-04 | 百奥森（江苏）食品安全科技有限公司 | A kind of pesticide method |
| CN106442507A (en) * | 2016-11-03 | 2017-02-22 | 百奥森（江苏）食品安全科技有限公司 | Detection test paper for pyrethroid pesticide residues in foods |
| CN108072727A (en) * | 2016-11-05 | 2018-05-25 | 天士力医药集团股份有限公司 | Method that is a kind of while measuring 23 kinds of organic chlorine agriculture chemicals residual quantities in Radix Notoginseng |
| CN110470765A (en) * | 2019-08-26 | 2019-11-19 | 谱尼测试集团吉林有限公司 | A kind of method of 179 persticide residues in measurement fruits and vegetables |
| CN112433013A (en) * | 2020-11-26 | 2021-03-02 | 湖北世友中药饮片有限公司 | Method for detecting pesticide residue content in traditional Chinese medicine decoction pieces |
| CN116718709A (en) * | 2023-07-31 | 2023-09-08 | 广州南沙明曦检测服务有限公司 | Mobile phase and pesticide residue detection method for improving pesticide residue detection efficiency of high performance liquid chromatography-mass spectrometer |
| CN117890511A (en) * | 2024-01-12 | 2024-04-16 | 广东柏佳检测科技有限公司 | Pesticide residue detection method for traditional Chinese medicine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101598707A (en) * | 2009-05-19 | 2009-12-09 | 烟台杰科检测服务有限公司 | The residual detection method of Multiple Pesticides in a kind of oil-containing food |
| CN103529153A (en) * | 2013-07-26 | 2014-01-22 | 宁波检验检疫科学技术研究院 | Common rapid detection method for various pesticide residues in soybeans |
| CN104198600A (en) * | 2014-07-31 | 2014-12-10 | 甘肃中天药业有限责任公司 | Method for detecting radix astragali |
-
2014
- 2014-12-26 CN CN201410827302.6A patent/CN105784894B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101598707A (en) * | 2009-05-19 | 2009-12-09 | 烟台杰科检测服务有限公司 | The residual detection method of Multiple Pesticides in a kind of oil-containing food |
| CN103529153A (en) * | 2013-07-26 | 2014-01-22 | 宁波检验检疫科学技术研究院 | Common rapid detection method for various pesticide residues in soybeans |
| CN104198600A (en) * | 2014-07-31 | 2014-12-10 | 甘肃中天药业有限责任公司 | Method for detecting radix astragali |
Non-Patent Citations (6)
| Title |
|---|
| STANISŁAW WALORCZYK ET AL: "Fast and sensitive determination of pesticide residues in vegetables using low-pressure gas chromatography with a triple quadrupole mass spectrometer", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| TUIJA PIHLSTRÖM ET AL: "Analysis of pesticide residues in fruit and vegetables with ethyl acetate extraction using gas and liquid chromatography with tandem mass spectrometric detection", 《ANALYTICAL BIOANALYTICAL CHEMISTRY》 * |
| 刘珺 等: "林蛙油中农药残留的GC-MS/MS检测方法", 《分析测试学报》 * |
| 卢俊文 等: "分散固相萃取-气相色谱-串联质谱法测定蔬菜中多种农药残留", 《中国卫生检验杂志》 * |
| 朱铭立 等: "高效液相色谱测定水产品中氨基甲酸酯类农药多组分残留", 《广东农业科学》 * |
| 白冰 等: "气相色谱-质谱法检测双孢蘑菇和香菇中的67种农药残留", 《食用菌学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290692A (en) * | 2016-11-02 | 2017-01-04 | 百奥森（江苏）食品安全科技有限公司 | A kind of pesticide method |
| CN106442507A (en) * | 2016-11-03 | 2017-02-22 | 百奥森（江苏）食品安全科技有限公司 | Detection test paper for pyrethroid pesticide residues in foods |
| CN108072727A (en) * | 2016-11-05 | 2018-05-25 | 天士力医药集团股份有限公司 | Method that is a kind of while measuring 23 kinds of organic chlorine agriculture chemicals residual quantities in Radix Notoginseng |
| CN108072727B (en) * | 2016-11-05 | 2021-05-11 | 天士力医药集团股份有限公司 | Method for simultaneously determining residual quantity of 23 organochlorine pesticides in pseudo-ginseng |
| CN110470765A (en) * | 2019-08-26 | 2019-11-19 | 谱尼测试集团吉林有限公司 | A kind of method of 179 persticide residues in measurement fruits and vegetables |
| CN112433013A (en) * | 2020-11-26 | 2021-03-02 | 湖北世友中药饮片有限公司 | Method for detecting pesticide residue content in traditional Chinese medicine decoction pieces |
| CN116718709A (en) * | 2023-07-31 | 2023-09-08 | 广州南沙明曦检测服务有限公司 | Mobile phase and pesticide residue detection method for improving pesticide residue detection efficiency of high performance liquid chromatography-mass spectrometer |
| CN117890511A (en) * | 2024-01-12 | 2024-04-16 | 广东柏佳检测科技有限公司 | Pesticide residue detection method for traditional Chinese medicine |
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