CN108802261A - Ethiprole and its metabolin purified material, and the preparation method and application thereof - Google Patents
Ethiprole and its metabolin purified material, and the preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- 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
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Abstract
The present invention relates to technical field of pesticide, in particular to a kind of ethiprole and its metabolin purified material, and the preparation method and application thereof.The purified material is mainly made of following raw material：Strong anion exchanges filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon.Purified material good purification provided by the invention, removal impurity is more, reduces matrix effect, improves Detection accuracy.The preparation method of the pre-treatment material of offer is simple for process, and controllability is strong, and economic cost is low, is produced on a large scale.High to the rate of recovery of ethiprole and its metabolin using above-mentioned purified material and extracting solution, the high throughput assay ethiprole and its metabolin of directly selecting property realize fast and convenient detection.
Description
Technical field
The present invention relates to technical field of pesticide, in particular to a kind of ethiprole and its metabolin purified material, and its
Preparation method and application.
Background technology
Ethiprole, English name Fipronil, chemical name 5- amino-(bis- chloro- 4a- trifluoromethyls of 2.6-)-
4- trifluoromethyl sulfinyl pyrazole -3- itrile group pyrazoles is to be developed to grind in 1987 by French rhone-poulenc agro-chemical companies
The phenyl pyrazoles high activity insecticide of system is mainly used for preventing the pests such as vegetables, rice, animal husbandry, public health.Ethiprole
It can be metabolized in external environment and generate the compounds such as the higher ethiprole sulfone of toxicity and ethiprole sulfoxide, most common metabolin
For fluorine formonitrile HCN, ethiprole sulfone, ethiprole sulfoxide, ethiprole amide.The research of ecotoxicology finds ethiprole and its metabolin
There is relatively latent insecurity for ecological environment, and possesses and play the role of chronic toxicity for nervous system.Agricultural
Portion is in No. 1157 bulletin of publication in 2 months 2009：There is high risk to shell-fish aquatile and honeybee in view of ethiprole, in water
It is slow with degraded in soil, from 1 day October in 2009, in addition to the parts dry land coating agent for seed such as hygienic use, corn, in China border
It is interior to stop sale and using the pesticidal preparations for otherwise containing fipronil ingredient.Ethiprole is included in by China as residual
One of project of monitoring, but and formulate relevant limit standard.
In July, 2017, Germany, which reports, to be detected in Holland, Belgian egg containing ethiprole, by conduct
The news of " malicious egg " undercarriage.With the fermentation of time, " malicious egg " event caused by ethiprole is still in European Union or even the whole world
Diffusion.It is assumed that main cause may be to be mixed with the thimerosal of ethiprole since chicken house peasant household has used, it is dirty in disinfecting process
The drinking water or feed of chicken have been contaminated, has caused in egg indirectly and pollutes ethiprole.In addition, whether the feed of feeding laying hen polluted fluorine
Worm nitrile also merits attention with the presence or absence of the case where artificially adding ethiprole in feed etc..To understand Fluorine Content in Feedstuff worm nitrile risk
Situation, the detection method for establishing Fluorine Content in Feedstuff worm nitrile and its metabolin is very necessary.
In order to assess residual and the ethiprole pollution of Fluorine Content in Feedstuff worm nitrile, it is therefore desirable to establish the detection of Fluorine Content in Feedstuff worm nitrile
Method.Although the detection research of ethiprole has been achieved with prodigious progress, the remaining sample purification processing of ethiprole mostly uses solid
Mutually extraction (SPE) method, liquid-liquid extraction method, QuEChERS methods etc..Solid Phase Extraction (SPE) method can be completed at the same time the enrichment of sample with it is net
Change, clean-up effect is preferable, but solid phase extraction column cost is higher, and the usage amount of organic solvent is larger, and at the same time needing
Extracting solution drying is redissolved with water phase, operation is comparatively laborious time-consuming.Liquid-liquid extraction method is too simple, purified sample
Impurity is still more in solution, and matrix effect is more serious, and is easy pollution instrument.QuEChERS methods are easy to operate, big at present
Part uses C18, PSA and anhydrous magnesium sulfate as sorbing material, poor to impurity absorption effect in feed.Therefore, this field
Urgently a kind of environmental protection, easy pre-treatment material are for detecting Fluorine Content in Feedstuff worm nitrile and its metabolin.
