CN106404938A - Dispersive solid-phase extraction purification tube for detection of six phenoxy carboxylic acid herbicides in cereals and use method thereof - Google Patents
Dispersive solid-phase extraction purification tube for detection of six phenoxy carboxylic acid herbicides in cereals and use method thereof Download PDFInfo
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- CN106404938A CN106404938A CN201610743012.2A CN201610743012A CN106404938A CN 106404938 A CN106404938 A CN 106404938A CN 201610743012 A CN201610743012 A CN 201610743012A CN 106404938 A CN106404938 A CN 106404938A
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- 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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- 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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- G—PHYSICS
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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
- G01N30/02—Column chromatography
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Abstract
Belonging to the field of analytical chemistry and food safety detection, the invention relates to a dispersive solid-phase extraction purification tube for detection of six phenoxy carboxylic acid herbicides in cereals and a use method thereof. Specifically, the dispersive solid-phase extraction purification tube consists of a tube cap (1), a tube body (2) and filler (3), wherein the filler (3) is 0.10g of a magnesium-aluminum type toluene-4-sodium sulfonate pillared hydrotalcite adsorbent. The use method of the dispersive solid-phase extraction purification tube includes the following three steps: activating the purification tube, adsorbing a target object and eluting the target object. The adsorbent adopted by the invention is an adsorbent with high efficiency adsorption effect on the six phenoxy carboxylic acid herbicides, and only a 0.10g dosage is needed. The employed dispersive solid-phase extraction purification tube pretreatment method has the characteristics of no use of organic solvent, safety and environmental protection, and also has the advantages of simple operation, rapidity and high efficiency.
Description
Technical field
The invention belongs to analytical chemistry and field of detection of food safety are and in particular to can be used for six kinds of benzene in corn to one kind
The dispersive solid-phase extraction of oxycarboxylic acid class herbicide purifies pipe and its using method.
Background technology
Phenoxy carboxylic acid herbicides is second largest selective herbicide kind in agricultural production, be widely applied to paddy field,
Bare place and pasture etc., with the increasingly increase of usage amount and range, such material has also become impact corn and has eaten peace
Full key factor.For this reason, the major country such as China, European Union, the U.S., Japan and area are to corn such as rice, Semen Tritici aestivi and Semen Maydiss
Middle phenoxy carboxylic acid herbicides all defines the requirement of maximum Limited Doses (MRL).
Currently, in corn, the detection method of phenoxy carboxylic acid herbicides is mainly chromatography and combined gas chromatography mass spectrometry；Before
Processing method experienced two stages, and early stage, using first being extracted using water or aqueous alkali, is acidified to extracting solution afterwards, then
Using organic solvent fluid liquid extracting and enriching；Later stage people adopt in solid-phase extraction column direct absorb-elute aqueous solution or aqueous alkali
Phenoxy carboxylic acid herbicides enrichment.But liquid-liquid extraction method enrichment exists using deficiencies such as the big, complex operations of organic solvent amount；Gu
The enrichment of phase extraction is available for that selected adsorbent single varieties, adsorption rate be low, pre-treatment the shortcomings of time-consuming it would be highly desirable to find new
High-efficiency adsorbent and explore efficiently pretreatment mode.
Layered double hydroxide (Layered Double Hydroxides, LDHS), also known as stratiform brucite, be
Typical anionic type laminated material, Typical Representative therein is that (molecular formula is Mg to magnalium type brucite6Al2(OH)16CO3·
4H2O, abbreviation MgAl-LDH), wherein the hydroxide of magnalium constitutes laminate, and carbanion is the anion between laminate.Neatly
Stone class compound has composition hydroxide Modulatory character, interlayer anion species and quantity Modulatory character, the crystal grain chi of laminate
Feature that is very little and being distributed Modulatory character；Meanwhile, this kind of material has small-size effect, skin effect and macro quanta tunnel effect
Etc. characteristic.Therefore, this kind of material is widely used in the various fields such as sewage disposal, synthesis catalytic, medical slow release, combustion-supporting material.
Inventor's early-stage Study shows, through the modified brucite magnalium type toluene-4-sulfonic acid of toluene-4-sulfonic acid sodium
Sodium pillared hydrotalcite adsorbent has good adsorption and enrichment effect, Ke Yiying to six kinds of phenoxy carboxylic acid herbicides such as 2,4-D
With being developed into a kind of new adsorbent of six kinds of phenoxy carboxylic acid herbicides of efficient absorption.
The relevant information of 1 six kinds of phenoxy carboxylic acid herbicides of table
Content of the invention
Have to overcome to exist to use using phenoxy carboxylic acid herbicides pretreatment liquid liquid extraction method enrichment in detection corn
The deficiencies such as machine quantity of solvent is big, complex operation；And selected adsorbent single varieties, suction are available for using solid phase extraction enrichment
Attached rate is low, pre-treatment is the shortcomings of time-consuming, it is an object of the invention to provide one kind can be used for six kinds of phenoxy carboxylic acids in corn
The dispersive solid-phase extraction of herbicide purifies pipe and its using method.
