CN102798682B - Method for determination of flumethrin in garlic or garlic product - Google Patents
Method for determination of flumethrin in garlic or garlic product Download PDFInfo
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Abstract
The invention provides a method for determination of flumethrin in garlic or a garlic product. The method comprises the following steps of 1, extraction comprising carrying out homogenization and/or centrifugation treatment on garlic or a garlic product by a normal hexane-dichloromethane mixture having a volume ratio of 1: 1, blow-drying an organic phase by nitrogen, and dissolving residues in normal hexane to obtain a solution needing to by purified, 2, purification comprising carrying out conditioning of an amino column, pouring the solution needing to by purified into the amino column, receiving an eluent, carrying out elution by a normal hexane-dichloromethane mixture having a volume ratio of 1: 1 to obtain a purified solution, blow-drying the purified solution by nitrogen, dissolving residues in an acetone-normal hexane mixture having a volume ratio of 10: 90, and filtering by a filter membrane having a aperture size of 0.22 microns, and 3, detection comprising determining flumethrin in the purified solution prepared from garlic or the garlic product by a gas chromatography or a gas chromatography/tandem mass spectrometry. The method adopts a gas chromatography or a tandem mass spectrometry. The method can be operated simply, has high sensitivity and good repeatability and can be widely used for residual detection of flumethrin in garlic or a garlic product.
Description
Technical field
The present invention relates to a kind of assay method of Pesticide Residues, be specifically related to the assay method of flumethrin in a kind of garlic or its goods.
Background technology
Flumethrin is that a kind of synthetic pyrethroid class is killed carcass epizoa medicine.At present, this medicine is widely used in the bee rearing process as acaricide
[1 ］, and the pesticide in agricultural.But the residual meeting of this class agricultural chemicals in honey and agricultural product causes certain harm to human body, thereby arouses widespread concern.Both at home and abroad for the existing more document of the flumethrin residue detection in bee product (as honey, bee milk and Bee Pollen)
[2-5]and standard
[6-8].Detection method also has multiple, as vapor-phase chromatography
[9-12], liquid phase chromatography
[13]with gas chromatography one mass spectroscopy
[14-15], but in agricultural product and the detection in garlic and products thereof there is not yet bibliographical information.
Summary of the invention
The objective of the invention is, for overcoming above-mentioned the deficiencies in the prior art, provides the assay method of flumethrin in a kind of garlic or its goods.
For achieving the above object, the present invention adopts following technical proposals:
The assay method of flumethrin in a kind of garlic or its goods, it comprises the following steps:
(1) extract: take fresh garlic and be put in container Microwave Treatment in micro-wave oven, or take garlic products and be put in container, to adding the normal hexane that volume ratio is 1:1 in container: methylene chloride, through homogeneous and/or centrifugal treating, standing rear system is divided into organic phase and inorganic phase, organic phase is dried up with nitrogen, the residue n-hexane dissolution, to be clean;
(2) purify: nh 2 column is used to acetone and the pre-drip washing of normal hexane successively, when solvent liquid level arrives post adsorbed layer surface, pour immediately the solution to be clean that step (1) makes into, receive eluent, and the normal hexane that is 1:1 by volume ratio: the methylene chloride wash-out obtains scavenging solution; Scavenging solution dries up with nitrogen, the acetone that residue is 10:90 by volume ratio: n-hexane dissolution, and cross the 0.22um filter membrane and treat machine mensuration;
(3) detect: scavenging solution is measured the flumethrin in garlic or its goods with vapor-phase chromatography or gas chromatography/tandem mass spectrometry.
Described garlic products refers to salt marsh garlic, mashed garlic, dewatered garlic flake/powder/grain etc.
Further preferred as the present invention, described in step (1), the leaching process of garlic is: take bright garlic sample 20.00g, be accurate to 0.01g, be placed in the 150mL conical flask, in micro-wave oven after 640w microwave 40-60s, shred, accurately add the normal hexane that the 50.0mL volume ratio is 1:1: methylene chloride, the 18000r/min homogeneous extracts the 3min. extract and filters in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, to be clean.
