CN109100448A - The detection method of dinocap residual quantity in a kind of tobacco - Google Patents
The detection method of dinocap residual quantity in a kind of tobacco Download PDFInfo
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- CN109100448A CN109100448A CN201811258941.XA CN201811258941A CN109100448A CN 109100448 A CN109100448 A CN 109100448A CN 201811258941 A CN201811258941 A CN 201811258941A CN 109100448 A CN109100448 A CN 109100448A
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- dinocap
- residual quantity
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
Abstract
The invention discloses a kind of detection methods of dinocap residual quantity in tobacco.Tobacco sample is extracted using improved QuEChERS technology extracting method, C18 scattered adsorption agent, using the combination method detection of gas-chromatography negative chemical ionization mass spectrometry, quantified by external standard method, the result shows that dinocap is good in 0.01-0.5 mg/L range linear relationship, related coefficient (r2) it is greater than 0.99, detection is limited to 0.02 mg/kg, and the rate of recovery of the dinocap in tobacco is 95.83%~102.34%, and relative standard deviation is 3.75%~5.30%.The detection method sample pre-treatments are simple, quick, and sensitivity, accuracy and precision meet Detecting Pesticide requirement, the detection of dinocap residual quantity suitable for tobacco.
Description
Technical field
The invention belongs to the Detection Technologies of Pesticide Residues technical fields, and in particular to the inspection of dinocap residual quantity in a kind of tobacco
Survey method.
Background technique
Dinocap (dinocap, CAS:39300-45-3) is made of six kinds of different dinitro crotonates isomers
Mixture, be a kind of contact killing type fungicide, be mainly used for preventing and treating the powdery mildew in crops and fruits and vegetables, in addition it can conduct
Non-internal-absorting acaricide.Dinocap is more toxic, have teratogenesis and carcinogenicity, apply it is improper can be caused in crops it is residual
It stays, seriously affects quality of tobacco and safety, therefore, each state has all formulated quite stringent MRL value, CORESTA directiveness residual
Dinocap is 0.6 mg/kg in (GRL) regulation of limiting the quantity tobacco, and China Tobacco Corporation defines the maximum of dinocap in tobacco
Residue limits (MRL) are 0.1 mg/kg, therefore extremely important to its remaining detection.
Since dinocap has thermal instability and chemical instability, hydrolysis or photodissociation are easy into corresponding phenol, and
Six isomer structures of dinocap are similar, the more difficult separation in chromatography and mass spectrum, therefore, examine to the residual of dinocap
Surveying is always the very challenging work in Detecting Pesticide field.The detection method of external report mainly has at present
Gas-chromatography-ECD method, liquid chromatography, Liquid Chromatography-Mass Spectrometry.Liquid chromatography or Liquid Chromatography-Mass Spectrometry
The cumbersome time-consuming of pre-treatment extraction step, needs to convert six isomers all complete hydrolysis of dinocap to phenol, hydrolysis time compared with
It is long, and the standard items since dinocap hydrolysis phenol cannot be bought, it is difficult to accurate quantitative analysis；It is selected when being analyzed using gas-chromatography-ECD method
Selecting property, precision and reproducibility are poor.
Based on problem above, it is necessary to invent a kind of detection method of dinocap residual quantity in tobacco.
Summary of the invention
The purpose of the present invention is to provide a kind of detection methods of dinocap residual quantity in tobacco.
The object of the present invention is achieved like this, comprising the following steps:
1) preparation of standard solution: accurately weighing dinocap standard items, and dissolution is settled in brown volumetric flask, is configured to 1mg/
The standard reserving solution of mL, is kept in dark place in -15 ~ -25 DEG C of refrigerators, and standard reserving solution is diluted to series standard working solution,
For making standard curve；
2) sample pre-treatments:
Extract: weigh sample to be tested into centrifuge tube, add water vibrate to sample sufficiently infiltrated by water after stand 8-12min；It pipettes
1% formic acid-acetonitrile with water equivalent is into centrifuge tube, and with 2~5 min of 1500-2500 r/min velocity fluctuation；In centrifuge tube
In be separately added into anhydrous magnesium sulfate, sodium chloride, sodium citrate, DisodiumHydrogen Citrate, additional amount is sample to be tested: anhydrous slufuric acid
Magnesium: sodium chloride: sodium citrate: DisodiumHydrogen Citrate=1:2:0.5:0.5:0.25, immediately with the vibration of 1500-2500 r/min speed
Swing 2~5 min；Then 3~5 min are centrifuged with 5000-7000r/min；
Purification: pipetting 1 mL of supernatant into 1.5 mL centrifuge tubes, and 50~200 mg C18 scattered adsorption agent, vortex oscillation is added
2~5 min are centrifuged 3~5 min with 5000~6000 r/min, and Aspirate supernatant crosses upper machine after 0.22 μm of organic phase filter membrane
Analysis；
3) detection of dinocap residual quantity: will be joined by step (2) treated sample using gas-chromatography negative chemical ionization mass spectrometry
Usage detection, and the standard curve obtained in conjunction with step (1) measures dinocap residual quantity.
