CN109001331A - The test method of imidaclothiz residual quantity in a kind of tealeaves - Google Patents
The test method of imidaclothiz residual quantity in a kind of tealeaves Download PDFInfo
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- CN109001331A CN109001331A CN201811019568.2A CN201811019568A CN109001331A CN 109001331 A CN109001331 A CN 109001331A CN 201811019568 A CN201811019568 A CN 201811019568A CN 109001331 A CN109001331 A CN 109001331A
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- 238000010998 test method Methods 0.000 title claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000012360 testing method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000284 extract Substances 0.000 claims abstract description 10
- 238000003556 assay Methods 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- 238000000265 homogenisation Methods 0.000 claims abstract description 5
- 239000000523 sample Substances 0.000 claims description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000012224 working solution Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 23
- HXYXTCJDWHHCBW-UHFFFAOYSA-N acetonitrile;toluene Chemical compound CC#N.CC1=CC=CC=C1 HXYXTCJDWHHCBW-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- SOSWVVMGPYTPKV-UHFFFAOYSA-N acetic acid;azane;formic acid Chemical compound [NH4+].OC=O.CC([O-])=O SOSWVVMGPYTPKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000011550 stock solution Substances 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims description 8
- 229940043376 ammonium acetate Drugs 0.000 claims description 8
- 238000000889 atomisation Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 238000004949 mass spectrometry Methods 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 239000012496 blank sample Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000011208 chromatographic data Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000012982 microporous membrane Substances 0.000 claims description 4
- 238000002552 multiple reaction monitoring Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- VMSKYEUTOGMGTQ-UHFFFAOYSA-N quinoline;thiophene Chemical compound C=1C=CSC=1.N1=CC=CC2=CC=CC=C21 VMSKYEUTOGMGTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 5
- 231100000703 Maximum Residue Limit Toxicity 0.000 description 4
- 238000007865 diluting Methods 0.000 description 3
- 239000000447 pesticide residue Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 2
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 2
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 description 1
- 235000000173 Camellia sinensis var sinensis Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229930014345 anabasine Natural products 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Classifications
-
- 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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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a kind of test methods of imidaclothiz residual quantity in tealeaves, include the following steps: 1.1, extract, accurately weighs 2g sample (being accurate to 0.01g), be placed in 50mL plastic centrifuge tube, 10mL water is added, at least 30min is impregnated, 20mL acetonitrile is added, high speed homogenization extracts 1min, 3.5g sodium chloride is added, it is vortexed and mixes 30 seconds, 4min is centrifuged with 4000r/min, supernatant is to be clean；1.2, it purifies；1.3.1, quantitative determine；1.3.2, qualitative determination；1.3.3, blank assay；1.4, result is calculated and is stated.Beneficial effect is: method detection accuracy is high, error rate is lower, it is simple to detect process, multiple control panel has been taken to carry out test operation, significantly reduce the labor intensity of tester, detection efficiency is improved, the method quantitative limit of 0.01mg/kg can meet the detection demand of inlet and outlet tealeaves simultaneously.
Description
Technical field
The present invention relates to Tea Detection Methods technical fields, more particularly to a kind of test of imidaclothiz residual quantity in tealeaves
Method.
Background technique
Imidaclothiz is a kind of anabasine insecticide, is become after organic phosphorus, carbamate and pyrethroid desinsection
The fourth-largest class pesticide new variety after agent.With the continuous improvement of China's tea products quality, it is directed to the inspection of pesticide residue
It surveys and requires also gradually increasing.
China's national food safety standard " GB2763-2016 Pesticide maximum residue limit " defines 48 in tealeaves
The maximum residue limit of kind pesticide, wherein the limitation of imidaclothiz is 3mg/kg, but standard does not specify relevant detection method, and
And domestic there is no national standard, professional standard or the provincial standards of imidaclothiz residues detection in food or in tealeaves at present.
