CN108181394A - The method that a kind of extraction-purification Synchronos method measures three kinds of phenoxy carboxylic acid persticide residues in tobacco - Google Patents
The method that a kind of extraction-purification Synchronos method measures three kinds of phenoxy carboxylic acid persticide residues in tobacco Download PDFInfo
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
A kind of method that extraction and cleaning Synchronos method measures three kinds of phenoxy carboxylic acid persticide residues in tobacco, it is characterised in that：Sample is extracted with the aqueous hydrochloric acid solution of 0.5mol/L, and with dichloromethane extraction, 2,4 drop, 2,4,5 tears and Mediben persticide residue in tobacco are measured with ultra performance liquid chromatography tandem mass spectrometry.The present invention prepares standard working solution with bare substrate, overcome the influence of matrix effect, the deficiency of prior art sample treatment is compensated for, sample-pretreating method and instrument testing conditions are optimized for tobacco sample, the method for the present invention has following excellent results compared with prior art：The method of the present invention sample pretreatment process is simple and quick, environmentally protective without derivatization, and has the advantages that operation accurate, high sensitivity and reproducible.
Description
Technical field
The invention belongs to the remaining physical and chemical inspection technical fields of pesticide in tobacco and tobacco product, relate generally to tobacco and cigarette
2,4- drops in straw-made articles, extraction-purification Synchronos method of three kinds of chlorobenzene oxycarboxylic acid pesticide residue amounts such as 2,4,5- tears and Mediben
It measures.
Background technology
Phenoxy carboxylic acid herbicides is affected to the safety of crop by environmental condition, Crop growing stage, using not
When heavier poisoning may be generated.In use, find there is certain endocrine disturbing effect to people, animal, with this
The increasingly increase of class herbicide usage amount and use scope, the residual in crop and the danger caused by human health and environment
Evil is also more and more concerned.China and other each states have all formulated stringent residue limits, such as Japan's regulation 2,4,
5- tears must not detect, Codex Alimentary Commission, and the limitation that 2,4- of the formulations such as Japan is dropped in most agricultural product is
0.05 mg/kg.It is more about the report for phenoxy carboxylic acid residues detecton in soil, water, rice, rice and textile, and
And the report of phenoxy carboxylic acid herbicides multi-residue analysis is mostly measured using gas-chromatography or gas chromatography mass spectrometry.Due to such compound
Polarity is larger, stability is poor, is not easy to gasify, and need to use ability gas-chromatography or gas after diazomethane or boron trifluoride butanol derivs
Matter combination method is measured【Analytical chemistry, 2006,34 (12), 1733-1736;Chromatography, 2008,26 (1), 116-118;Point
Analysis science journal, 2010,26 (1), 47-50】.Derivatization reagent diazomethane and boron trifluoride butanol toxicity are stronger, and entire
Operating procedure is cumbersome, analysis cost is higher, the detection cycle of single sample is longer.
Since the selectivity of LC-MS/MS methods is greatly improved, there is good anti-matrix interference ability, and have more rich
Rich qualitative and quantitative information, sensitivity are higher so that sample pretreatment process greatly simplifies.Due to interference groups certain in matrix
It is dramatically different that the presence divided can be such that the ionogenic speed of component to be measured has compared with standard sample so that signal response generates
Compared with Big mutation rate, so as to influence detection limit, quantitative limit, accuracy and precision etc..In sample analysis generally use optimization chromatography-
Mass spectral analysis condition, bare substrate matching the standard corrects method and internal standard method cancel or compensate for possible matrix effect.It is empty
White matrix matching the standard corrects method is by blank sample after pre-treatment, adds in series concentration determinand standard as matrix
With standard solution, to be corrected to testing result, this method can compensate matrix effect to a certain extent.
Invention content：
The purpose of the present invention is intended to overcome prior art defect, provide it is a kind of quick, efficiently, without complicated processes such as derivatizations,
Extraction and cleaning is carried out at the same time, finally directly with 2,4- drops in liquid chromatography tandom mass spectrometry determination tobacco and tobacco product, 2,4,5-
The assay method of three kinds of phenoxy carboxylic acid persticide residues such as tears and Mediben, the analysis method only take 4 min, can it is quick,
Three kinds of phenoxy carboxylic acid persticide residues in accurate detection tobacco and tobacco product, measurement result is accurate and interferes less, You Jirong
Agent consumption is few.The method of the present invention is easy, quick, clean-up effect is preferable, and all technical meets the requirement of residue detection.