Compared with prior art, beneficial effects of the present invention:
1, the extraction using quick, simple, reliable extracting method for dinocap in tobacco sample of the invention, so
The agent of C18 scattered adsorption is added afterwards, using dinocap in highly sensitive gas-chromatography negative chemical ionization mass spectrometry combination method measurement tobacco
Residual quantity, compared with prior art, detection method of the invention has that sample pre-treatments are easier, sensitivity and accuracy are higher
The characteristics of, the requirement of dinocap Detecting Pesticide can be fully met.
2, gas-chromatography negative chemical ionization mass spectrometry of the invention combination method has the substance of the group containing electronegativity highly selective
And high sensitivity, QuEChERS method is applied to the extraction of dinocap in tobacco sample for the first time, it is net that the agent of C18 scattered adsorption is added
Change, using dinocap in highly sensitive GC-NCI-MS measurement tobacco, effectively improves treatment effeciency and sensitivity.
3, detection method is simple, and the extraction step of sample is efficient, safe, at low cost, the purifying step letter of sample
Single quickly clean-up effect and the rate of recovery are high, pass through the control of chromatographic condition in the optimization and detection to pre-treatment in detection process
System realizes dinocap in tobacco and accurately, timely detects.
4, chromatographic process of the invention is right using negative chemical source soft ionization to dinocap isomer good separating effect
Dinocap has highly selective and highly sensitive, the accurate detection of dinocap residual quantity suitable for tobacco.
Detailed description of the invention
Fig. 1 is that addition chlorfenethol popularizes dinocap standard solution chromatogram in tobacco blank sample in the embodiment of the present invention 1.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is further illustrated, but is not subject in any way to the present invention
Limitation, based on present invention teach that it is made it is any transform or replace, all belong to the scope of protection of the present invention.
The detection method of dinocap residual quantity in tobacco of the present invention, comprising the following steps:
1) preparation of standard solution: accurately weighing dinocap standard items, and dissolution is settled in brown volumetric flask, is configured to 1mg/
The standard reserving solution of mL, is kept in dark place in -15 ~ -25 DEG C of refrigerators, and standard reserving solution is diluted to series standard working solution,
For making standard curve；
2) sample pre-treatments:
Extract: weigh sample to be tested into centrifuge tube, add water vibrate to sample sufficiently infiltrated by water after stand 8-12min；It pipettes
1% formic acid-acetonitrile with water equivalent is into centrifuge tube, and with 2~5 min of 1500-2500 r/min velocity fluctuation；In centrifuge tube
In be separately added into anhydrous magnesium sulfate, sodium chloride, sodium citrate, DisodiumHydrogen Citrate, additional amount is sample to be tested: anhydrous slufuric acid
Magnesium: sodium chloride: sodium citrate: DisodiumHydrogen Citrate=1:2:0.5:0.5:0.25, immediately with the vibration of 1500-2500 r/min speed
Swing 2~5 min；Then 3~5 min are centrifuged with 5000-7000r/min；
Purification: pipetting 1 mL of supernatant into 1.5 mL centrifuge tubes, and 50~200 mg C18 scattered adsorption agent, vortex oscillation is added
2~5 min are centrifuged 3~5 min with 5000~6000 r/min, and Aspirate supernatant crosses upper machine after 0.22 μm of organic phase filter membrane
Analysis；
3) detection of dinocap residual quantity: will be joined by step (2) treated sample using gas-chromatography negative chemical ionization mass spectrometry
Usage detection, and the standard curve obtained in conjunction with step (1) measures dinocap residual quantity.