The main exit country of China's tealeaves and regional such as European Union, Japan, the U.S., Russia, Africa are all without formulating chlorine in tealeaves
The limit standard of thiophene quinoline.According to " uniform limit " requirement of Japan, all pesticide residues without formulating limitation are required to meet
The limitation requirement of 0.01mg/kg, European Union define the maximum residue limit of 480 Multiple Pesticides in tealeaves, but for imidaclothiz this
The pesticide of kind not within the specified scope is also required to meet the maximum residue limit requirement of 0.01mg/kg.This detection method can be simultaneously
Meet the detection demand to imidaclothiz pesticide residue in inlet and outlet tealeaves.
Summary of the invention
The object of the invention is that providing a kind of test of imidaclothiz residual quantity in tealeaves to solve the above-mentioned problems
Method.
The present invention through the following technical solutions to achieve the above objectives:
The test method of imidaclothiz residual quantity, includes the following steps: in a kind of tealeaves
1.1, it extracts, accurately weighs 2g sample (being accurate to 0.01g), be placed in 50mL plastic centrifuge tube, 10mL water is added,
At least 30min is impregnated, 20mL acetonitrile is added, high speed homogenization extracts 1min, and 3.5g sodium chloride is added, and it is vortexed and mixes 30 seconds, with
4000r/min is centrifuged 4min, and supernatant is to be clean；
1.2, it purifies, 2.0mL supernatant is transferred in the solid-phase extraction column activated, receive efflux, then use 8.0mL
Whole eluents are collected in the elution of acetonitrile-methylbenzene mixed solution, and 45 DEG C of water-baths are concentrated to dryness, and the dissolution of 2.0mL methanol is added,
Through filtering with microporous membrane, measured for liquid chromatography-tandem mass spectrometry instrument；
1.3.1, quantitative determine, measure matrix hybrid standard working solution and sample liquid, calculated in sample liquid with external standard curve method
Imidaclothiz content, if in sample liquid imidaclothiz content exceed standard curve range, analyzed again with after methanol dilution, together
When be considered as the matrix effect of sample, it is quantitative again to carry out matrix hybrid standard working solution, to using this method pre-treatment to purify
The sample for diluting 100 times or more afterwards, has been not present significant matrix effect, can be directly quantitative with standard working solution, upper
Under the conditions of stating, the reference retention time of imidaclothiz is 4.6min；
1.3.2, qualitative determination, sample liquid and standard working solution according to the above instrument conditions, if sample liquid and standard
Test substance chromatographic peak relative retention time deviation is in ± 2.5% range in working solution；The relative abundance of qualitative ion pair with
The relative abundance of the comparable standard working solution of concentration is consistent, then can determine whether that there are corresponding measured objects in sample；
1.3.3, blank assay is carried out by aforesaid operations step in addition to sample is not added；
1.4, result is calculated and is stated, and the content of imidaclothiz in sample is calculated with chromatographic data processor or by formula (1):
In formula:
X -- the content of imidaclothiz in sample, unit are milligrams per kilogram (mg/kg)；
C -- the concentration of imidaclothiz from the sample liquid obtained on standard curve, unit are micrograms per millilitre (μ g/mL)；
V -- the final constant volume of sample liquid, unit are milliliter (mL)；
M -- sample mass representated by final sample liquid, unit are gram (g)；
Calculated result should deduct blank value.
Preferably, in addition to special indicate, agents useful for same is chromatographically pure, and water used is to meet level-one as defined in GB/T6682
Water, reagent needed for testing and material have: acetonitrile, toluene, methanol, ammonium acetate, formic acid, sodium chloride, ammonium acetate-formic acid mixing are molten
Liquid, acetonitrile-methylbenzene mixed solution, standard substance, Standard Stock solutions, standard intermediate fluid, standard working solution, matrix mixing mark
Quasi- working solution, solid-phase extraction column, acetonitrile-methylbenzene mixed solution, miillpore filter.