Leaching process when described in step (1), garlic products is the dry sample goods is: take garlic dry sample goods 10.00g, be accurate to 0.01g, be placed in the 100mL plastic centrifuge tube, add the normal hexane that the 20mL volume ratio is 1:1: methylene chloride 18000r/min homogeneous, the centrifugal 5min of 3000r/min, extract is filtered in the 50mL color comparison tube, the normal hexane that residue is 1:1 by the 20mL volume ratio again: methylene chloride extracts once, extract is filtered in color comparison tube in the lump, sample liquid blows near dry in 50 ℃ of water-bath nitrogen, with 2.0mL n-hexane dissolution residue, to be clean.
Leaching process when garlic products described in step (1) is wet sample goods is: take the wet sample goods 20.00g of garlic, be accurate to 0.01g, be placed in the 150mL conical flask, accurately add the normal hexane that the 50.0mL volume ratio is 1:1: methylene chloride, the 18000r/min homogeneous extracts 3min. sample liquid and filters in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, to be clean.
The concrete steps that purify in step (2) are: nh 2 column is used to 3.0mL acetone and the pre-drip washing of 5mL normal hexane successively, make it activation, when solvent liquid level arrives post adsorbed layer surface, pour immediately above-mentioned solution to be clean into, receive eluent with the pointed centrifuge tube of 10mL, use the 3.0mL normal hexane: methylene chloride (1+1) wash-out, and repeat once.Scavenging solution nitrogen in 50 ℃ of water-baths blows near dry, and after accurately adding 1.0mL acetone+normal hexane (10+90, v/v) dissolved residue, the machine on the 0.22um filter membrane of crossing is measured.
Chromatographic condition in step (3) when with gas chromatography determination is: GC/ μ ECD: chromatographic column: HP-5 fused-silica capillary column, 30m * 0.32mm i.d., 0.25 μ m; Carrier gas: high pure nitrogen (99.999%); Flow velocity: 1.5ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; 310 ℃ of detector temperatures; Sample size 1.0 μ L.
Chromatographic condition in step (3) when by gas chromatography/tandem mass spectrometry is: GC/MS/MS: chromatographic column: HP-5MS (30m * 0.25mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high-purity helium (99.999%); Collision gas: High Purity Nitrogen (99.999%); Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; Sample size 1.0 μ L; Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: multiple-reaction monitoring pattern (MRM), parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
Experimental example
1 instrument and reagent
The Agilent6890 gas chromatograph, be furnished with electron capture detector; The triple level Four bar of Agilent7890/7000B gas chromatography/tandem mass spectrometer (GC-MS/MS); Homogenizer; 2.0mL syringe; The 50mL color comparison tube; Nitrogen evaporator; The 150mL conical flask; The 25mL color comparison tube; 10mL tip centrifuge tube.
Methylene chloride: chromatographically pure; Acetone: chromatographically pure; Normal hexane: chromatographically pure; Flumethrin: certified reference material; Solvent: acetone+normal hexane (10+90, v/v); Eluent: normal hexane: methylene chloride (1+1)
2 standard solution preparations
Standard reserving solution: accurately take appropriate flumethrin (being accurate to 0.0001g), use acetone solution, be configured to the storing solution that concentration is 500 μ g/mL, preserve in 0-4 ℃ of refrigerator lucifuge, sealing, storage life is 1 year.
Accurately pipette appropriate standard solution, with acetone+normal hexane (10+90, v/v), be diluted to 50,100,200,500,1000ng/mL standard operation liquid, now with the current.
3 sample extraction and purification
3.1 extract
Bright garlic sample: take about 20.00g (being accurate to 0.01g), be placed in the 150mL conical flask, in micro-wave oven after 640w microwave 40-60s, shred, accurately add the 50.0mL normal hexane: methylene chloride (1+1), the 18000r/min homogeneous extracts 3min. sample liquid and filters in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, to be clean.
Garlic dry sample goods (dewatered garlic flake/powder/grain etc.): take about 10.00g(and be accurate to 0.01g), be placed in the 100mL plastic centrifuge tube, add the 20mL normal hexane: methylene chloride (1+1) 18000r/min homogeneous, the centrifugal 5min of 3000r/min, extract is filtered in the 50mL color comparison tube, and residue is used the 20mL normal hexane again: methylene chloride (1+1) extracts once, extract is filtered in color comparison tube in the lump, sample liquid blows near dry in 50 ℃ of water-bath nitrogen, with 2.0mL n-hexane dissolution residue, to be clean.