In view of this, special propose the present invention.
Invention content
The purpose of the present invention is to provide a kind of ethiprole and its preparation sides of metabolin purified material and the material
Method；The lower cost for material, is produced on a large scale；This method is simple for process, and controllability is strong.
Another object of the present invention is to provide a kind of method of detection Feed Sample ethiprole and its metabolin, this method
Using purified material as described above, good purification, removal impurity is more, and economic cost is low.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
The present invention relates to a kind of ethiprole and its metabolin purified materials, are mainly made of following raw material：Strong anion is handed over
Change filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon.
Ethiprole and its metabolin purified material good purification provided by the invention, removal impurity is more, reduces matrix
Effect improves Detection accuracy.
According to an aspect of the present invention, the invention further relates to ethiprole as described above and its systems of metabolin purified material
Preparation Method, including：
The strong anion is exchanged filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon to mix
It is even, it is dried after being cleaned with methanol.
This method is simple for process, and controllability is strong, and economic cost is low, is produced on a large scale.
According to an aspect of the present invention, the invention further relates to the sides of a kind of detection Feed Sample ethiprole and its metabolin
Method, including：
It is carried out after carrying out pre-treatment to the Feed Sample using ethiprole as described above and its metabolin purified material
Quantitative detection.
Compared with prior art, beneficial effects of the present invention are：
Application process of the pre-treatment material in terms of detection Fluorine Content in Feedstuff worm nitrile and its metabolin, before above-mentioned
Material tests Fluorine Content in Feedstuff worm nitrile and its metabolin are handled, the rate of recovery is high, the high throughput assay of directly selecting property, realizes quick
Easy detection.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is different sorbing materials in the embodiment of the present invention 1 to the rate of recovery of 2 kinds of ethiproles and its metabolin in feed.
Fig. 2 is ethiprole and its metabolin hybrid standard working solution characteristic ion chromatogram in one embodiment of the invention；*
It is respectively from top to bottom：Ethiprole amide, ethiprole, fluorine formonitrile HCN, ethiprole sulfone, ethiprole sulfoxide；
Fig. 3 is that purified material and other QuEChERS materials purification effects compare figure in one embodiment of the invention.
Specific implementation mode
The present invention relates to a kind of ethiprole and its metabolin purified materials, are mainly made of following raw material：Strong anion is handed over
Change filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon.
Wherein, strong anion exchanges the substances such as filling adsorption anion, organic acid, nucleic acid, nucleotide；Strong cation exchange
Material, the absorption for being suitble to alkali compounds.Graphitized carbon is mainly physical absorption, primary attachment gas, colors；
C18 solid phase extraction fillers interact mainly by nonpolar carbon key, contribute to eluting, instead to the sample of non-polar absorbent process
It mutually extracts, primary attachment phosphatide and moderately polar compound.It is solid that strong anion exchanges filler, strong cation exchange material, C18
The combination of phase extraction stuffing, the graphitized carbon under the conditions of ratio makes adsorption effect of the material to ethiprole and its metabolin
It is small, while good purification.
Preferably, ethiprole and its metabolin purified material as described above, the strong anion exchange filler, Qiang Yangli
The mass ratio that son exchanges filler, C18 solid phase extraction fillers and graphitized carbon is 0.8~1.2:0.8~1.2:0.8~1.2:
0.2~0.6；More preferably 1:1:1:0.3~0.5；More preferably 1:1:1:0.4.
Preferably, ethiprole and its metabolin purified material as described above, it is SAX that the strong anion, which exchanges filler,.
Preferably, ethiprole and its metabolin purified material as described above, the strong cation exchange material are SCX.
According to an aspect of the present invention, the invention further relates to ethiprole as described above and its systems of metabolin purified material
Preparation Method, including：
The strong anion is exchanged filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon to mix
It is even, it is dried after being cleaned with methanol；
Preferably, the method used in the mixing shakes 4h with shaking table again after being eddy mixer whirlpool mixing 40s~80s
~6h；
Preferably, the condition of the drying is：35 DEG C~45 DEG C dry 7h~11h.