Preferably, ammonium acetate-formic acid mixed solution: weighing 0.385g ammonium acetate, and 1mL first is added after being dissolved with suitable quantity of water
Acid is settled to 1L with water, and ultrasound mixes；
Acetonitrile-methylbenzene mixed solution: pipetting 75mL acetonitrile and 25mL toluene, is uniformly mixed；
Standard substance: imidaclothiz, C7H8ClN5O2S, CAS accession number 105843-36-5, purity are greater than 98.0%；
Standard Stock solutions: accurately weighing appropriate standard substance, and with acetonitrile dissolution and constant volume, being configured to solution concentration is
The standard reserving solution of 200 μ g/mL, 0~4 DEG C of preservation；
Standard intermediate fluid: Standard Stock solutions 0.50mL accurately is pipetted, with methanol dilution and 10mL is settled to, is configured to；
Solution concentration is the standard intermediate fluid of 10 μ g/mL: accurately pipetting the standard intermediate fluid 1.0mL of 10 μ g/mL, uses methanol
Dilution；
And it is settled to 10mL, it is configured to the standard intermediate fluid that solution concentration is 1.0 μ g/mL, standard working solution: uses standard
Intermediate fluid is configured to the standard working solution that solution concentration is 1.0,2.0,5.0,10 and 50ng/mL, stores in 0~4 DEG C；
Matrix hybrid standard working solution: the blank sample base handled in right amount through the step 1.1 and the step 1.2 is taken
Matter solution slowly dries up in sample injection bottle, with nitrogen, and isometric standard working solution dissolution is added and mixes, for doing standard work
Make curve, matching while using；
Solid-phase extraction column: Carb/NH2 column, 500mg/500mg, 6mL (or suitable person) use 5mL acetonitrile-methylbenzene using preceding
Mixed solution activation；
Miillpore filter: 0.22 μm, organic phase.
Preferably, equipment needed for testing: liquid chromatography-tandem mass spectrometry instrument, sensibility reciprocal equipped with electric spray ion source are
The desk centrifuge of assay balance, turbine mixer, homogenizer, revolving speed not less than 4000r/min of 0.0001g and 0.01g, rotation
Turn the liquid-transfering gun of evaporimeter, solid-phase extracting instrument, 1mL.
Preferably, sample needs to take representative sample 500g in the preparation, and 40 mesh standard sieves are crushed and passed through with pulverizer,
It mixes, is fitted into clean sample container, seal and indicate label, while saving at room temperature.
Preferably, liquid chromatography-mass spectrography/Mass Spectrometry Conditions needed for experiment test:
A) chromatographic column: C18,150mm × 4.6mm (internal diameter), 5 μm or suitable person；
B) mobile phase: ammonium acetate-formic acid mixed solution and acetonitrile；
C) column temperature: 30 DEG C；
D) flow velocity: 0.80mL/min；
E) sample volume: 10 μ L；
F) ion source: electric spray ion source；
G) scanning mode: cation scanning；
H) monitoring mode: multiple-reaction monitoring；
Preferably, the related setting of instrument parameter and monitoring ion are as follows:
A) electron spray voltage: 4500V；
B) ion source temperature: 650 DEG C；
C) atomization gas pressure: 50psi；
D) assist gas pressure power: 55psi；
E) gas curtain atmospheric pressure: 35psi；
F) atmospheric pressure is collided: medium；
G) atomization gas and auxiliary gas are zero level air；Gas curtain gas and collision gas are high pure nitrogen；It should be adjusted before use each
Parameter makes sensitivity of mass spectrometry reach testing requirements.
The beneficial effects of the present invention are: method detection accuracy is high, and error rate is lower, and detection process is simple, has taken more
Weight control panel carries out test operation, significantly reduces the labor intensity of tester, improves detection efficiency.