The purpose of the present invention is achieved through the following technical solutions：
The method that a kind of extraction-purification Synchronos method measures three kinds of phenoxy carboxylic acid persticide residues in tobacco, uses aqueous hydrochloric acid solution
Sample is extracted, and uses CH2Cl2It is stripped, tobacco and tobacco product is directly measured with liquid chromatography-tandem mass spectrometry
In 2,4- drops, 2,4,5- tears and Mediben persticide residue.It is as follows：
A, the extraction of sample：1.0 g samples are weighed, are placed in 50 mL tool plug centrifuge tubes, add in the salt of 10 mL, 0.5 moL/L
The CH of aqueous acid and 10 mL2Cl2, 15 min of vortex oscillation.1 mL lower floors organic phase is pipetted, is filtered, is examined into UPLC MS/MS
It surveys；
B, the preparation of vehicle solution：Weigh 2.0 g blank samples（The tobacco sample of three kinds of pesticides after testing without the present invention
Product）, it is placed in 50 mL tool plug centrifuge tubes, adds in the aqueous hydrochloric acid solution of 20 mL, 0.5 moL/L and the CH of 20 mL2Cl2, it is vortexed
Vibrate 15 min.It pipettes spare in lower floor's organic phase to liquid storage pipe；
C, prepared by standard working solution：Tri- kinds of pesticides of 0.01g (2,4- drops, 2,4,5- tears and Mediben) standard items are weighed respectively to arrive
In 10 different mL volumetric flasks, CH is used2Cl2Dilute and be finally configured to have with vehicle solution concentration gradient containing three kinds
The hybrid standard working solution of pesticide；Specific manner of formulation is as follows：0.01 g 2,4- drops, 2,4,5- tears and wheat straw are weighed respectively
Fear in three kinds of standard sample of pesticide to 10 different mL volumetric flasks, use CH2Cl2Constant volume is diluted, the standard storage of 1000 μ g/mL is made
Standby liquid；100 μ L of three of the above pesticide single standard storing solution are pipetted respectively in 10 mL volumetric flasks, use CH2Cl2Dilute constant volume
To scale, with hybrid standard storing solution（10.0 μg/mL）；Hybrid standard storing solution 25 μ L, 50 μ L, 100 μ are pipetted respectively
In L, 250 μ L, 500 μ L and 1000 μ L to 6 10 mL volumetric flasks and with vehicle solution constant volume；Each standard work
The concentration of solution is respectively 0.025 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.25 μ g/mL, 0.5 μ g/mL, and 1.0
μg/mL；
D, liquid chromatography tandom mass spectrometry determination:The pesticide standard working solution of above prepared various concentration is drawn, injects liquid
Phase chromatography-tandem mass spectrometer；
E, the calculating of persticide residue measurement result
The quantitative analysis of persticide residue is carried out with external standard method, i.e., with the quota ion pair peak area of object to its respective concentration
Regression analysis is carried out, obtains standard curve, related coefficient is more than or equal to 0.994, the sample after extraction is measured, measures inspection
Go out the chromatographic peak area of the quota ion pair of analyte, substitute into standard curve, acquire 2, the 4- drops in sample, 2,4,5- tears and wheat
The residual quantity of the pesticides such as grass fear.
The liquid phase chromatogram condition used for：Chromatographic column：ACQUITY UPLC BEH C18(100 mm×2.1 mm, 1.7 μ
m)；Column temperature：40 ℃；Sample size：10 μL；Mobile phase is methanol：Water=98%：2%（Volume ratio）；Flow velocity：0.3 mL/min.
Scanning of the mass spectrum mode：Anion scans；Ion source：Electron spray ionisation source (ESI)；Ion source temperature：150 ℃；It is de-
Solvent temperature degree：350 ℃；Desolventizing gas flow：800 L/h；Residence time：30 ms；Capillary voltage：2.4 kV；Acquisition
Pattern: MRM.MRM parameters are shown in Table 1.