The garlic sample goods (salt marsh garlic/mashed garlic etc.) that wet: take about 20.00g (being accurate to 0.01g), be placed in the 150mL conical flask, accurately add the 50.0mL normal hexane: methylene chloride (1+1), the 18000r/min homogeneous extracts 3min. sample liquid and filters in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, to be clean.
3.2 purify
4 chromatographic conditions
GC/ μ ECD: chromatographic column: HP-5 (30m * 0.32mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high pure nitrogen (99.999%); Flow velocity: 1.5ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; 310 ℃ of detector temperatures; Sample size 1.0 μ L.
GC/MS/MS: chromatographic column: HP-5MS (30m * 0.25mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high-purity helium (99.999%); Collision gas: High Purity Nitrogen (99.999%); Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; Sample size 1.0 μ L;
Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: multiple-reaction monitoring pattern (MRM), parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
5. result and discussion
5.1 the optimization of chromatographic condition
The flumethrin boiling point is higher, is difficult to volatilization, improves its initial column temperature (180 ℃) in testing process, has reduced detection time, adopts the method for temperature programme in testing process simultaneously, has effectively improved peak shape.Injector temperature is made as 280 ℃, can avoid residual.
Vapor-phase chromatography is separated 100ng/mL flumethrin chromatogram as shown in Figure 1.Gas chromatography-tandem mass spectrum separates 500ng/mL flumethrin chromatogram as shown in Fig. 2 a, Fig. 2 b.
5.2 Pretreatment optimization
5.2.1 the extraction effect of methylene chloride-normal hexane (1+1, volume ratio), acetonitrile and acetone that extracted sweetening agent, adopt the extracting method in " 3.1 extract ", replaces different extraction solution and tested.Result shows, utilizes methylene chloride-normal hexane as extracting solvent, and the recovery is higher.Contrast experiment's data in Table:
The impact of table 1 different solvents on the recovery (%)
5.2.2 the pungent sample sulfocompound such as fresh garlic is more, matrix interference is serious, and the present invention adopts the microwave-oven-heating inactivation treatment, has eliminated interference.Compared different microwave and different microwave time to the purification of sample and impact that flumethrin is reclaimed, through test of many times, finally determined microwave power 640w, microwave time 40 ~ 60s can effectively eliminate matrix interference, has improved detection sensitivity.
5.2.3 in purification process, the clean-up effect of nh 2 column, florisil silica post, HLB post has been carried out to the test of many times contrast, comparing result shows, after nh 2 column purifies, background is lower, and sensitivity is better.
5.3 the detection limit of method and the range of linearity
Determine the detection limit of method according to 3 times of signal to noise ratio (S/N ratio)s of blank sample, 10 times of signal to noise ratio (S/N ratio)s are determined the quantitative limit of method.In garlic and goods thereof, the quantitative limit of flumethrin meets 0.010ug/g.
With acetone-normal hexane (1+9), prepared the serial flumethrin standard solution of 0.050,0.10,0.20,0.50,1.0 μ g/mL.With the peak area y of target components to corresponding mass concentration x(μ g/mL), the drawing standard curve, its linearly dependent coefficient is greater than 0.99, shows that flumethrin has linear relationship preferably in vapor-phase chromatography detects.
5.4 the recovery and precision
Add 10 in garlic or its goods, 20, the flumethrin mark liquid of tri-concentration of 100 μ g/kg, method extraction, purification, upper machine by pre-treatment, each concentration is done parallel laboratory test 6 times, record the recovery between 60～100%, relative deviation is between 3.06～8.86%, and preci-sion and accuracy all reaches the requirement of Detecting Pesticide.Experimental result in Table:
The recovery and the precision of table 2 flumethrin in bright garlic sample
5.5 the application of method
Bright garlic sample, and add the bright garlic sample of 10 μ g/kg flumethrin standard solution, by upper machine after the experimental procedure end of operation of " 3 sample extraction and purification ", record chromatogram as shown in Figure 3:
From chromatogram, can find out, 10 μ g/kg flumethrin standard items (1-std), bright garlic sample (3-sam) and bright garlic sample mark-on (2-pls) are all separated preferably in chromatography of gases, and the mark-on sample reclaims better, and sample is noiseless.