Specific embodiment
Below with reference to embodiment, the invention will be further described:
Embodiment one:
The test method of imidaclothiz residual quantity, includes the following steps: in a kind of tealeaves
1.1, it extracts, accurately weighs 2g sample (being accurate to 0.01g), be placed in 50mL plastic centrifuge tube, 10mL water is added,
At least 30min is impregnated, 20mL acetonitrile is added, high speed homogenization extracts 1min, and 3.5g sodium chloride is added, and it is vortexed and mixes 30 seconds, with
4000r/min is centrifuged 4min, and supernatant is to be clean；
1.2, it purifies, 2.0mL supernatant is transferred in the solid-phase extraction column activated, receive efflux, then use 8.0mL
Whole eluents are collected in the elution of acetonitrile-methylbenzene mixed solution, and 45 DEG C of water-baths are concentrated to dryness, and the dissolution of 2.0mL methanol is added,
Through filtering with microporous membrane, measured for liquid chromatography-tandem mass spectrometry instrument；
1.3.1, quantitative determine, measure matrix hybrid standard working solution and sample liquid, calculated in sample liquid with external standard curve method
Imidaclothiz content, if in sample liquid imidaclothiz content exceed standard curve range, analyzed again with after methanol dilution, together
When be considered as the matrix effect of sample, it is quantitative again to carry out matrix hybrid standard working solution, to using this method pre-treatment to purify
The sample for diluting 100 times or more afterwards, has been not present significant matrix effect, can be directly quantitative with standard working solution, upper
Under the conditions of stating, the reference retention time of imidaclothiz is 4.6min；
1.3.2, qualitative determination, sample liquid and standard working solution according to the above instrument conditions, if sample liquid and standard
Test substance chromatographic peak relative retention time deviation is in ± 2.5% range in working solution；The relative abundance of qualitative ion pair with
The relative abundance of the comparable standard working solution of concentration is consistent, then can determine whether that there are corresponding measured objects in sample；
1.3.3, blank assay is carried out by aforesaid operations step in addition to sample is not added；
1.4, result is calculated and is stated, and the content of imidaclothiz in sample is calculated with chromatographic data processor or by formula (1):
In formula:
X -- the content of imidaclothiz in sample, unit are milligrams per kilogram (mg/kg)；
C -- the concentration of imidaclothiz from the sample liquid obtained on standard curve, unit are micrograms per millilitre (μ g/mL)；
V -- the final constant volume of sample liquid, unit are milliliter (mL)；
M -- sample mass representated by final sample liquid, unit are gram (g)；
Calculated result should deduct blank value.
In the present embodiment, in addition to special indicate, agents useful for same is chromatographically pure, and water used is to meet as defined in GB/T6682
Level-one water, reagent needed for testing and material have: acetonitrile, toluene, methanol, ammonium acetate, formic acid, sodium chloride, ammonium acetate-formic acid mixing
Solution, acetonitrile-methylbenzene mixed solution, standard substance, Standard Stock solutions, standard intermediate fluid, standard working solution, matrix mixing
Standard working solution, solid-phase extraction column, acetonitrile-methylbenzene mixed solution, miillpore filter.
In the present embodiment, ammonium acetate-formic acid mixed solution: weighing 0.385g ammonium acetate, and 1mL is added after being dissolved with suitable quantity of water
Formic acid is settled to 1L with water, and ultrasound mixes；
Acetonitrile-methylbenzene mixed solution: pipetting 75mL acetonitrile and 25mL toluene, is uniformly mixed；
Standard substance: imidaclothiz, C7H8ClN5O2S, CAS accession number 105843-36-5, purity are greater than 98.0%；
Standard Stock solutions: accurately weighing appropriate standard substance, and with acetonitrile dissolution and constant volume, being configured to solution concentration is
The standard reserving solution of 200 μ g/mL, 2 DEG C of preservations；
Standard intermediate fluid: Standard Stock solutions 0.50mL accurately is pipetted, with methanol dilution and 10mL is settled to, is configured to；
Solution concentration is the standard intermediate fluid of 10 μ g/mL: accurately pipetting the standard intermediate fluid 1.0mL of 10 μ g/mL, uses methanol
Dilution；
And it is settled to 10mL, it is configured to the standard intermediate fluid that solution concentration is 1.0 μ g/mL, standard working solution: uses standard
Intermediate fluid is configured to the standard working solution that solution concentration is 1.0,2.0,5.0,10 and 50ng/mL, stores in 2 DEG C；
Matrix hybrid standard working solution: the blank sample base handled in right amount through the step 1.1 and the step 1.2 is taken
Matter solution slowly dries up in sample injection bottle, with nitrogen, and isometric standard working solution dissolution is added and mixes, for doing standard work
Make curve, matching while using；
Solid-phase extraction column: Carb/NH2 column, 500mg/500mg, 6mL (or suitable person) use 5mL acetonitrile-methylbenzene using preceding
Mixed solution activation；
Miillpore filter: 0.22 μm, organic phase.
