CN103308641A - High performance liquid chromatography-tandem mass spectrometry measuring method of three amide herbicides in tobacco and tobacco products - Google Patents
High performance liquid chromatography-tandem mass spectrometry measuring method of three amide herbicides in tobacco and tobacco products Download PDFInfo
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Abstract
The invention relates to a high performance liquid chromatography-tandem mass spectrometry measuring method of three amide herbicides (i.e., alachlor, metolachlor and napropamide) in tobacco and tobacco products, which belongs to the technical filed of physical and chemical inspection of pesticide residue in the tobacco and tobacco products. The high performance liquid chromatography-tandem mass spectrometry measuring method is characterized by being the method which is used for directly extracting the pesticide residue by a substrate dispersion solid-phase extraction method to directly measure the pesticide residue in the tobacco and tobacco products by virtue of chromatography-tandem mass spectrometry. The high performance liquid chromatography-tandem mass spectrometry measuring method of three amide herbicides in tobacco and tobacco products disclosed by the invention can be used for overcoming the defects of the sample treatment method in the prior art, and optimizing the sample pre-treatment method and the apparatus detection condition for the tobacco sample. Moreover, compared with the prior art, the method disclosed by the invention has the excellent effects that the sample pre-treatment process of the method is simple and quick, capable of reducing the interferences of the impurities including pigment and the like in the tobacco, and provided with the advantages of being accurate to operate, high in flexibility and good in repeatability.
Description
Technical field
The invention belongs to the physical and chemical inspection technical field of tobacco and tobacco product Pesticide Residues, relate generally to the determination techniques of acetamide-group herbicides residual quantity in tobacco and the tobacco product, with acetonitrile sample to be carried out lixiviate specifically, add again the vibrations such as anhydrous magnesium sulfate and sodium chloride and impel its layering, disperse subsequently Solid-Phase Extraction, directly measure the method for three kinds of acetamide-group herbicides residual quantities in tobacco and the tobacco product with liquid chromatography-tandem mass spectrometry.
Background technology
Acetamide-group herbicides are that a class of the exploitation sixties in 20th century is efficient, the contact killing type herbicide of high selectivity.It has strong virus killing effect to multiple Gramineae dicotyledon, is mainly used in preventing and kill off the annual gramineous weed young shoot.The rat in vivo studies shows, acetamide-group herbicides can further change into the dialkyl group quinone imines of carcinogenesis, so its residual condition is subject to extensive concern.It is more that relevant this type of herbicide residue of bibliographical information detects analysis, mainly contains gas chromatography-nitrogen phosphorous detector (GC-NPD) method, gas chromatography-electron capture detector (GC-ECD) method, gas chromatography-mass spectrography, high performance liquid chromatography etc.The mensuration of YC/T 179-2004[People's Republic of China (PRC) tobacco business standard YC/T 179-2004 tobacco and tobacco product acetamide-group herbicides persticide residue] use GC-NPD to detect, NPD detects the higher detecting device of nitrogen phosphorus compound sensitivity at present, and NPD is relevant with its molecular structure to the response of nitrogen-containing compound, and particularly the amide-type response is little to amine.The tobacco leaf nitrogen substance is extremely many, is difficult to purify totally fully, easily causes false positive.And there is with the shortcoming that increases degradation service time the accuracy that impact detects in NPD.[the assay laboratory such as Shi Junli, the residual GC-MS of acetamide-group herbicides detects in the tobacco, 29 supplementary issues: 2010,5] tobacco sample is extracted with acetonitrile, then florisil silica Solid-Phase Extraction column purification utilizes GC-MS to detect the isopropyl methoxalamine in the tobacco, enide and three kinds of herbicides of napropamide.But the method need to consume a large amount of solvents, and the method complex operation, and is time-consuming.LC-MS/MS has higher sensitivity and stronger specificity, does not need to make to realize completely chromatographic resolution between the analyte, so that the sample pretreatment process simplification, the analytical test time shortens dramatically simultaneously.Can realize analyzing how residual to polymorphic type the time.
Summary of the invention:
Purpose of the present invention is intended to overcome the prior art defective, a kind of assay method that adopts acetamide-group herbicides residual quantity in Dispersive solid phase extraction-liquid chromatography tandom mass spectrometry determination tobacco and the tobacco product is provided, the method can fast, accurately detect acetamide-group herbicides residual quantity in tobacco and the tobacco product, and measurement result is accurate, mensuration is disturbed few.