Further, the preparation method of standard reserving solution as described in step (1) is accurately to weigh dinocap standard items 0.1
G is accurate to 0.1 mg, is settled to 100mL brown volumetric flask with methanol dissolution, is configured to the standard reserving solution of 1mg/mL.
Further, the production method of standard curve as described in step (1) is specially and is stored up dinocap standard with methanol
Standby liquid is configured to the dinocap standard working solution of 0.01,0.02,0.05,0.1,0.2 and 0.5 mg/L series mass concentration,
Linear regression is carried out to each concentration with peak area, obtains standard curve, the standard curve is in dinocap mass concentration
It is in good linear, correlation coefficient r within the scope of 0.01-0.5 mg/L2Greater than 0.99.
Further, the detection method further includes addition recovery experiment, and the addition recovery experiment is using cigarette
Careless blank sample is added recycling, is used to add recovery test for the dinocap standard reserving solution, specially exists respectively
0.05, recovery testu is carried out under 0.1,0.5 mg/kg, 3 pitch-based spheres, each addition concentration sets 6 parallel samples, so
Sample pre-treatments and detection are carried out afterwards, and the rate of recovery of the dinocap in tobacco is 95.83%~102.34%, relative standard
Deviation is 3.75%~5.30%.
Further, extraction described in step (2) is specially to weigh 2 g samples to be tested, 0.01 g is accurate to, in 50
ML has in lid centrifuge tube, and 10 mL water are added, and oscillation stands 10 min after sufficiently being infiltrated to sample by water；Pipette 10 mL, 1% first
Acid-acetonitrile is placed on whirlpool mixing shaker into centrifuge tube with 2000 r/min velocity fluctuation, 2~5 min；It is being centrifuged
4 g anhydrous magnesium sulfates, 1 g sodium chloride, 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate are separately added into pipe, immediately in whirlpool
It mixes on shaker with 2000 r/min velocity fluctuation, 2~5 min, is then centrifuged 3~5 min with 6000 r/min.
Further, purification described in step (2) is specially to pipette 1 mL of supernatant into 1.5 mL centrifuge tubes, is added
50 mg C18 scattered adsorption agent, vortex vibrate 2 min, are centrifuged 3 min with 6000 r/min, Aspirate supernatant crosses 0.22 μm
Upper machine analysis after organic phase filter membrane.
Further, the chromatographic condition of the combination of gas-chromatography negative chemical ionization mass spectrometry described in step (3) method is chromatographic column:
Mm × 0.25 μm DB-5MS(30 m × 0.25).
Further, mass spectrometric analysis condition described in step (3) are as follows: Negative chemical ionization (NCI), using selection from
Sub (SIM) mode, characteristic ion are m/z 278 and m/z 279, and wherein m/z 278 is quota ion.
Further, the detection of dinocap residual quantity described in step (3) is limited to 0.02 mg/kg, is quantitatively limited to 0.07
mg/kg。
Further, the purity of the dinocap standard items is 98%；Methanol, acetonitrile and the formic acid is HPLC grades；
The anhydrous magnesium sulfate be analyze it is pure and using it is preceding 650 DEG C calcination 4 hours, be stored in spare in drier；The chlorine
Changing sodium, sodium citrate, DisodiumHydrogen Citrate is that analysis is pure.
Embodiment 1
1, instrument and reagent: Bruker 450GC-300MS gas chromatography tandem mass spectrometry instrument (Bruker company of the U.S.),
Millipore ultrapure water machine (Millipore Simplicity company of the U.S.), 5804 supercentrifuge of Eppendorf (Germany
Eppendorf company), Talboys digital display multitube vortex mixer (Town in Shanghai spectrum Scientific Instruments Corporation).Methanol, acetonitrile,
Formic acid, HPLC grades, Fisher company of the U.S..Anhydrous magnesium sulfate is analyzed pure.Before should 650 DEG C calcination 4 hours, be stored in dry
It is spare in dry device.Sodium chloride, sodium citrate, DisodiumHydrogen Citrate are analyzed pure.Dinocap standard items (purity 98%, German Dr
Company provides).