The present invention is achieved through the following technical solutions above-mentioned target.
A kind of dispersive solid-phase extraction that can be used for six kinds of phenoxy carboxylic acid herbicides detections in corn purifies pipe, including lid
1, body 2 and filler 3, its middle tube body 2 is connected with lid 1 by screw thread, and filler 3 is placed in body 2 it is characterised in that described
Filler is the magnalium type toluene-4-sulfonic acid sodium pillared hydrotalcite adsorbent that quality is 0.10g, and its molecular composition skeleton symbol is Mg6Al2
(OH)16(C7H7SO3)2·4H2O.
Wherein,
Six kinds of described phenoxy carboxylic acid herbicides are 2,4 dichlorophenoxyacetic acid, 2,4 dichloro benzene oxygen propanoic acid, 2,4- bis-
Chlorobenzene oxy butyrate, 2-methyl-4-chlorophenoxyacetic acid, 2- methyl -4- chlorophenoxy butanoic acid, 2,4,5 trichlorophenoxyacetic acid.
The using method that above-mentioned dispersive solid-phase extraction purifies pipe comprises the following steps：
Step one, activation：Purify in pipe to dispersive solid-phase extraction and add deionized water, be vortexed, centrifugation, abandoning supernatant；
Step 2, absorption：Purify to add in pipe to dispersive solid-phase extraction and be extracted carrying of six kinds of phenoxy carboxylic acid herbicides
Take solution, be vortexed, vibration, centrifugation, discard the supernatant；
Step 3, De contamination：To in centrifuge tube add De contamination solvent, be vortexed, vibration, centrifugation, gained supernatant be containing
There is the De contamination solution of six kinds of phenoxy carboxylic acid herbicides.
Wherein,
Six kinds of described phenoxy carboxylic acid herbicides are 2,4 dichlorophenoxyacetic acid, 2,4 dichloro benzene oxygen propanoic acid, 2,4- bis-
Chlorobenzene oxy butyrate, 2-methyl-4-chlorophenoxyacetic acid, 2- methyl -4- chlorophenoxy butanoic acid, 2,4,5 trichlorophenoxyacetic acid.
The amount activating deionized water in step one is 15mL.
Extraction solution in step 2 is deionized water.
The time being vortexed is 3min, and the time of vibration is 15min, and centrifugal rotational speed is 4500r/min, and centrifugation time is
3min.
In step 3, De contamination agent is the metabisulfite solution of 1.00mol/L, and the De contamination agent volume of interpolation is 2.00mL.
It is an advantage of the current invention that：
(1) magnalium type toluene-4-sulfonic acid sodium pillared hydrotalcite of the present invention is a kind of to six kinds of phenoxy carboxylic acids
Herbicide has the adsorbent of efficient absorption effect, only need to use the consumption of 0.10g；
(2) dispersive solid-phase extraction purification pipe of the present invention carries out pre-treatment, has compared to liquid-liquid extraction enrichment
The advantage not using organic solvent, safety and environmental protection, has the characteristics that easy and simple to handle, quickness and high efficiency compared to Solid phase extraction.
Brief description
Fig. 1 is that dispersive solid-phase extraction purifies pipe schematic diagram；
Fig. 2 is absorption in embodiment 1 and De contamination effectiveness comparison figure, and wherein 1 is 2,4-D, 2 to be MCPA, and 3 is 2,4-
DP, 4 is 2,4,5-T, 5 to be MCPB, 6 be 2,4-DB, A be extraction standard solution, B is the solution after bare substrate sample elution, C
It is the solution after substrate mark-on eluting；
Fig. 3 is absorption in embodiment 2 and De contamination effectiveness comparison figure, and wherein 1 is 2,4-D, 2 to be MCPA, and 3 is 2,4-
DP, 4 is 2,4,5-T, 5 to be MCPB, 6 be 2,4-DB, A be extraction standard solution, B is the solution after bare substrate sample elution, C
It is the solution after substrate mark-on eluting.
Specific embodiment
For disclosing further rather than limiting the present invention, below in conjunction with example, the present invention is described in further detail.
(1) involved reagent chemicals in the embodiment of the present invention is as follows：
Toluene-4-sulfonic acid sodium, sodium sulfate, analyze pure, Chinese medicines group；
Mg6Al2(OH)16CO3·4H2O, analyzes pure, U.S.'s Aldrich.
Acetonitrile, formic acid, ammonium formate：Chromatographically pure；Water is the one-level water meeting GB/T 6682 regulation.