In the present embodiment, equipment needed for testing: liquid chromatography-tandem mass spectrometry instrument, sensibility reciprocal equipped with electric spray ion source are
The desk centrifuge of assay balance, turbine mixer, homogenizer, revolving speed not less than 4000r/min of 0.0001g and 0.01g, rotation
Turn the liquid-transfering gun of evaporimeter, solid-phase extracting instrument, 1mL.
In the present embodiment, sample needs to take representative sample 500g in the preparation, is crushed with pulverizer and passes through 40 targets
Quasi- sieve, mixes, and is fitted into clean sample container, seals and indicate label, while saving at room temperature.
In the present embodiment, liquid chromatography-mass spectrography/Mass Spectrometry Conditions needed for experiment test:
A) chromatographic column: C18,150mm × 4.6mm (internal diameter), 5 μm or suitable person；
B) mobile phase: ammonium acetate-formic acid mixed solution and acetonitrile；
C) column temperature: 30 DEG C；
D) flow velocity: 0.80mL/min；
E) sample volume: 10 μ L；
F) ion source: electric spray ion source；
G) scanning mode: cation scanning；
H) monitoring mode: multiple-reaction monitoring；
In the present embodiment, the related setting of instrument parameter and monitoring ion are as follows:
A) electron spray voltage: 4500V；
B) ion source temperature: 650 DEG C；
C) atomization gas pressure: 50psi；
D) assist gas pressure power: 55psi；
E) gas curtain atmospheric pressure: 35psi；
F) atmospheric pressure is collided: medium；
G) atomization gas and auxiliary gas are zero level air；Gas curtain gas and collision gas are high pure nitrogen；It should be adjusted before use each
Parameter makes sensitivity of mass spectrometry reach testing requirements.
Embodiment two:
The test method of imidaclothiz residual quantity, includes the following steps: in a kind of tealeaves
1.1, it extracts, accurately weighs 1.5g sample (being accurate to 0.01g), be placed in 50mL plastic centrifuge tube, 8mL is added
Water impregnates at least 45min, adds 20mL acetonitrile, and high speed homogenization extracts 1min, and 3.5g sodium chloride is added, and is vortexed and mixes 1min,
It is centrifuged 4min with 3000r/min, supernatant is to be clean；
1.2, it purifies, 2.0mL supernatant is transferred in the solid-phase extraction column activated, receive efflux, then use 6.0mL
Whole eluents are collected in the elution of acetonitrile-methylbenzene mixed solution, and 50 DEG C of water-baths are concentrated to dryness, and the dissolution of 2.0mL methanol is added,
Through filtering with microporous membrane, measured for liquid chromatography-tandem mass spectrometry instrument；
1.3.1, quantitative determine, measure matrix hybrid standard working solution and sample liquid, calculated in sample liquid with external standard curve method
Imidaclothiz content, if in sample liquid imidaclothiz content exceed standard curve range, analyzed again with after methanol dilution, together
When be considered as the matrix effect of sample, it is quantitative again to carry out matrix hybrid standard working solution, to using this method pre-treatment to purify
The sample for diluting 100 times or more afterwards, has been not present significant matrix effect, can be directly quantitative with standard working solution, upper
Under the conditions of stating, the reference retention time of imidaclothiz is 5min；
1.3.2, qualitative determination, sample liquid and standard working solution according to the above instrument conditions, if sample liquid and standard
Test substance chromatographic peak relative retention time deviation is in ± 2.5% range in working solution；The relative abundance of qualitative ion pair with
The relative abundance of the comparable standard working solution of concentration is consistent, then can determine whether that there are corresponding measured objects in sample；
1.3.3, blank assay is carried out by aforesaid operations step in addition to sample is not added；
1.4, result is calculated and is stated, and the content of imidaclothiz in sample is calculated with chromatographic data processor or by formula (1):
In formula:
X -- the content of imidaclothiz in sample, unit are milligrams per kilogram (mg/kg)；
C -- the concentration of imidaclothiz from the sample liquid obtained on standard curve, unit are micrograms per millilitre (μ g/mL)；
V -- the final constant volume of sample liquid, unit are milliliter (mL)；
M -- sample mass representated by final sample liquid, unit are gram (g)；
Calculated result should deduct blank value.