The objective of the invention is to be achieved through the following technical solutions: the high performance liquid chromatography-tandem mass assay method of three kinds of amide-types (being alachlor, isopropyl methoxalamine and napropamide) herbicide in tobacco and the tobacco product, by Dispersive solid phase extraction method extraction herbicide residues of pesticides, directly measure persticide residue in tobacco and the tobacco product with liquid chromatography-tandem mass spectrometry, concrete grammar is as follows:
The extraction of a, sample: accurately take by weighing 2 g samples (being accurate to 0.01 g) in 50 mL tools lid centrifuge tube, add 10 mL water, vibrate until sample is fully infiltrated by water.Leave standstill to pipette in 10 mL acetonitriles and the 50 μ L behind 10 min and mark to centrifuge tube, then centrifuge tube is placed on the vortex mixing shaker, with 2000 rpm rate oscillations, 1 min.Centrifuge tube is placed maintenance 10 min under 0 ℃ of condition, then in centrifuge tube, add Agilent SampliQ QuEChERS EN extraction agent box (Agilent 5982-5650), immediately on whirlpool mixing shaker, with 2000 rpm rate oscillations, 2 min, then with centrifugal 10 min of 4000 rpm speed;
B, sample purification: pipette supernatant 1.0 mL in 1.5 mL centrifuge tubes, add Agilent QuEChERS 2 mL and disperse solid phase extraction kit (Agilent 5982-5321), on whirlpool mixing shaker with 2000 rpm rate oscillations, 2 min, with centrifugal 2 min of 6000 rpm speed.Draw supernatant through 0.22 μ m organic phase membrane filtration, pipette 200 μ L, with dilution in acetonitrile to 1.0 mL, detect with LC-MS/MS;
The preparation of c, inner mark solution: owing to isazofos has not used in tobacco, so do interior mark with isazofos.Preparation isazofos concentration is about the methanol solution of 20 μ g/mL;
D, matrix hybrid standard working solution preparation: that preparation has a concentration gradient and contain interior target matrix hybrid standard working solution;
E, liquid chromatography tandom mass spectrometry determination: the matrix hybrid standard working solution of the variable concentrations for preparing more than the absorption, inject liquid chromatography-tandem mass spectrometer;
The calculating of f, persticide residue measurement result
Carry out the quantitative test of residual quantity with internal standard method, namely with agricultural chemicals and interior target quota ion peak area ratio is carried out regretional analysis to its respective concentration, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect agricultural chemicals and interior target quota ion to peak area ratio, the substitution typical curve is tried to achieve the residual quantity of the various agricultural chemicals in the sample.
The manner of formulation of matrix hybrid standard working solution of the present invention is as follows: take by weighing respectively three kinds of standard sample of pesticide of 10 mg in 10 mL volumetric flasks, with acetonitrile dissolving and be settled to scale, be mixed with the single standard storing solution of every kind of agricultural chemicals; Pipette the single standard storing solution of a certain amount of each agricultural chemicals in 100 mL volumetric flasks, be settled to scale with acetonitrile and join to get the hybrid standard storing solution; Pipette respectively hybrid standard storing solution 25 μ L, 50 μ L, 100 μ L, 250 μ L in 500 μ L and 1000 μ L to the 6 10 mL volumetric flask, and add in the 50 μ L mark (isazofos, 20 μ g/mL) and use the acetonitrile constant volume, make standard operation solution; Then pipette respectively above-mentioned standard operation solution 200 μ L and mix with the blank sample extraction solution of 200 μ L, and with dilution in acetonitrile to 1.0 mL, be mixed with matrix hybrid standard working solution.
When LC-MS was measured, the liquid phase chromatogram condition of employing was: chromatographic column: Atiantis dC18 (150 mm * 2.1 mm, 3 μ m, U.S. Waters company); Mobile phase: acetonitrile-water (0.1 % formic acid), the gradient elution program list sees Table 1; Flow velocity: 0.2 mL/min; Column temperature: 30 ℃; Sample size: 10 μ L; The mass spectrum condition that adopts: scan mode: positive ion scanning; Electric spray ion source (ESI); The atomization gas flow is 60 psi; Gas curtain airshed 18 psi; The auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; The collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, the MRM type collection, the MRM parameter sees Table 2.