Experiment shows, adopts flumethrin accuracy and precision in this law detection garlic or its goods higher, adopts gas chromatography-tandem mass spectrum conclusive evidence method to detect, and effectively raises the accuracy of detection.The method recovery in testing process is higher, analysis speed is fast, simple to operate, detects bottom line low, can meet the developed countries such as Japan, America and Europe to the qualitative of left drug in food and quantitatively detect, garlic or its goods security control are also had to good practicality.
In experimentation of the present invention, standard solution storing solution used is 500ug/mL.
Process for preparation: the flumethrin solid that to take 0.0258g purity be 97%, with being settled to 50mL after acetone solution, shakes up.
The preparation of standard solution: with the example that is formulated as of 1.0ug/mL standard solution, the flumethrin storing solution 20uL that to pipette concentration be 500ug/mL, with after acetone-normal hexane (10+90) dilution, being settled to 10mL, shake up.
High-purity helium and high pure nitrogen all refer to that purity is more than 99.999%.
The present invention is studied the residue detection of flumethrin in garlic or its goods, bright garlic sample is usingd normal hexane-methylene chloride as extracting solvent with garlic products after Microwave Treatment, nh 2 column purifies, and uses gas chromatographic detection, or adopts gas chromatography/tandem mass spectrometry to detect and conclusive evidence.The method is simple to operate, highly sensitive, and favorable reproducibility can be widely used in the residue detection of flumethrin in garlic or its goods.
The accompanying drawing explanation
Fig. 1 is that vapor-phase chromatography is separated 100ng/mL flumethrin chromatogram;
Fig. 2 a is that gas chromatography-tandem mass spectrum separates 500ng/mL flumethrin peak shape figure;
Fig. 2 b is two peak abundance of ions figure of flumethrin (wherein upper figure is peak 1, the abundance of ions figure that figure below is peak 2);
Fig. 3 is bright garlic sample, bright garlic sample mark-on, flumethrin standard items chromatogram
Fig. 4 is the analysis chromatogram of embodiment 1;
Fig. 5 is the analysis chromatogram of experimental example 2;
Fig. 6 is the analysis chromatogram of experimental example 3;
Fig. 7 is the analysis chromatogram of experimental example 4;
Fig. 8 is the analysis chromatogram of experimental example 5.
Embodiment
Below by instantiation, the present invention will be further elaborated, should be noted that following explanation is only in order to explain the present invention, is not limited its content.
Embodiment 1:
1.1 extract
Take the bright garlic sample of about 20.00g (being accurate to 0.01g), add 1.0ug/mL flumethrin standard solution 200uL, be placed in the 150mL conical flask, in micro-wave oven after 640w microwave 50s, shred, accurately add the 50.0mL normal hexane: methylene chloride (1+1), the 18000r/min homogeneous extracts 3min. sample liquid and filters in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, to be clean.
2.3.2 purify
2.4 chromatographic condition
GC/ μ ECD: chromatographic column: HP-5 (30m * 0.32mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high pure nitrogen (99.999%); Flow velocity: 1.5ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; 310 ℃ of detector temperatures; Sample size 1.0 μ L.
GC/MS/MS: chromatographic column: HP-5MS (30m * 0.25mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high-purity helium (99.999%); Collision gas: High Purity Nitrogen (99.999%); Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; Sample size 1.0 μ L; Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: multiple-reaction monitoring pattern (MRM), parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
The measured value that shows after testing this sample recovery test is 82ng/mL, by calculating its recovery, is 82%.
Take about 20.00g (being accurate to 0.01g) salt marsh garlic, add 1.0ug/mL flumethrin standard solution 200uL, be placed in the 150mL conical flask, accurately add the 50.0mL normal hexane: methylene chloride (1+1), the 18000r/min homogeneous extracts 3min. sample liquid and filters in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, to be clean.
2.3.2 purify
2.4 chromatographic condition
GC/ μ ECD: chromatographic column: HP-5 (30m * 0.32mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high pure nitrogen (99.999%); Flow velocity: 1.5ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; 310 ℃ of detector temperatures; Sample size 1.0 μ L.