In the present embodiment, in addition to special indicate, agents useful for same is chromatographically pure, and water used is to meet as defined in GB/T6682
Level-one water, reagent needed for testing and material have: acetonitrile, toluene, methanol, ammonium acetate, formic acid, sodium chloride, ammonium acetate-formic acid mixing
Solution, acetonitrile-methylbenzene mixed solution, standard substance, Standard Stock solutions, standard intermediate fluid, standard working solution, matrix mixing
Standard working solution, solid-phase extraction column, acetonitrile-methylbenzene mixed solution, miillpore filter.
In the present embodiment, ammonium acetate-formic acid mixed solution: weighing 0.385g ammonium acetate, and 1mL is added after being dissolved with suitable quantity of water
Formic acid is settled to 1L with water, and ultrasound mixes；
Acetonitrile-methylbenzene mixed solution: pipetting 70mL acetonitrile and 30mL toluene, is uniformly mixed；
Standard substance: imidaclothiz, C7H8ClN5O2S, CAS accession number 105843-36-5, purity are greater than 98.0%；
Standard Stock solutions: accurately weighing appropriate standard substance, and with acetonitrile dissolution and constant volume, being configured to solution concentration is
The standard reserving solution of 200 μ g/mL, 4 DEG C of preservations；
Standard intermediate fluid: Standard Stock solutions 0.70mL accurately is pipetted, with methanol dilution and 10mL is settled to, is configured to；
Solution concentration is the standard intermediate fluid of 10 μ g/mL: accurately pipetting the standard intermediate fluid 1.0mL of 10 μ g/mL, uses methanol
Dilution；
And it is settled to 10mL, it is configured to the standard intermediate fluid that solution concentration is 1.0 μ g/mL, standard working solution: uses standard
Intermediate fluid is configured to the standard working solution that solution concentration is 1.0,2.0,5.0,10 and 50ng/mL, stores in 4 DEG C；
Matrix hybrid standard working solution: the blank sample base handled in right amount through the step 1.1 and the step 1.2 is taken
Matter solution slowly dries up in sample injection bottle, with nitrogen, and isometric standard working solution dissolution is added and mixes, for doing standard work
Make curve, matching while using；
Solid-phase extraction column: Carb/NH2 column, 500mg/500mg, 6mL (or suitable person) use 5mL acetonitrile-methylbenzene using preceding
Mixed solution activation；
Miillpore filter: 0.22 μm, organic phase.
In the present embodiment, equipment needed for testing: liquid chromatography-tandem mass spectrometry instrument, sensibility reciprocal equipped with electric spray ion source are
The desk centrifuge of assay balance, turbine mixer, homogenizer, revolving speed not less than 3600r/min of 0.0001g and 0.01g, rotation
Turn the liquid-transfering gun of evaporimeter, solid-phase extracting instrument, 1mL.
In the present embodiment, sample needs to take representative sample 500g in the preparation, is crushed with pulverizer and passes through 40 targets
Quasi- sieve, mixes, and is fitted into clean sample container, seals and indicate label, while saving at room temperature.