Method of the present invention has overcome the deficiency of prior art sample treatment, has optimized sample-pretreating method and instrument testing conditions for tobacco sample.Compared with prior art the inventive method has following excellent results:
⑴ the inventive method sample pretreatment process is simple, has greatly shortened the extraction pre-treatment time of each tobacco sample.The inventive method is carried out lixiviate with offal with acetonitrile, adds anhydrous magnesium sulfate, sodium chloride etc. again and impels its layering, gets at last extract and disperses Solid-Phase Extraction.The method improves extraction efficiency, can extract altogether thing (fatty acid, chlorophyll etc.) to other of the pigment in the tobacco and tobacco plant tissue again and play preferably adsorption cleaning effect, the pesticide composition loss to be measured of having avoided sample concentration, purification, the process such as derivative to cause makes again experimental implementation more simple, quick.
(2) the inventive method has advantages of accurate, the highly sensitive and good reproducibility of operation.
1. the detectability of the inventive method:
The agricultural chemicals hybrid standard working solution of variable concentrations is injected LC-MS/MS, calculate detectability (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), detectability is between 0.002 μ g/g-0.005 μ g/g.
2. the repeatability of the inventive method and recovery of standard addition:
Then the standard solution that adds blended in tobacco sample carries out pre-treatment and LC-MS/MS and analyzes, and calculate its recovery according to adding the scalar sum measured value, the results are shown in Table 3.As can be seen from Table 3, the recovery of various herbicides is all greater than 95%, and average relative standard deviation (RSD) illustrates that the recovery of the inventive method is high, good reproducibility less than 6.0%.
Description of drawings
Fig. 1 is assay method process flow diagram of the present invention (this figure is as Figure of abstract).
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
Example 1:
1. instrument and reagent:
Three kinds of agricultural chemicals are standard items; Acetonitrile, formic acid are the residual level of farming.
API 4000 quadrupole rod tandem mass spectrometers; Vortex shaker (U.S. Labnet company); Sigma 3-30K hydro-extractor (German Sigma company); AE 163 electronic balances (sensibility reciprocal: 0.0001g) with AE 166 electronic balances (sensibility reciprocal: 0.01g) (Switzerland Mettler company).
2. sample preparation:
Accurately take by weighing 2 g samples (being accurate to 0.01 g) in 50 mL tools lid centrifuge tube, add 10 mL water, vibrate until sample is fully infiltrated by water.Leave standstill and add that mark (isazofos, 20 μ g/mL) then places centrifuge tube on the vortex mixing shaker, with 2000 rpm rate oscillations, 1 min in 10 mL acetonitriles and the 50 μ L behind 10 min to centrifuge tube.Centrifuge tube is placed maintenance 10 min under 0 ℃ of condition, then in centrifuge tube, add Agilent SampliQ QuEChERS EN extraction agent box (Agilent 5982-5650), immediately on whirlpool mixing shaker, with 2000 rpm rate oscillations, 2 min, then with centrifugal 10 min of 4000 rpm speed.
Pipette supernatant 1.0 mL in 1.5 mL centrifuge tubes, add Agilent QuEChERS 2 mL and disperse solid phase extraction kit (Agilent 5982-5321), on whirlpool mixing shaker with 2000 rpm rate oscillations, 2 min, with centrifugal 2 min of 6000 rpm speed.Draw supernatant through 0.22 μ m organic phase membrane filtration, pipette 200 μ L, with dilution in acetonitrile to 1.0 mL, detect with LC-MS/MS.
3. prepare standard operation solution: take by weighing respectively three kinds of standard sample of pesticide of 10mg in 10 mL volumetric flasks, with the acetonitrile dissolving and be settled to scale, be mixed with the single standard storing solution of every kind of agricultural chemicals; Pipette the single standard storing solution of a certain amount of each agricultural chemicals in the 100mL volumetric flask, be settled to scale with acetonitrile and join to get the hybrid standard storing solution; Pipette respectively hybrid standard storing solution 25 μ L, 50 μ L, 100 μ L, 250 μ L in 500 μ L and 1000 μ L to the 6 10 mL volumetric flask, and add in the 50 μ L mark (isazofos, 20 μ g/mL) and use the acetonitrile constant volume, make standard operation solution; Then pipette respectively above-mentioned standard operation solution 200 μ L and mix with the blank sample extraction solution of 200 μ L, and with dilution in acetonitrile to 1.0 mL, be mixed with matrix hybrid standard working solution.