The method of the present invention overcomes the deficiency of prior art sample treatment, before optimizing sample for tobacco sample
Processing method and instrument testing conditions, compared with prior art with following excellent results：
（1）Inventive method sample pretreatment process is simple, substantially reduces the extraction pre-treatment time of each tobacco sample.Industry
Standard《YC/T 181-2004 tobaccos and the measure gas chromatography of the organic chloroacetamide herbicide persticide residue of tobacco product》, should
Standard method is extracted using 60 mL dichloromethane, and with trimethyl parent's sulfur oxide solution active carbon, gas chromatography-mass spectrum is surveyed
Fixed, pretreatment process complexity is time-consuming, is unfavorable for high-throughput sample and quickly detects, and derivatization process uncertainty is very big, knot
Fruit is less reproducible.
The method of the present invention by after the offal aqueous hydrochloric acid solution of 10mL extraction with a small amount of CH2Cl2Extraction, avoids sample
Pesticide composition to be measured caused by the processes such as concentration, purification, derivative loses, and make experimental implementation simpler, quick, reduces big
Measure the use of organic solvent.
（2）The derivatization reagent that gas chromatography uses is to human health, so as to limit their use；This hair
It is bright without derivatization so as to which pretreatment process be made to become fairly simple.
（3）The present invention is combined using ultra performance liquid chromatography and tandem mass spectrum, is quantified more accurate while is also improved spirit
Sensitivity and repeatability.
1. the detection limit of the method for the present invention：
By 2, the 4- drops of various concentration, 2,4,5- tears and Mediben pesticide standard working solution injection UPLC-MS/MS, with 3 times of letters
It makes an uproar ratio（S/N = 3）Calculate detection limit（LOD）, detection limit is between 0.006 μ g/g-0.023 μ g/g.
2. the repeatability and recovery of standard addition of the method for the present invention：
The standard solution of 2,4- drops, 2,4,5- tears and Mediben pesticide is added in tobacco sample, then carry out pre-treatment and
UPLC-MS/MS is analyzed, and according to scalar sum measured value is added to calculate its rate of recovery, the results are shown in Table 2.As can be seen from Table 2, three kinds
The rate of recovery of pesticide is between 91.8%-95.6%, average relative standard's deviation（RSD）Less than 6.0%, illustrate the method for the present invention
The rate of recovery it is high, it is reproducible.
。
Description of the drawings
Fig. 1 is the assay method flow chart of the present invention（The figure is as Figure of abstract）.
Fig. 2 is the selection chromatography of ions figure of three kinds of phenoxy carboxylic acid pesticides.
Specific embodiment
The present invention is described further below in conjunction with example, but is not the limitation present invention.
Example 1：
1. instrument and reagent：
Pesticide：2,4- drops, 2,4,5- tears and Mediben are standard items (purity is more than 98%)；Methanol, dichloromethane are that agriculture is residual
Grade, hydrochloric acid are pure to analyze.
Waters liquid chromatography-tandem quadrupole mass spectrometers；Vortex oscillation instrument (Labnet companies of the U.S.)；163 electricity of AE
Sub- balance（Sensibility reciprocal：0.0001g）（Mettler companies of Switzerland）.
2. sample treatment：
1.0 g samples are weighed, are placed in 50 mL tool plug centrifuge tubes, add in the aqueous hydrochloric acid solution and 10 mL of 10 mL 0.5moL/L
CH2Cl2, vortex oscillation 15min.1 mL lower floors organic phase is pipetted, is filtered, is detected into UPLC-MS/MS；
3. prepare standard working solution：Three kinds of 0.01 g 2,4- drops, 2,4,5- tears and Mediben standard sample of pesticide are weighed respectively extremely
In 10 different mL volumetric flasks, CH is used2Cl2Constant volume is diluted, the standard reserving solution of 1000 μ g/mL is made；Three more than pipetting respectively
100 μ L of kind pesticide single standard storing solution use CH in 10 mL volumetric flasks2Cl2Dilution be settled to scale, with hybrid standard
Storing solution（10.0 μg/mL）；Hybrid standard storing solution 25 μ L, 50 μ L, 100 μ L, 250 μ L, 500 μ L are pipetted respectively
And 1000 in μ L to 6 10 mL volumetric flasks and with vehicle solution constant volume；The concentration of each standard working solution is respectively
0.025 μg/mL, 0.05 μg/mL, 0.1μg/mL, 0.25 μg/mL, 0.5 μg/mL, 1.0 μg/mL；
4. assay method:The quantitative analysis of persticide residue is carried out with external standard method, i.e., with the quota ion pair peak area of object
Regression analysis is carried out to its respective concentration, obtains standard curve, related coefficient is more than or equal to 0.994, to the sample after extraction into
Row measures, and measures the chromatographic peak area of the quota ion pair of detection analyte, substitutes into standard curve, acquire 2,4- in sample
Drop, 2,4,5- tears content amounts are respectively 0.40mg/kg and 0.08mg/kg.