According to an aspect of the present invention, the invention further relates to the sides of a kind of detection Feed Sample ethiprole and its metabolin
Method, including：
It is carried out after carrying out pre-treatment to the Feed Sample using ethiprole as described above and its metabolin purified material
Quantitative detection.
Preferably, the method quantitatively detected includes：Mass spectrography.
Preferably, the process of method as described above, the pre-treatment specifically includes：
1) is by the Feed Sample and acetonitrile mixing, after ultrasonic extraction centrifugation obtain the first supernatant；
2) first supernatant and the ethiprole and its metabolin purified material mixing are obtained second by after centrifugation
Supernatant, second supernatant, which is crossed 0.2~0.24 μm of filter membrane, must wait for test sample.
Preferably, in step 1), the adding proportion of the Feed Sample and the acetonitrile is 2~5g:20mL；More preferably
For 3~4g:20mL.
Preferably, in step 2), first supernatant and the ethiprole and its dosage of metabolin purified material
Than for 1mL~3mL:50mg；More preferably 1.5mL~2.5mL:50mg；More preferably 2mL:50mg.
It is furthermore preferred that first supernatant is 3~4g with the ethiprole and its amount ratio of metabolin purified material:
20mL。
Preferably, method as described above, the Feed Sample include mixed feed, concentrated feed, additive premixing
Feed, concentrate supplement, feedstuff.
Preferably, ethiprole and its metabolin purified material as described above and detection Feed Sample ethiprole and its generation
The method for thanking to object, the ethiprole and its metabolin include：Ethiprole, fluorine formonitrile HCN, ethiprole sulfone, ethiprole sulfoxide, ethiprole
Amide.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
The selection of the selection and ratio of adsorption of 1 different materials of embodiment
Selection ethiprole and its metabolin and ten kinds of sorbing materials (being specifically shown in Table 1) have carried out purifying and adsorb research in fact
It tests：Blank feed 25g is taken, 100mL acetonitriles are added, centrifugation is transferred in reagent bottle, draws 3mL extracting solutions respectively, is added
4 kinds of ethiprole standard solution of 0.1mL 100ng/mL are separately added into 100mg solid phase extraction fillers, whirlpool mixing 30s, in shaking table
Upper oscillation 10min, centrifugation go supernatant to cross film, the detection of liquid phase chromatographic mass spectrometry, while drawing 3mL extracting solutions, are added without solid phase
Extraction stuffing is as blank reference.
1 sorbing material title of table and type
Absorption result is shown in Fig. 1.The result shows that other than active carbon nanotube, all adsorption stuffings are not all bright to ethiprole
Aobvious absorption can be used in next step to feed Study on purification.From adsorption mechanism, C8 and C18 are mainly by nonpolar carbon
Key interacts, and contributes to the elution reversed phase extraction to the sample of non-polar absorbent process, primary attachment is in phosphatide and medium pole
The compound of property.Since C8 carbon keys are short compared with C18, thus to non-polar compound reservation be weaker than C18, therefore selected C18 as
Candidate material.NH2 be on silica matrix be bonded polar binding phase aminopropyl polar adsorbent, and have simultaneously hydrogen bond and
Two kinds of mechanisms of action of anion exchange, can be used in polarity sample detaching its nonpolarity point compound；PSA is extracted with NH2
The similar filler of column is taken, organic acid, pigment, metal ion etc. in main or removal sample；SAX is that strong anion exchanges extraction
It takes, is adsorbed in anionic species.SCX is strong cation exchange material, is suitble to the absorption of alkali compounds.Compared to NH2 and PSA,
The adsorption capacity of SCX and SAX mixing is more preferable, while the mixed of the two can effectively adsorb zwitterion.We select thus
SCX and SAX materials are as candidate filler.Carb main components are that ketjenblack EC is filler, due to the surface of ketjenblack EC
There is the structure of positive hexatomic ring so that it has extremely strong affinity for planar molecule, is extremely useful in the net of many organic matters
Change and in extraction, be especially adapted for use in the substances such as removal, the various matrix pigments of separation, sterol, for the adsorbance of compound
It is high compared to silica gel and aluminium oxide.Therefore we select C18, SCX, SAX and Carb filler as optional fillers.