2, in tobacco dinocap residual quantity detection method:
1) preparation of standard solution: accurately weighing dinocap standard items (being accurate to 0.1 mg) respectively, dissolves constant volume with methanol
To 100mL brown volumetric flask, it is made into the single standard stock solution of 1mg/L, is kept in dark place in -20 DEG C of refrigerators, for making mark
Directrix curve and quantitative detection.
2) sample pre-treatments: weighing about 2 g samples, be accurate to 0.01 g, and in 50 mL tool lid centrifuge tube, 10 mL are added
Water, oscillation stand 10 min after sufficiently being infiltrated to sample by water.10 mL1% formic acid-acetonitrile is pipetted into centrifuge tube, is placed in whirlpool
With 2000 r/min velocity fluctuation, 2 min on whirlpool mixing shaker.By centrifuge tube, freezing is protected in freezer compartment of refrigerator (- 18 DEG C)
After depositing 10 min, take out.4 g anhydrous magnesium sulfates, 1 g sodium chloride, 1 g sodium citrate and 0.5 g are separately added into centrifuge tube
DisodiumHydrogen Citrate, immediately on whirlpool mixing shaker with 2000 r/min velocity fluctuation, 2 min, to prevent anhydrous slufuric acid
Magnesium meets water reaction and causes hot-spot and agglomerate, and is then centrifuged 3 min with 6000 r/min.Pipette 1 mL of supernatant to 1.5 mL
In centrifuge tube, 50 mg C18 scattered adsorption agent are added, vortex vibrates 2 min, 3 min is centrifuged with 6000 r/min, in absorption
Clear liquid crosses upper machine analysis after 0.22 μm of organic phase filter membrane.
3) it the detection of dinocap residual quantity: the detection of dinocap residual quantity: will be adopted by step (2) treated sample
It is detected with gas-chromatography negative chemical ionization mass spectrometry combination method, and the standard curve obtained in conjunction with step (1) measures dinocap residual quantity.
Spectrometry condition: chromatographic column: mm × 0.25 μm DB-5MS(30 m × 0.25)；Sample volume: 1 μ L,
Split ratio 20:1；Injection port: 250 DEG C；Temperature program: 100 DEG C of holdings 2 min, 10 DEG C/min rise to 280 DEG C, keep 6 min；
Carrier gas: helium, 1.0 mL/min, Negative chemical ionization (NCI), reaction gas: methane, it is special using selection ion (SIM) mode
Sign ion is m/z 278 and m/z 279, and wherein m/z 278 is quota ion.
3, result and analysis:
1) range of linearity and detection limit (production of standard curve):
Dinocap is configured to the dinocap of 0.01,0.02,0.05,0.1,0.2 and 0.5 mg/L series mass concentration with methanol
Standard working solution carries out linear regression with concentration of the peak area to various pesticides, in good within the scope of 0.01-0.5 mg/L
Linearly, curvilinear equation isY=2.1011e5 X-1.94e5, correlation coefficient r2It is 0.9923, respectively with 3 times and 10 times of signal-to-noise ratio (S/
N its detection limit and quantitative limit) are determined, show that detection of the dinocap in tobacco is limited to 0.02 mg/kg, is quantitatively limited to 0.07
mg/kg。
2) rate of recovery, precision and matrix effect (addition recovery test):
Recycling and Precision Experiment are added using tobacco blank sample.It is added respectively at 0.05,0.1,0.5 mg/kg 3
Level is lower to carry out recovery testu, and each addition concentration sets 6 parallel samples, carries out sample treatment and survey by this experimental method
It is fixed, it the results are shown in Table 1, the rate of recovery of the dinocap in tobacco is 95.83%~102.34%, relative standard deviation is 3.75%~
5.30%, the rate of recovery and precision of method are all preferable.It is as molten in added the universal dinocap standard of chlorfenethol in Fig. 1 tobacco blank sample
Liquid chromatography figure.
Recovery of standard addition of 1 dinocap of table in tobacco, precision (n=6)
3) selection of Extraction solvent: acetonitrile is that common pesticide residue extracts reagent, and acetonitrile extracting solution chaff interferent is organic compared with other
Reagent is few.The dinocap of 0.1 mg/kg is added in tobacco bare substrate, after mixing place 2h after, be respectively compared acetonitrile,
1% formic acid-acetonitrile solution, 1% acetic acidacetonitrile solution for target pesticide extraction efficiency.The experimental results showed that 1% first
Rate of recovery highest (99.03%) of the acid-acetonitrile solution as Extraction solvent, the extraction efficiency of acetonitrile next (92.67%), 1% second
Acid-acetonitrile solution extraction efficiency is worst (90.52%), comprehensively considers, and selects extraction of the 1% formic acid-acetonitrile as this experiment
Solvent.