The liquid phase chromatogram condition used for：Chromatographic column：ACQUITY UPLC BEH C18(100 mm×2.1 mm, 1.7μ
m)；Column temperature：40 ℃；Sample size：10μL；Mobile phase is methanol：Water=98%：2%（Volume ratio）；Flow velocity：0.3 mL/min.Matter
Compose scan mode：Anion scans；Ion source：Electron spray ionisation source (ESI)；Ion source temperature：150 ℃；Desolventizing temperature
Degree：350 ℃；Desolventizing gas flow：800 L/h；Residence time：30 ms；Capillary voltage：2.4 kV；Drainage pattern:
MRM。
For the accuracy of judgment method, 2, the 4- drops of 0.5 μ g/g, 2,4,5- tears and Mediben mark are added in this sample
Quasi- solution carries out sample pre-treatments ibid, and 2,4- drops, 2,4,5- tears and Mediben selection quasi-molecular ions are measured with UPLC MS/MS
Area substitutes into standard curve, acquires 2,4- drops and 2 in sample at this time, 4,5- tears contents are respectively 0.88 μ g/g and 0.56 μ g/
The recovery of standard addition of g i.e. 2,4- drops, 2,4,5- tears and Mediben is 97.7%, 96.6%, and it is accurate to illustrate the method.
Example 2：According to 1 the method for example, another tobacco sample is selected, Mediben detected level is 0.11 in sample
mg/kg。
Claims (2)
1. the method that a kind of extraction-purification Synchronos method measures three kinds of phenoxy carboxylic acid persticide residues in tobacco, it is characterised in that：
Sample is extracted, and use CH with aqueous hydrochloric acid solution2Cl2It is stripped, it is direct with ultra performance liquid chromatography-tandem mass spectrum
2,4- drops, 2,4,5- tears and Mediben residual quantity in tobacco are measured, is as follows：
A, the extraction of sample：1.0 g samples are weighed, are placed in 50 mL tool plug centrifuge tubes, add in the hydrochloric acid of 10 mL 0.5moL/L
The CH of aqueous solution and 10 mL2Cl2, 15 min of vortex oscillation pipettes 1 mL lower floors organic phase, filters, into UPLC-MS/MS detections；
B, the preparation of vehicle solution：2.0 g blank samples are weighed, is placed in 50 mL tool plug centrifuge tubes, adds in 20 mL
The CH of the aqueous hydrochloric acid solution of 0.5moL/L and 20 mL2Cl2, 15 min of vortex oscillation pipettes standby in lower floor's organic phase to liquid storage pipe
With；
C, prepared by standard working solution：Tri- kinds of standard sample of pesticide of 0.01g are weighed respectively, use CH2Cl2It dilutes and uses bare substrate molten
Liquid is finally configured to the hybrid standard working solution containing three kinds of pesticides with concentration gradient；
D, liquid chromatography tandom mass spectrometry determination:The pesticide standard working solution of above prepared various concentration is drawn, injects liquid
Phase chromatography-tandem mass spectrometer；Liquid phase chromatogram condition is：Chromatographic column：ACQUITY UPLC BEH C18, 100 mm × 2.1 of specification
mm, 1.7μm；Column temperature：40 ℃；Sample size：10μL；Mobile phase is methanol：Water=98%：2%, volume ratio；Flow velocity：0.3 mL/
min；Scanning of the mass spectrum mode：Anion scans；Ion source：Electron spray ionisation source (ESI)；Ion source temperature：150 ℃；Desolventizing
Temperature degree：350 ℃；Desolventizing gas flow：800 L/h；Residence time：30 ms；Capillary voltage：2.4 kV；Drainage pattern:
MRM；
E, the calculating of persticide residue measurement result
The quantitative analysis of persticide residue is carried out with external standard method, i.e., with the quota ion pair peak area of object to its respective concentration
Regression analysis is carried out, obtains standard curve, related coefficient is more than or equal to 0.994, the sample after extraction is measured, measures inspection
Go out the chromatographic peak area of the quota ion pair of analyte, substitute into standard curve, acquire 2, the 4- drops in sample, 2,4,5- tears and wheat
The residual quantity of grass fear.