4. assay method: the agricultural chemicals matrix hybrid standard working solution of the variable concentrations for preparing is injected LC-MS/MS, carry out the quantitative test of residual quantity with internal standard method, namely with agricultural chemicals and interior target quota ion peak area ratio is carried out regretional analysis to its respective concentration, obtain typical curve, related coefficient is more than or equal to 0.999, and the sample after extracting is measured, and records to detect agricultural chemicals and interior target quota ion to peak area ratio, the substitution typical curve is tried to achieve the residual quantity of each agricultural chemicals in the sample.The alachlor content of trying to achieve in the sample is 0.14 μ g/g.
The LC-MS/MS condition that adopts is: the liquid phase chromatogram condition of employing is: chromatographic column: Atiantis dC18 (150 mm * 2.1 mm, 3 μ m, U.S. Waters company); Mobile phase: acetonitrile-water (0.1 % formic acid), the gradient elution program list sees Table 1; Flow velocity: 0.2 mL/min; Column temperature: 30 ℃; Sample size: 10 μ L; The mass spectrum condition that adopts: scan mode: positive ion scanning; Electric spray ion source (ESI); The atomization gas flow is 60 psi; Gas curtain airshed 18 psi; The auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; The collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, the MRM type collection, the MRM parameter sees Table 2.
Accuracy for determination methods, the alachlor standard solution that in this sample, adds 0.10 μ g/g, carry out the same sample pre-treatments, record alachlor with LC-MS/MS and select quasi-molecular ions area and interior mark peak area ratio, the substitution typical curve, try to achieve this moment sample in alachlor content be respectively 0.22 μ g/g.The recovery of standard addition that is alachlor is 91.7%, illustrates that the method is accurately.
Example 2:
As described in Example 1, select another tobacco sample, record that the residual quantity of napropamide is respectively 0.05 μ g/g in the sample.
Example 3:
As described in Example 1, select another tobacco sample, record that alachlor content is 0.09 μ g/g in the sample.
Claims (3)
- One grow tobacco and tobacco product in the high performance liquid chromatography-tandem mass assay method of three kinds of acetamide-group herbicides, be alachlor, isopropyl methoxalamine and three kinds of herbicides of napropamide, it is characterized in that: the method is by Dispersive solid phase extraction method extraction herbicide residues of pesticides, directly measure persticide residue in tobacco and the tobacco product with liquid chromatography-tandem mass spectrometry, concrete grammar is as follows:The extraction of a, sample: accurately take by weighing 2 g samples (being accurate to 0.01 g) in 50 mL tools lid centrifuge tube, add 10 mL water, vibrate until sample is fully infiltrated by water; Leave standstill to pipette in 10 mL acetonitriles and the 50 μ L behind 10 min and mark to centrifuge tube, then centrifuge tube is placed on the vortex mixing shaker, with 2000 rpm rate oscillations, 1 min;Centrifuge tube is placed maintenance 10 min under 0 ℃ of condition, then in centrifuge tube, add Agilent SampliQ QuEChERS EN extraction agent box, immediately on whirlpool mixing shaker, with 2000 rpm rate oscillations, 2 min, then with centrifugal 10 min of 4000 rpm speed;B, sample purification: pipette supernatant 1.0 mL in 1.5 mL centrifuge tubes, add Agilent QuEChERS 2 mL and disperse solid phase extraction kit, on whirlpool mixing shaker with 2000 rpm rate oscillations, 2 min, with centrifugal 2 min of 6000 rpm speed; Draw supernatant through 0.22 μ m organic phase membrane filtration, pipette 200 μ L, with dilution in acetonitrile to 1.0 mL, detect with LC-MS/MS;The preparation of c, inner mark solution: do interior mark with isazofos or EPTC, preparation isazofos concentration is about the methanol solution of 20 μ g/mL;D, matrix hybrid standard working solution preparation: that preparation has a concentration gradient and contain interior target matrix hybrid standard working solution;E, liquid chromatography tandom mass spectrometry determination: the matrix hybrid standard working solution of the variable concentrations for preparing more than the absorption, inject liquid chromatography-tandem mass spectrometer;The calculating of f, persticide residue measurement resultCarry out the quantitative test of residual quantity with internal standard method, namely with agricultural chemicals and interior target quota ion peak area ratio is carried out regretional analysis to its respective concentration, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect agricultural chemicals and interior target quota ion to peak area ratio, the substitution typical curve is tried to achieve the residual quantity of the various agricultural chemicals in the sample.