According to the characterization of adsorption of different materials, a variety of materials are tentatively added and carry out Study on purification by we in proportion, still
As a result it beams back yield to be declined, be found by experiment that, when Carb is 20% or more, since Carb adsorption capacities are stronger, meeting
Influence slightly testing result.Therefore in material the ratio of graphitized carbon not above 20%.But come from matrix clean-up effect, it is added
10%~20% graphitized carbon, can effectively adsorbing contaminant, reduce matrix effect.Finally according to experiment, by this 4 kinds of solid absorptions
Agent is used in mixed way, and mixed proportion is set as 0.8~1.2:0.8~1.2:0.8~1.2:0.2~0.6, preferably 1:1:1:0.3~
0.5。
Embodiment 2
The preparation method of a kind of ethiprole and its metabolin purified material is present embodiments provided, including：
It is 15 to take mass ratio:15:15:9 SAX, SCX, C18 solid phase extraction filler, graphitized carbon.
Above-mentioned raw materials are added in centrifuge tube.Using eddy mixer whirlpool mixing 40s, shaken in constant temperature shakes bed
6h.4min is centrifuged under conditions of 9000r/min.Cleaning 1 time is carried out to centrifugation product with eluent methanol again, 35 DEG C~45
Dry 7h, obtains purified material under the conditions of DEG C.
Embodiment 3
The preparation method of a kind of ethiprole and its metabolin purified material is present embodiments provided, including：
It is 15 to take mass ratio:15:15:3 SAX, SCX, C18 solid phase extraction filler, graphitized carbon.
Above-mentioned raw materials are added in centrifuge tube.Using eddy mixer whirlpool mixing 80s, shaken in constant temperature shakes bed
4h.4min is centrifuged under conditions of 9000r/min.Cleaning 1 time is carried out to centrifugation product with eluent methanol again, 35 DEG C~45
Dry 11h, obtains purified material under the conditions of DEG C.
Embodiment 4
The preparation method of a kind of ethiprole and its metabolin purified material is present embodiments provided, including：
It is 15 to take mass ratio:15:15:6 SAX, SCX, C18 solid phase extraction filler, graphitized carbon.
Above-mentioned raw materials are added in centrifuge tube.Using eddy mixer whirlpool mixing 1min, shaken in constant temperature shakes bed
5h.4min is centrifuged under conditions of 9000r/min.Cleaning 1 time is carried out to centrifugation product with eluent methanol again, 35 DEG C~45
Dry 9h, obtains purified material under the conditions of DEG C.
The influence of 5 ethiprole of embodiment and its metabolin purified material additional proportion
Compare 5,10,20,50,80,100mg difference purified material additions 2mL feeds are extracted solution impurity it is net
Change the influence of effect.The result shows that when purified material addition reaches 50mg, the dosage for continuing to increase purified material is miscellaneous to sample
The clean-up effect and the rate of recovery of matter are not improved.Therefore purified material addition is set as 50mg. when addition adsorbent is inhaled
After attached purification, sample solution clarification greatly reduces the matrix effect of target compound.
The method that the application purified material of embodiment 6 measures Fluorine Content in Feedstuff worm nitrile and its metabolin
2~5g of feed is weighed, (being accurate to 0.01g) is accurate that 20mL acetonitriles, whirlpool mixing is added in 50mL centrifuge tubes
30s, ultrasonic extraction 15min, 8000r/min centrifuge 5min.It takes 2mL supernatants in 10mL plastic tubes, 50mg embodiments 4 is added
The purified material being prepared, whirlpool mix 30 seconds, and supernatant is collected in 8000r/min centrifugations 2min.0.22 μm of filter membrane is crossed, on
Machine measures.
The identical blank Feed Sample of sample to be tested type is chosen simultaneously, is handled by above-mentioned steps, after purification, drying
In residue, suitable hybrid standard working solution is added respectively, is configured to the matrix addition of various concentration (1 μ g/L-100 μ g/L)
It is quantitative to carry out matrix mark-on for standard curve.