2. extraction according to claim 1-purification Synchronos method measures in tobacco three kinds of phenoxy carboxylic acid persticide residues
Method, it is characterised in that：The manner of formulation of the standard working solution is as follows：0.01 g 2,4- drops, 2,4,5- tears are weighed respectively
In three kinds of standard sample of pesticide of Mediben to 10 different mL volumetric flasks, CH is used2Cl2Constant volume is diluted, is made 1000 μ g/mL's
Standard reserving solution；100 μ L of three of the above pesticide single standard storing solution are pipetted respectively in 10 mL volumetric flasks, use CH2Cl2It is dilute
Release and be settled to scale, with concentration be 10.0 μ g/mL hybrid standard storing solution；Hybrid standard storing solution 25 is pipetted respectively
In μ L, 50 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L to 6 10 mL volumetric flasks and use vehicle solution
Constant volume；The concentration of each standard working solution is respectively 0.025 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.25 μ g/mL,
0.5 μg/mL, 1.0 μg/mL。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109212070A (en) * | 2018-09-24 | 2019-01-15 | 丁立平 | Gas chromatography that is a kind of while measuring four kinds of benzoic acid herbicides in cereal |
| CN109283276A (en) * | 2018-11-25 | 2019-01-29 | 丁立平 | Eight kinds of remaining gas chromatographies of phenoxy carboxylic acid herbicides in a kind of measurement corn |
| CN114577928A (en) * | 2022-01-27 | 2022-06-03 | 大连市检验检测认证技术服务中心 | Method for detecting Edwardsient in food by using deuterium internal standard substance |
-
2017
- 2017-12-27 CN CN201711443491.7A patent/CN108181394A/en active Pending
Non-Patent Citations (3)
| Title |
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| FEI YANG 等: "Determination of Chlorinated Phenoxy Acid Herbicides in Tobacco by Modified QuEChERS Extraction and High-Performance Liquid Chromatography/Tandem Mass Spectrometry", 《JOURNAL OF AOAC INTERNATIONAL》 * |
| URAIRAT KOESUKWIWAT 等: "Rapid determination of phenoxy acid residues in rice by modified QuEChERS extraction and liquid chromatography–tandem mass spectrometry", 《ANALYTICA CHIMICA ACTA》 * |
| 国家烟草专卖局: "YC/T181-2004 烟草及烟草制品残留量的测定 有机氯除草剂农药 气相色谱法", 《中华人民共和国烟草行业标准》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109212070A (en) * | 2018-09-24 | 2019-01-15 | 丁立平 | Gas chromatography that is a kind of while measuring four kinds of benzoic acid herbicides in cereal |
| CN109283276A (en) * | 2018-11-25 | 2019-01-29 | 丁立平 | Eight kinds of remaining gas chromatographies of phenoxy carboxylic acid herbicides in a kind of measurement corn |
| CN109283276B (en) * | 2018-11-25 | 2021-05-07 | 丁立平 | Gas chromatography for determining residues of eight phenoxy carboxylic acid herbicides in corn |
| CN114577928A (en) * | 2022-01-27 | 2022-06-03 | 大连市检验检测认证技术服务中心 | Method for detecting Edwardsient in food by using deuterium internal standard substance |
| CN114577928B (en) * | 2022-01-27 | 2023-10-03 | 大连市检验检测认证技术服务中心 | Method for detecting adewande sweet in food by using deuterium-containing internal standard |
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Application publication date: 20180619 |