GC/MS/MS: chromatographic column: HP-5MS (30m * 0.25mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high-purity helium (99.999%); Collision gas: High Purity Nitrogen (99.999%); Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; Sample size 1.0 μ L; Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: multiple-reaction monitoring pattern (MRM), parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
The measured value that shows after testing this sample recovery test is 96ng/mL, by calculating its recovery, is 96%.
Take about 20.00g (being accurate to 0.01g) mashed garlic, add 1.0ug/mL flumethrin standard solution 200uL, be placed in the 150mL conical flask, accurately add the 50.0mL normal hexane: methylene chloride (1+1), the 18000r/min homogeneous extracts 3min. sample liquid and filters in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, to be clean.
2.3.2 purify
2.4 chromatographic condition
GC/ μ ECD: chromatographic column: HP-5 (30m * 0.32mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high pure nitrogen (99.999%); Flow velocity: 1.5ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; 310 ℃ of detector temperatures; Sample size 1.0 μ L.
GC/MS/MS: chromatographic column: HP-5MS (30m * 0.25mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high-purity helium (99.999%); Collision gas: High Purity Nitrogen (99.999%); Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; Sample size 1.0 μ L; Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: multiple-reaction monitoring pattern (MRM), parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
The measured value that shows after testing this sample recovery test is 102ng/mL, by calculating its recovery, is 102%.
Embodiment 4
Take about 10.00g(and be accurate to 0.01g) dewatered garlic flake, add 1.0ug/mL flumethrin standard solution 100uL, be placed in the 100mL plastic centrifuge tube, add the 20mL normal hexane: methylene chloride (1+1) 18000r/min homogeneous, the centrifugal 5min of 3000r/min, extract is filtered in the 50mL color comparison tube, residue is used the 20mL normal hexane again: methylene chloride (1+1) extracts once, extract is filtered in color comparison tube in the lump, sample liquid blows near dry in 50 ℃ of water-bath nitrogen, with 2.0mL n-hexane dissolution residue, to be clean.
2.3.2 purify
2.4 chromatographic condition
GC/ μ ECD: chromatographic column: HP-5 (30m * 0.32mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high pure nitrogen (99.999%); Flow velocity: 1.5ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; 310 ℃ of detector temperatures; Sample size 1.0 μ L.
GC/MS/MS: chromatographic column: HP-5MS (30m * 0.25mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high-purity helium (99.999%); Collision gas: High Purity Nitrogen (99.999%); Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; Sample size 1.0 μ L; Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: multiple-reaction monitoring pattern (MRM), parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
The measured value that shows after testing this sample recovery test is 75ng/mL, by calculating its recovery, is 75%.
Embodiment 5
Take about 10.00g(and be accurate to 0.01g) the dehydrated garlic grain, add 1.0ug/mL flumethrin standard solution 100uL, be placed in the 100mL plastic centrifuge tube, add the 20mL normal hexane: methylene chloride (1+1) 18000r/min homogeneous, the centrifugal 5min of 3000r/min, extract is filtered in the 50mL color comparison tube, residue is used the 20mL normal hexane again: methylene chloride (1+1) extracts once, extract is filtered in color comparison tube in the lump, sample liquid blows near dry in 50 ℃ of water-bath nitrogen, with 2.0mL n-hexane dissolution residue, to be clean.
2.3.2 purify
2.4 chromatographic condition
GC/ μ ECD: chromatographic column: HP-5 (30m * 0.32mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high pure nitrogen (99.999%); Flow velocity: 1.5ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; 310 ℃ of detector temperatures; Sample size 1.0 μ L.
GC/MS/MS: chromatographic column: HP-5MS (30m * 0.25mm i.d., 0.25 μ m) fused-silica capillary column; Carrier gas: high-purity helium (99.999%); Collision gas: High Purity Nitrogen (99.999%); Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ (1min) are with 10 ℃/min temperature programme to 300 ℃ (15min); Injector temperature: 280 ℃; Sample size 1.0 μ L; Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: multiple-reaction monitoring pattern (MRM), parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
The measured value that shows after testing this sample recovery test is 71ng/mL, by calculating its recovery, is 71%.