In the present embodiment, liquid chromatography-mass spectrography/Mass Spectrometry Conditions needed for experiment test:
A) chromatographic column: C18,150mm × 4.6mm (internal diameter), 5 μm or suitable person；
B) mobile phase: ammonium acetate-formic acid mixed solution and acetonitrile；
C) column temperature: 35 DEG C；
D) flow velocity: 0.70mL/min；
E) sample volume: 10 μ L；
F) ion source: electric spray ion source；
G) scanning mode: cation scanning；
H) monitoring mode: multiple-reaction monitoring；
In the present embodiment, the related setting of instrument parameter and monitoring ion are as follows:
A) electron spray voltage: 4300V；
B) ion source temperature: 620 DEG C；
C) atomization gas pressure: 50psi；
D) assist gas pressure power: 55psi；
E) gas curtain atmospheric pressure: 40psi；
F) atmospheric pressure is collided: medium；
G) atomization gas and auxiliary gas are zero level air；Gas curtain gas and collision gas are high pure nitrogen；It should be adjusted before use each
Parameter makes sensitivity of mass spectrometry reach testing requirements.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements
It all fall within the protetion scope of the claimed invention.
Claims (7)
1. the test method of imidaclothiz residual quantity in a kind of tealeaves, characterized by the following steps:
1.1, it extracts, accurately weighs 2g sample (being accurate to 0.01g), be placed in 50mL plastic centrifuge tube, 10mL water is added, impregnate
At least 30min adds 20mL acetonitrile, and high speed homogenization extracts 1min, and 3.5g sodium chloride is added, and is vortexed and mixes 30 seconds, with
4000r/min is centrifuged 4min, and supernatant is to be clean；
1.2, it purifies, 2.0mL supernatant is transferred in the solid-phase extraction column activated, receive efflux, then with 8.0mL second
Nitrile-toluene mixed solution elution, collects whole eluents, and 45 DEG C of water-baths are concentrated to dryness, and the dissolution of 2.0mL methanol, warp is added
Filtering with microporous membrane is measured for liquid chromatography-tandem mass spectrometry instrument；
1.3.1, quantitative determine, measure matrix hybrid standard working solution and sample liquid, the chlorine in sample liquid is calculated with external standard curve method
Thiophene quinoline content is analyzed again with after methanol dilution, is answered simultaneously if the content of imidaclothiz exceeds standard curve range in sample liquid
The matrix effect for considering sample carries out matrix hybrid standard working solution again quantitatively, dilute after purifying to this method pre-treatment is used
Significant matrix effect has been not present in the sample for releasing 100 times or more, can be directly quantitative with standard working solution, in above-mentioned item
Under part, the reference retention time of imidaclothiz is 4.6min；
1.3.2, qualitative determination, sample liquid and standard working solution according to the above instrument conditions, if sample liquid and standard work
Test substance chromatographic peak relative retention time deviation is in ± 2.5% range in liquid；The relative abundance and concentration of qualitative ion pair
The relative abundance of comparable standard working solution is consistent, then can determine whether that there are corresponding measured objects in sample；
1.3.3, blank assay is carried out by aforesaid operations step in addition to sample is not added；
1.4, result is calculated and is stated, and the content of imidaclothiz in sample is calculated with chromatographic data processor or by formula (1):
In formula:
X -- the content of imidaclothiz in sample, unit are milligrams per kilogram (mg/kg)；
C -- the concentration of imidaclothiz from the sample liquid obtained on standard curve, unit are micrograms per millilitre (μ g/mL)；
V -- the final constant volume of sample liquid, unit are milliliter (mL)；
M -- sample mass representated by final sample liquid, unit are gram (g)；
Calculated result should deduct blank value.
2. the test method of imidaclothiz residual quantity in a kind of tealeaves according to claim 1, it is characterised in that: remove special note
Bright outer, agents useful for same is chromatographically pure, and water used is to meet level-one water as defined in GB/T6682, reagent needed for testing and material
Have: acetonitrile, toluene, methanol, ammonium acetate, formic acid, sodium chloride, ammonium acetate-formic acid mixed solution, acetonitrile-methylbenzene mixed solution, mark
Quasi- substance, Standard Stock solutions, standard intermediate fluid, standard working solution, matrix hybrid standard working solution, solid-phase extraction column,
Acetonitrile-methylbenzene mixed solution, miillpore filter.