- 2. assay method according to claim 1, it is characterized in that: standard operation solution prepares specific as follows: take by weighing respectively three kinds of standard sample of pesticide of 10 mg in 10 mL volumetric flasks, with acetonitrile dissolving and be settled to scale, be mixed with the single standard storing solution of every kind of agricultural chemicals; Pipette the single standard storing solution of a certain amount of each agricultural chemicals in 100 mL volumetric flasks, be settled to scale with acetonitrile and join to get the hybrid standard storing solution; Pipette respectively hybrid standard storing solution 25 μ L, 50 μ L, 100 μ L, 250 μ L in 500 μ L and 1000 μ L to the 6 10 mL volumetric flask, and add in the 50 μ L mark and use the acetonitrile constant volume, make standard operation solution; Then pipette respectively above-mentioned standard operation solution 200 μ L and mix with the blank sample extraction solution of 200 μ L, and with dilution in acetonitrile to 1.0 mL, be mixed with matrix hybrid standard working solution.
- 3. assay method according to claim 1, it is characterized in that: the liquid phase chromatogram condition of employing is: chromatographic column: Atiantis dC18 (150 mm * 2.1 mm, 3 μ m, U.S. Waters company); Mobile phase: acetonitrile-water (0.1 % formic acid), gradient elution; Flow velocity: 0.2 mL/min; Column temperature: 30 ℃; Sample size: 10 μ L; The mass spectrum condition that adopts: scan mode: positive ion scanning; Electric spray ion source (ESI); The atomization gas flow is 60 psi; Gas curtain airshed 18 psi; The auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; The collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, the MRM type collection.
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| CN104698119A (en) * | 2015-03-31 | 2015-06-10 | 中国科学院长春应用化学研究所 | Method for detecting amide compounds in environment water sample |
| CN105032381A (en) * | 2015-06-05 | 2015-11-11 | 中国农业科学院农业质量标准与检测技术研究所 | Compound molecularly imprinted solid phase extraction column as well as preparation method and application thereof |
| CN108414664A (en) * | 2018-04-11 | 2018-08-17 | 国家烟草质量监督检验中心 | A kind of method that ultra high efficiency conjunction phase chromatography-tandem mass spectrum technology splits, measures Chiral pesticide isopropyl methoxalamine enantiomer |
| CN108508130A (en) * | 2018-04-11 | 2018-09-07 | 国家烟草质量监督检验中心 | A kind of method that ultra high efficiency conjunction phase chromatography-tandem mass spectrum technology splits, measures Chiral pesticide metalaxyl and dimethomorph enantiomer |
| CN108918709A (en) * | 2018-07-12 | 2018-11-30 | 河北医科大学 | Screening, quantitative detecting method and the application of common herbicide in a kind of blood |
| CN109828067A (en) * | 2019-03-15 | 2019-05-31 | 黑龙江八一农垦大学 | A method of the acetamide-group herbicides in separation and enrichment naked oats |
| CN110068622A (en) * | 2019-03-27 | 2019-07-30 | 黑龙江八一农垦大学 | Acetamide-group herbicides efficiently separates method and rapid detection method in miscellaneous beans |
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| CN104698119A (en) * | 2015-03-31 | 2015-06-10 | 中国科学院长春应用化学研究所 | Method for detecting amide compounds in environment water sample |
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| CN105032381A (en) * | 2015-06-05 | 2015-11-11 | 中国农业科学院农业质量标准与检测技术研究所 | Compound molecularly imprinted solid phase extraction column as well as preparation method and application thereof |
| CN108414664A (en) * | 2018-04-11 | 2018-08-17 | 国家烟草质量监督检验中心 | A kind of method that ultra high efficiency conjunction phase chromatography-tandem mass spectrum technology splits, measures Chiral pesticide isopropyl methoxalamine enantiomer |
| CN108508130A (en) * | 2018-04-11 | 2018-09-07 | 国家烟草质量监督检验中心 | A kind of method that ultra high efficiency conjunction phase chromatography-tandem mass spectrum technology splits, measures Chiral pesticide metalaxyl and dimethomorph enantiomer |
| CN108918709A (en) * | 2018-07-12 | 2018-11-30 | 河北医科大学 | Screening, quantitative detecting method and the application of common herbicide in a kind of blood |
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| CN109828067A (en) * | 2019-03-15 | 2019-05-31 | 黑龙江八一农垦大学 | A method of the acetamide-group herbicides in separation and enrichment naked oats |
| CN110068622A (en) * | 2019-03-27 | 2019-07-30 | 黑龙江八一农垦大学 | Acetamide-group herbicides efficiently separates method and rapid detection method in miscellaneous beans |
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