4) selection of scattered adsorption agent:
The C18 adsorbent and PSA adsorbent for weighing 50,100,150,200 mg respectively are in 2.0 mL centrifuge tubes, in tobacco sky
The dinocap of 0.1 mg/kg is added in Bai Jizhi, is extracted according to sample pre-treatments extraction step, takes 1 mL of supernatant to being equipped with not
With the centrifuge tube of adsorbent, 2 kinds of adsorbents are investigated on the influence of the rate of recovery of dinocap and clean-up effect.The results showed that PSA
As weak anion exchanger, there is stronger absorption to make fatty acid, organic acid, organic carbohydrate isopolarity compound
With its suction-operated is reinforced as adsorbent amount increases, therefore it is neter to clean, but is below to the rate of recovery of dinocap
50%.C18 has preferable clean-up effect to lipid, and has the preferable rate of recovery to dinocap, as adsorbent amount increases
Add, the rate of recovery of impurity elimination effect and dinocap has no significant change, comprehensively considers the decontamination effect of two kinds of adsorbents and to mesh
The absorption situation of compound is marked, 50~200mg C18 adsorbent is selected to purify extracting solution.
Embodiment 2
The detection method of dinocap residual quantity in a kind of tobacco, comprising the following steps:
1) preparation of standard solution: accurately weighing 0.1 g of dinocap standard items, be accurate to 0.1 mg, is settled to methanol dissolution
100mL brown volumetric flask is configured to the standard reserving solution of 1mg/mL, is kept in dark place in -15 DEG C of refrigerators, by standard reserving solution
It is diluted to series standard working solution, for making standard curve；
The production method of the standard curve be specially dinocap standard reserving solution is configured to 0.01 with methanol, 0.02,
0.05, the dinocap standard working solution of 0.1,0.2 and 0.5 mg/L series mass concentration carries out each concentration with peak area
Linear regression obtains standard curve, and the standard curve, which is within the scope of 0.01-0.5 mg/L in dinocap mass concentration, is in
Good linear, correlation coefficient r2Greater than 0.99；
2) sample pre-treatments:
Extract: weigh sample to be tested into centrifuge tube, add water vibrate to sample sufficiently infiltrated by water after stand 8min；It pipettes and water
1% formic acid-the acetonitrile of equivalent is into centrifuge tube, and with 5 min of 1500r/min velocity fluctuation；Nothing is separately added into centrifuge tube
Water magnesium sulfate, sodium chloride, sodium citrate, DisodiumHydrogen Citrate, additional amount are sample to be tested: anhydrous magnesium sulfate: sodium chloride: lemon
Sour sodium: DisodiumHydrogen Citrate=1:2:0.5:0.5:0.25, immediately with 1500 r/min velocity fluctuation, 5 min；Then with
5000r/min is centrifuged 5 min；
Purification: pipetting 1 mL of supernatant into 1.5 mL centrifuge tubes, and 50 mg C18 scattered adsorption agent, vortex oscillation 2 is added
Min is centrifuged 5 min with 5000 r/min, and Aspirate supernatant crosses upper machine analysis after 0.22 μm of organic phase filter membrane；
3) detection of dinocap residual quantity: will be joined by step (2) treated sample using gas-chromatography negative chemical ionization mass spectrometry
Usage detection, and the standard curve obtained in conjunction with step (1) measures dinocap residual quantity.
The chromatographic condition of the gas-chromatography negative chemical ionization mass spectrometry combination method is chromatographic column: m × 0.25 DB-5MS(30
Mm × 0.25 μm).The mass spectrometric analysis condition are as follows: Negative chemical ionization (NCI), using selection ion (SIM) mould
Formula, characteristic ion are m/z 278 and m/z 279, and wherein m/z 278 is quota ion.