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Claims (5)
1. the assay method of flumethrin in a garlic or its goods, is characterized in that, it comprises the following steps:
(1) extract: take garlic and be put in container Microwave Treatment in micro-wave oven, or take garlic products and be put in container, to adding the normal hexane that volume ratio is 1: 1 in container: methylene chloride, through homogeneous and/or centrifugal treating, standing rear system is divided into organic phase and inorganic phase, organic phase is dried up with nitrogen, and the residue n-hexane dissolution, obtain solution to be clean;
(2) purify: nh 2 column is used to acetone and the pre-drip washing of normal hexane successively, when solvent liquid level arrives post adsorbed layer surface, pour immediately the solution to be clean that step (1) makes into, receive eluent, and the normal hexane that is 1: 1 by volume ratio: the methylene chloride wash-out obtains scavenging solution; Scavenging solution dries up with nitrogen, the acetone that residue is 10: 90 by volume ratio: n-hexane dissolution, and the machine on 0.22 μ m filter membrane of crossing is measured;
(3) detect: gas chromatography for scavenging solution/tandem mass spectrometry is measured the flumethrin in garlic or its goods, and chromatographic condition is:
GC/MS/MS: chromatographic column: HP-5MS fused-silica capillary column, 30m * 0.25mm i.d., 0.25 μ m; Carrier gas: high-purity helium; Collision gas: High Purity Nitrogen; Flow velocity: 1.0ml/min; Input mode: Splitless injecting samples; Column temperature: initial 180 ℃ keep 1min, then with 10 ℃/min temperature programme to 300 ℃, keep 15min; Injector temperature: 280 ℃; Sample size 1.0 μ L; Ion gun: EI source; Ion source temperature: 230 ℃; Level Four bar temperature: 150 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃; Solvent delay: 5min; Scan mode: the multiple-reaction monitoring pattern, parent ion 239, daughter ion is 203,168,159, collision energy is 15ev.
2. assay method as claimed in claim 1, it is characterized in that, described in step (1), the leaching process of garlic is: take bright garlic sample 20.00g, be accurate to 0.01g, be placed in the 150mL conical flask, in micro-wave oven after 640w microwave 40-60s, shred, accurately add the normal hexane that the 50.0mL volume ratio is 1:1: methylene chloride, the 18000r/min homogeneous extracts 3min, extract is filtered in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, obtain solution to be clean.
3. assay method as claimed in claim 1, it is characterized in that, leaching process when described in step (1), garlic products is the dry sample goods is: take garlic dry sample goods 10.00g, be accurate to 0.01g, be placed in the 100mL plastic centrifuge tube, add the normal hexane that the 20mL volume ratio is 1:1: methylene chloride 18000r/min homogeneous, the centrifugal 5min of 3000r/min, extract is filtered in the 50mL color comparison tube, the normal hexane that residue is 1:1 by the 20mL volume ratio again: methylene chloride extracts once, extract is filtered in color comparison tube in the lump, sample liquid blows near dry in 50 ℃ of water-bath nitrogen, with 2.0mL n-hexane dissolution residue, obtain solution to be clean.
4. assay method as claimed in claim 1, it is characterized in that, leaching process when garlic products described in step (1) is wet sample goods is: take the wet sample goods 20.00g of garlic, be accurate to 0.01g, be placed in the 150mL conical flask, accurately add the normal hexane that the 50.0mL volume ratio is 1:1: methylene chloride, the 18000r/min homogeneous extracts 3min, sample liquid is filtered in the color comparison tube that is placed with in advance 5-10gNaCl, cover stopper, violent jolting 1min, standing 30min, after organic phase and water layering, accurately pipette the 25mL organic phase in the 25mL color comparison tube, 50 ℃ of water-bath nitrogen blow near dry, with 2.0mL n-hexane dissolution residue, obtain solution to be clean.
5. assay method as claimed in claim 1, it is characterized in that, the concrete steps that purify in step (2) are: nh 2 column is used to 3.0mL acetone and the pre-drip washing of 5mL normal hexane successively, when solvent liquid level arrives post adsorbed layer surface, pour immediately above-mentioned solution to be clean into, receive eluent, the normal hexane that is 1:1 by the 3.0mL volume ratio with the pointed centrifuge tube of 10mL: the methylene chloride wash-out, and repeat once; Scavenging solution nitrogen in 50 ℃ of water-baths blows near dry, accurately adds the acetone that the 1.0mL volume ratio is 10:90: after the n-hexane dissolution residue, cross 0.22 μ m filter membrane and treat machine mensuration.
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