Further, in the preferred embodiment of the present invention, specific detection method includes：
Column chromatography：It is 150mm, internal diameter 3.0mm, chromatographic column that grain size is 2.1 μm in 30 DEG C, 10 μ L sample introductions to use column length
Column chromatography under conditions of amount.Mobile phase and flow velocity are shown in Table 2.
2 condition of gradient elution table of table
Mass Spectrometer Method：Using electric spray ion source, anion scan pattern, multiple-reaction monitoring, piecewise acquisition data.It needs
It is noted that desolventizing gas, taper hole gas, collision gas are high pure nitrogen and other suitable gas, each gas should be adjusted before use
Flow is so that sensitivity of mass spectrometry reaches testing requirements.The voltage values such as capillary voltage, orifice potential, collision energy should be optimized to most
Good sensitivity.Qualitative ion pair, quota ion pair and corresponding orifice potential and collision energy are shown in Table 3.Ethiprole and its metabolism
Object hybrid standard working solution characteristic ion chromatogram is shown in Fig. 2.
3 ethiprole of table and its metabolin LC-MS/MS instrument parameters
7 purified material of embodiment and other QuEChERS materials are in the effect ratio for measuring Fluorine Content in Feedstuff worm nitrile and its metabolin
Compared with
The QuEChERS materials of purified material and document report to our application inventions are compared, and feed 5g is weighed
In 50mL centrifuge tubes, accurate that 20mL acetonitriles are added, whirlpool mixing 30s, ultrasonic extraction 15min, 8000r/min centrifuge 5min.
It takes 2mL supernatants in 10mL plastic tubes respectively, following four methods is taken to operate：
The purified material that 50mg embodiments 4 are prepared is added；
100mg PSA and 75mg graphitized carbons are added；
50mg PSA and 50mgC18 materials are added；
Without any processing.
Then, whirlpool mixes 30 seconds, and supernatant is collected in 8000r/min centrifugations 2min.It crosses
0.22 μm of filter membrane, upper machine measure.Observe clean-up effect and rate of recovery situation simultaneously.
Clean-up effect is shown in Fig. 3, as can be seen from the figure uses purification of the purified material that embodiment 4 is prepared to feed
Best results, solution are in colorless state substantially, while Fluorine Content in Feedstuff worm nitrile and its metabolin rate of recovery highest.Method 2, although 3
It is preferable to the rate of recovery of ethiprole, but to the detection result of Fluorine Content in Feedstuff worm nitrile metabolin ethiprole sulfoxide and ethiprole amide
It is bad.
Embodiment 8:There should be material to measure the determination data result in feed
1. linear, detection limit and quantitative limit
Standard curve, detection limit and the quantitative limit of 4 kinds of ethiproles and its metabolin in matrix are shown in Table 4.
4 ethiprole of table and its metabolin contrast solution Linear Experiment result
2. the rate of recovery and precision
We, as test object, carry out recovery of standard addition experiment, to investigate the standard of method with all kinds of blank Feed Samples
Exactness and reproducibility.The sample of 5 μ g/kg, 10 μ g/kg and 50 tri- concentration of μ g/kg are prepared, same concentration is done 6 times in every batch of
Parallel laboratory test, altogether repeatedly 3 batch.The result shows that this method is suitable for the measurement of Fluorine Content in Feedstuff worm nitrile and its metabolin.
5 feed of table and the corn rate of recovery and Precision Experiment result (n=6)
6 concentrate supplement of table, concentrated feed, the premixed feed rate of recovery and Precision Experiment result (n=6)
The 7 feedstuff rate of recovery of table and Precision Experiment result (n=6)
In conclusion purified material good purification provided by the invention, removal impurity is more, reduces matrix effect, carries
High detection accuracy rate.The preparation method of the pre-treatment material of offer is simple for process, and controllability is strong, and economic cost is low, can scale
Production.It is high to the rate of recovery of ethiprole and its metabolin using above-mentioned purified material and extracting solution, the height of directly selecting property
Flux measures ethiprole and its metabolin, realizes fast and convenient detection.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, but it will be understood by those of ordinary skill in the art that：Its
It still can be with technical scheme described in the above embodiments is modified, either to which part or all technical features
Carry out equivalent replacement；And these modifications or replacements, various embodiments of the present invention skill that it does not separate the essence of the corresponding technical solution
The range of art scheme.