The purity of the dinocap standard items is 98%；Methanol, acetonitrile and the formic acid is HPLC grades；The nothing
Water magnesium sulfate be analyze it is pure and using it is preceding 650 DEG C calcination 4 hours, be stored in spare in drier；The sodium chloride, lemon
Sour sodium, DisodiumHydrogen Citrate are that analysis is pure.
The detection method further includes addition recovery experiment, and the addition recovery experiment is using tobacco blank sample
Be added recycling, the dinocap standard reserving solution be used to add recovery test, specially respectively 0.05,0.1,
Recovery testu is carried out under 0.5 pitch-based sphere of mg/kg 3, each addition concentration sets 6 parallel samples, then carries out sample
Product pre-treatment and detection, the results show that the rate of recovery and precision of this method are all preferable.
Embodiment 3
The detection method of dinocap residual quantity in a kind of tobacco, comprising the following steps:
1) preparation of standard solution: accurately weighing 0.1 g of dinocap standard items, be accurate to 0.1 mg, is settled to methanol dissolution
100mL brown volumetric flask is configured to the standard reserving solution of 1mg/mL, is kept in dark place in -25 DEG C of refrigerators, by standard reserving solution
It is diluted to series standard working solution, for making standard curve；
The production method of the standard curve be specially dinocap standard reserving solution is configured to 0.01 with methanol, 0.02,
0.05, the dinocap standard working solution of 0.1,0.2 and 0.5 mg/L series mass concentration carries out each concentration with peak area
Linear regression obtains standard curve, and the standard curve, which is within the scope of 0.01-0.5 mg/L in dinocap mass concentration, is in
Good linear, correlation coefficient r2Greater than 0.99；
2) sample pre-treatments:
Extract: weigh sample to be tested into centrifuge tube, add water vibrate to sample sufficiently infiltrated by water after stand 12min；Pipette with
1% formic acid-the acetonitrile of water equivalent is into centrifuge tube, and with 2500 r/min velocity fluctuation 2min；It is separately added into centrifuge tube
Anhydrous magnesium sulfate, sodium chloride, sodium citrate, DisodiumHydrogen Citrate, additional amount are sample to be tested: anhydrous magnesium sulfate: sodium chloride: lemon
Lemon acid sodium: DisodiumHydrogen Citrate=1:2:0.5:0.5:0.25, immediately with 2500 r/min velocity fluctuation 2min；Then with
7000r/min is centrifuged 3 min；
Purification: pipetting 1 mL of supernatant into 1.5 mL centrifuge tubes, and 200 mg C18 scattered adsorption agent, vortex oscillation 5 is added
Min is centrifuged 3 min with 6000 r/min, and Aspirate supernatant crosses upper machine analysis after 0.22 μm of organic phase filter membrane；
3) detection of dinocap residual quantity: will be joined by step (2) treated sample using gas-chromatography negative chemical ionization mass spectrometry
Usage detection, and the standard curve obtained in conjunction with step (1) measures dinocap residual quantity.
The chromatographic condition of the gas-chromatography negative chemical ionization mass spectrometry combination method is chromatographic column: m × 0.25 DB-5MS(30
Mm × 0.25 μm).The mass spectrometric analysis condition are as follows: Negative chemical ionization (NCI), using selection ion (SIM) mould
Formula, characteristic ion are m/z 278 and m/z 279, and wherein m/z 278 is quota ion.
The purity of the dinocap standard items is 98%；Methanol, acetonitrile and the formic acid is HPLC grades；The nothing
Water magnesium sulfate be analyze it is pure and using it is preceding 650 DEG C calcination 4 hours, be stored in spare in drier；The sodium chloride, lemon
Sour sodium, DisodiumHydrogen Citrate are that analysis is pure.
The detection method further includes addition recovery experiment, and the addition recovery experiment is using tobacco blank sample
Be added recycling, the dinocap standard reserving solution be used to add recovery test, specially respectively 0.05,0.1,
Recovery testu is carried out under 0.5 pitch-based sphere of mg/kg 3, each addition concentration sets 6 parallel samples, then carries out sample
Product pre-treatment and detection, the results show that the rate of recovery and precision of this method are all preferable.