3. the test method of imidaclothiz residual quantity in a kind of tealeaves according to claim 2, it is characterised in that: ammonium acetate-
Formic acid mixed solution: weighing 0.385g ammonium acetate, and 1mL formic acid is added after being dissolved with suitable quantity of water, is settled to 1L with water, ultrasound is mixed
It is even；
Acetonitrile-methylbenzene mixed solution: pipetting 75mL acetonitrile and 25mL toluene, is uniformly mixed；
Standard substance: imidaclothiz, C7H8ClN5O2S, CAS accession number 105843-36-5, purity are greater than 98.0%；
Standard Stock solutions: accurately weighing appropriate standard substance, and with acetonitrile dissolution and constant volume, being configured to solution concentration is 200 μ g/
The standard reserving solution of mL, 0~4 DEG C of preservation；
Standard intermediate fluid: Standard Stock solutions 0.50mL accurately is pipetted, with methanol dilution and 10mL is settled to, is configured to；
Solution concentration is the standard intermediate fluid of 10 μ g/mL: the standard intermediate fluid 1.0mL of 10 μ g/mL is accurately pipetted, it is dilute with methanol
It releases；
And it is settled to 10mL, it is configured to the standard intermediate fluid that solution concentration is 1.0 μ g/mL, standard working solution: among standard
Liquid is configured to the standard working solution that solution concentration is 1.0,2.0,5.0,10 and 50ng/mL, stores in 0~4 DEG C；
Matrix hybrid standard working solution: take the blank sample matrix handled in right amount through the step 1.1 and the step 1.2 molten
Liquid slowly dries up in sample injection bottle, with nitrogen, and isometric standard working solution dissolution is added and mixes, bent for doing standard work
Line, matching while using；
Solid-phase extraction column: Carb/NH2 column, 500mg/500mg, 6mL (or suitable person) are mixed using preceding with 5mL acetonitrile-methylbenzene
Solution activation；
Miillpore filter: 0.22 μm, organic phase.
4. the test method of imidaclothiz residual quantity in a kind of tealeaves according to claim 1, it is characterised in that: needed for test
Equipment: liquid chromatography-tandem mass spectrometry instrument, sensibility reciprocal equipped with electric spray ion source are the assay balance of 0.0001g and 0.01g, whirlpool
Revolve the shifting of the desk centrifuge, Rotary Evaporators, solid-phase extracting instrument, 1mL of mixer, homogenizer, revolving speed not less than 4000r/min
Liquid rifle.
5. the test method of imidaclothiz residual quantity in a kind of tealeaves according to claim 1, it is characterised in that: sample is being made
It needs to take representative sample 500g when standby, 40 mesh standard sieves is crushed and passed through with pulverizer, mix, be packed into clean sample container
In, seal and indicate label, while saving at room temperature.
6. the test method of imidaclothiz residual quantity in a kind of tealeaves according to claim 1, it is characterised in that: experiment test
Required liquid chromatography-mass spectrography/Mass Spectrometry Conditions:
A) chromatographic column: C18,150mm × 4.6mm (internal diameter), 5 μm or suitable person；
B) mobile phase: ammonium acetate-formic acid mixed solution and acetonitrile；
C) column temperature: 30 DEG C；
D) flow velocity: 0.80mL/min；
E) sample volume: 10 μ L；
F) ion source: electric spray ion source；
G) scanning mode: cation scanning；
H) monitoring mode: multiple-reaction monitoring.
7. the test method of imidaclothiz residual quantity in a kind of tealeaves according to claim 1, it is characterised in that: instrument parameter
With the related setting of monitoring ion are as follows:
A) electron spray voltage: 4500V；
B) ion source temperature: 650 DEG C；
C) atomization gas pressure: 50psi；
D) assist gas pressure power: 55psi；
E) gas curtain atmospheric pressure: 35psi；
F) atmospheric pressure is collided: medium；
G) atomization gas and auxiliary gas are zero level air；Gas curtain gas and collision gas are high pure nitrogen；Each parameter should be adjusted before use
Sensitivity of mass spectrometry is set to reach testing requirements.
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