Claims (10)
1. a kind of ethiprole and its metabolin purified material, which is characterized in that be mainly made of following raw material：Strong anion exchanges
Filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon.
2. ethiprole according to claim 1 and its metabolin purified material, which is characterized in that the strong anion exchanges
Filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon mass ratio be 0.8~1.2:0.8~1.2:
0.8~1.2:0.2~0.6；More preferably 1:1:1:0.3~0.5.
3. ethiprole according to claim 1 or 2 and its metabolin purified material, which is characterized in that the strong anion
Exchange filler is SAX.
4. ethiprole according to claim 1 or 2 and its metabolin purified material, which is characterized in that the strong cation
Exchange filler is SCX.
5. ethiprole according to claim 1 or 2 and its metabolin purified material, which is characterized in that the ethiprole and
Its metabolin includes：Ethiprole, fluorine formonitrile HCN, ethiprole sulfone, ethiprole sulfoxide, ethiprole amide.
6. the preparation method of Claims 1 to 5 any one of them ethiprole and its metabolin purified material, which is characterized in that
Including：
The strong anion is exchanged into filler, strong cation exchange material, C18 solid phase extraction fillers and graphitized carbon mixing,
It is dried after being cleaned with methanol；
Preferably, the method used in the mixing be eddy mixer whirlpool mixing 40s~80s after again with shaking table shaking 4h~
6h；
Preferably, the condition of the drying is：35 DEG C~45 DEG C dry 7h~11h.
7. a kind of method of detection Feed Sample ethiprole and its metabolin, which is characterized in that including：
Before being carried out to the Feed Sample using 5 any one of them ethiprole of Claims 1 to 5 and its metabolin purified material
Quantitative detection is carried out after processing.
8. the method according to the description of claim 7 is characterized in that the process of the pre-treatment specifically includes：
1) is by the Feed Sample and acetonitrile mixing, after ultrasonic extraction centrifugation obtain the first supernatant；
2) first supernatant and the ethiprole and its metabolin purified material mixing are obtained the second supernatant by after centrifugation
Liquid, second supernatant, which is crossed 0.2 μm~0.24 μm filter membrane, must wait for test sample.
9. according to the method described in claim 8, it is characterized in that, in step 1), the Feed Sample and the acetonitrile
Adding proportion is 2~5g:20mL；
Preferably, in step 2), the amount ratio of first supernatant and the ethiprole and its metabolin purified material is
1mL~3mL:50mg.
10. method according to claim 8 or claim 9, which is characterized in that the Feed Sample includes mixed feed, concentration feeding
Material, additive premix, concentrate supplement, feedstuff.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810597290.0A CN108802261B (en) | 2018-06-11 | 2018-06-11 | Fipronil and its metabolite purifying material, its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810597290.0A CN108802261B (en) | 2018-06-11 | 2018-06-11 | Fipronil and its metabolite purifying material, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108802261A true CN108802261A (en) | 2018-11-13 |
| CN108802261B CN108802261B (en) | 2020-10-02 |
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| CN104614472A (en) * | 2015-02-13 | 2015-05-13 | 浙江省农业科学院 | Chromatographic column for analyzing multiple pesticide residues in complex matrix and applying method of chromatographic column |
| CN106397670A (en) * | 2016-09-13 | 2017-02-15 | 暨南大学 | Broad spectrum solid phase extract filling synthesis method |
| CN107917974A (en) * | 2017-11-10 | 2018-04-17 | 韩超 | The detection method of ethiprole and its metabolite residue amount in egg |
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| EP2305662A1 (en) * | 2009-10-02 | 2011-04-06 | Cognis IP Management GmbH | Alkoxylated glycerol acetals and their derivatives |
| CN104614472A (en) * | 2015-02-13 | 2015-05-13 | 浙江省农业科学院 | Chromatographic column for analyzing multiple pesticide residues in complex matrix and applying method of chromatographic column |
| CN106397670A (en) * | 2016-09-13 | 2017-02-15 | 暨南大学 | Broad spectrum solid phase extract filling synthesis method |
| CN107917974A (en) * | 2017-11-10 | 2018-04-17 | 韩超 | The detection method of ethiprole and its metabolite residue amount in egg |
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