Embodiment 4
The detection method of dinocap residual quantity in a kind of tobacco, comprising the following steps:
1) preparation of standard solution: accurately weighing 0.1 g of dinocap standard items, be accurate to 0.1 mg, is settled to methanol dissolution
100mL brown volumetric flask is configured to the standard reserving solution of 1mg/mL, is kept in dark place in -20 DEG C of refrigerators, by standard reserving solution
It is diluted to series standard working solution, for making standard curve；
The production method of the standard curve be specially dinocap standard reserving solution is configured to 0.01 with methanol, 0.02,
0.05, the dinocap standard working solution of 0.1,0.2 and 0.5 mg/L series mass concentration carries out each concentration with peak area
Linear regression obtains standard curve, and the standard curve, which is within the scope of 0.01-0.5 mg/L in dinocap mass concentration, is in
Good linear, correlation coefficient r2Greater than 0.99；
2) sample pre-treatments:
Extract: weigh sample to be tested into centrifuge tube, add water vibrate to sample sufficiently infiltrated by water after stand 10min；Pipette with
1% formic acid-the acetonitrile of water equivalent is into centrifuge tube, and with 2000 r/min velocity fluctuation, 4 min；It is separately added into centrifuge tube
Anhydrous magnesium sulfate, sodium chloride, sodium citrate, DisodiumHydrogen Citrate, additional amount are sample to be tested: anhydrous magnesium sulfate: sodium chloride: lemon
Lemon acid sodium: DisodiumHydrogen Citrate=1:2:0.5:0.5:0.25, immediately with 2000 r/min velocity fluctuation, 3 min；Then with
6000r/min is centrifuged 4min；
Purification: pipetting 1 mL of supernatant into 1.5 mL centrifuge tubes, and 100 mg C18 scattered adsorption agent, vortex oscillation 3 is added
Min is centrifuged 4min with 5500 r/min, and Aspirate supernatant crosses upper machine analysis after 0.22 μm of organic phase filter membrane；
3) detection of dinocap residual quantity: will be joined by step (2) treated sample using gas-chromatography negative chemical ionization mass spectrometry
Usage detection, and the standard curve obtained in conjunction with step (1) measures dinocap residual quantity.
The chromatographic condition of the gas-chromatography negative chemical ionization mass spectrometry combination method is chromatographic column: m × 0.25 DB-5MS(30
Mm × 0.25 μm).The mass spectrometric analysis condition are as follows: Negative chemical ionization (NCI), using selection ion (SIM) mould
Formula, characteristic ion are m/z 278 and m/z 279, and wherein m/z 278 is quota ion.
The purity of the dinocap standard items is 98%；Methanol, acetonitrile and the formic acid is HPLC grades；The nothing
Water magnesium sulfate be analyze it is pure and using it is preceding 650 DEG C calcination 4 hours, be stored in spare in drier；The sodium chloride, lemon
Sour sodium, DisodiumHydrogen Citrate are that analysis is pure.
The detection method further includes addition recovery experiment, and the addition recovery experiment is using tobacco blank sample
Be added recycling, the dinocap standard reserving solution be used to add recovery test, specially respectively 0.05,0.1,
Recovery testu is carried out under 0.5 pitch-based sphere of mg/kg 3, each addition concentration sets 6 parallel samples, then carries out sample
Product pre-treatment and detection, the results show that the rate of recovery and precision of this method are all preferable.
Claims (10)
1. the detection method of dinocap residual quantity in a kind of tobacco, it is characterised in that the following steps are included:
1) preparation of standard solution: accurately weighing dinocap standard items, and dissolution is settled in brown volumetric flask, is configured to 1mg/
The standard reserving solution of mL, is kept in dark place in -15 ~ -25 DEG C of refrigerators, and standard reserving solution is diluted to series standard working solution,
For making standard curve；
2) sample pre-treatments:
Extract: weigh sample to be tested into centrifuge tube, add water vibrate to sample sufficiently infiltrated by water after stand 8-12min；It pipettes
1% formic acid-acetonitrile with water equivalent is into centrifuge tube, and with 2~5 min of 1500-2500 r/min velocity fluctuation；In centrifuge tube
In be separately added into anhydrous magnesium sulfate, sodium chloride, sodium citrate, DisodiumHydrogen Citrate, additional amount is sample to be tested: anhydrous slufuric acid
Magnesium: sodium chloride: sodium citrate: DisodiumHydrogen Citrate=1:2:0.5:0.5:0.25, immediately with the vibration of 1500-2500 r/min speed
Swing 2~5 min；Then 3~5 min are centrifuged with 5000-7000r/min；
Purification: pipetting 1 mL of supernatant into 1.5 mL centrifuge tubes, and 50~200 mg C18 scattered adsorption agent, vortex oscillation is added
2~5 min are centrifuged 3~5 min with 5000~6000 r/min, and Aspirate supernatant crosses upper machine after 0.22 μm of organic phase filter membrane
Analysis；
3) detection of dinocap residual quantity: will be joined by step (2) treated sample using gas-chromatography negative chemical ionization mass spectrometry
Usage detection, and the standard curve obtained in conjunction with step (1) measures dinocap residual quantity.
2. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that described in step (1)
Standard reserving solution preparation method be accurately weigh 0.1 g of dinocap standard items, be accurate to 0.1 mg, with methanol dissolution constant volume
To 100mL brown volumetric flask, it is configured to the standard reserving solution of 1mg/mL.
3. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that described in step (1)
Standard curve production method be specially dinocap standard reserving solution is configured to 0.01 with methanol, 0.02,0.05,0.1,
The dinocap standard working solution of 0.2 and 0.5 mg/L series mass concentration carries out linear regression to each concentration with peak area,
Obtaining standard curve, the standard curve is in 0.01-0.5 mg/L in good linear in dinocap mass concentration,
Correlation coefficient r2Greater than 0.99.
4. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that the detection side
Method further includes addition recovery experiment, and the addition recovery experiment is to be added recycling using tobacco blank sample, will be described
Dinocap standard reserving solution for adding recovery test, specially respectively in 0.05,0.1,0.5 mg/kg, 3 pitch-based spheres
Lower carry out recovery testu, each addition concentration set 6 parallel samples, then carry out sample pre-treatments and detection, described
The rate of recovery of the dinocap in tobacco is 95.83%~102.34%, and relative standard deviation is 3.75%~5.30%.
5. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that described in step (2)
Extraction be specially weigh 2 g samples to be tested, be accurate to 0.01 g, in 50 mL tool lid centrifuge tube in, be added 10 mL water, oscillation
10 min are stood after sufficiently being infiltrated to sample by water；10 1% formic acid of mL-acetonitrile is pipetted into centrifuge tube, is placed in whirlpool mixing
With 2000 r/min velocity fluctuation, 2~5 min on shaker；4 g anhydrous magnesium sulfates, 1 g chlorination are separately added into centrifuge tube
Sodium, 1 g sodium citrate and 0.5 g DisodiumHydrogen Citrate, immediately on whirlpool mixing shaker with 2000 r/min velocity fluctuations
Then 2~5 min are centrifuged 3~5 min with 6000 r/min.
6. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that described in step (2)
Purification be specially pipette 1 mL of supernatant into 1.5 mL centrifuge tubes, be added 50 mg C18 scattered adsorption agent, vortex oscillation 2
Min is centrifuged 3 min with 6000 r/min, and Aspirate supernatant crosses upper machine analysis after 0.22 μm of organic phase filter membrane.
7. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that described in step (3)
The chromatographic condition that gas-chromatography negative chemical ionization mass spectrometry is combined method is chromatographic column: mm × 0.25 μm DB-5MS(30 m × 0.25).
8. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that step (3) is described
Mass spectrometric analysis condition are as follows: Negative chemical ionization (NCI), using selection ion (SIM) mode, characteristic ion m/z
278 and m/z 279, wherein m/z 278 is quota ion.
9. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that described in step (3)
The detection of dinocap residual quantity is limited to 0.02 mg/kg, is quantitatively limited to 0.07 mg/kg.
10. the detection method of dinocap residual quantity in tobacco according to claim 1, it is characterised in that the dinocap
The purity of standard items is 98%；Methanol, acetonitrile and the formic acid is HPLC grades；The anhydrous magnesium sulfate is to analyze pure and make
With it is preceding 650 DEG C calcination 4 hours, be stored in spare in drier；The sodium chloride, sodium citrate, DisodiumHydrogen Citrate are equal
It is pure to analyze.
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| CN111983063A (en) * | 2020-08-06 | 2020-11-24 | 西宁海关技术中心 | Method for measuring various pesticide residues in sea buckthorn products by gas chromatography-tandem mass spectrometry |
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