Six kinds of phenoxy carboxylic acid herbicides solid-state standard substance：Purity is more than or equal to 98.0%, German Dr.Ehrenstorfer
Company.
The configuration of six kinds of phenoxy carboxylic acid herbicides standard reserving solutions：Weigh appropriate six kind herbicide standard substance, to go
Ion water dissolution constant volume, are configured to save backup at the storing solution of 1000mg/L, -4 DEG C.
(2) involved instrument in the embodiment of the present invention is as follows：
EXCEL type microwave dissolver, Shanghai EU Apparatus Technology Development Co., Ltd., clearing up tank volume is 100mL；Microwave
Muffle furnace (sintering furnace), U.S. CE M company；VD53 type vacuum drying oven, Buchbinder, Germany scientific ＆ technical corporation；HJ-5 multifunction constant temperature stirs
Mix device, Jintan high honour instrument manufacturing company limited；FS-12 type separating funnel oscillator, new Micron Technology Co., Ltd of Japan；3K-
15 type centrifuges, German sigma scientific ＆ technical corporation；BF518945C-1 type chamber type electric resistance furnace (Muffle furnace), the U.S. matches Mo Feishier section
Skill company；T-18 type disperser, Dedu IK company；1200L type high performance liquid chromatograph, Anjelen Sci. ＆ Tech. Inc of the U.S..
(3) synthesis of magnalium type toluene-4-sulfonic acid sodium pillared hydrotalcite：
A) roasting：By precursor magnalium type brucite Mg6Al2(OH)16CO3·4H2O is placed in Muffle furnace, with heating rate 5
DEG C/min be heated to temperature be 500 DEG C, roasting 6h, obtain product of roasting Mg6Al2O8(OH)2；
B) weigh：The product of roasting of 11.711g intercalator toluene-4-sulfonic acid sodium and 7.236g is weighed in micro-wave diminishing pot
Mg6Al2O8(OH)2, the amount ratio of both materials is 3:1.
C) microwave crystallization Hydrothermal Synthesiss：Deionized water is boiled and keeps 30min, afterwards add 100mL to above-mentioned equipped with
In the micro-wave diminishing pot of intercalator and product of roasting, airtight, micro-wave diminishing pot is placed in microwave dissolver, micro- at 100 DEG C
Wave heating 30min completes to synthesize；
D) wash and be dried：All solids in microwave tank and liquid are poured out, to boil the removal dioxy of more than 30min
Change the heated stirring of deionized water of carbon, vibration is washed and is centrifuged, and is vacuum dried 12h at 90 DEG C, grind and preserve.
(4) liquid-phase chromatographic analysis test condition：
A) chromatographic column：C18Detached dowel is, 150mm × 4.6mm, 5 μm of particle diameter；Before the C that connects18Guard column is, 12.5mm ×
4.6mm, 5 μm of particle diameter.
B) chromatogram column temperature：25℃.
C) mobile phase：Solvent orange 2 A is, acetonitrile+water=80+20, volume ratio；Solvent B is, water；Wherein all contain in solvent orange 2 A and B
There are the formic acid of 3mM and the ammonium formate buffer solution of 3mM.
D) gradient：Solvent orange 2 A rises to 75% from 25% in 40min.
E) flow velocity：1.0mL/min.
F) Detection wavelength：230nm.
G) sample size：100μL.
Embodiment 1
The present embodiment 1 mesostroma is blank rice sample, and spiked levels are 0.2mg/kg：
(1) extract：Weigh the rice meal 10g grinding to form powdery in the centrifuge tube of 50mL, add 30mL in centrifuge tube
Deionized water, with 12000r/min high-speed homogenization 1min, with the centrifugation 3min of 4500r/min；
(2) activate：Take dispersive solid-phase extraction to purify pipe, be added to 15mL deionized water, vortex 3min, with 4500r/
The centrifugation 3min of min, abandoning supernatant.
(3) adsorb：Supernatant in extraction step is all inclined to be purified in pipe to the extremely dispersive solid-phase extraction through washing,
Vortex 3min, vibrates 15min, with the centrifugation 3min of 4500r/min, discards the supernatant；
(4) De contamination：Add the metabisulfite solution 2.00mL of 1.00mol/L in centrifuge tube, vortex 3min, vibration
15min, with the centrifugation 3min of 4500r/min, gained supernatant is the De contamination containing six kinds of phenoxy carboxylic acid herbicides
Solution.
(5) analyze：Draw above-mentioned De contamination solution, cross 0.22 μm of filter membrane, efficient liquid phase chromatographic analysis.
(6) test result analysis：From figure 2 it can be seen that six kinds of phenoxy carboxylic acid herbicides all obtain baseline separation, mesh
Mark peak is not affected by impurity peaks interference, wherein 2,4-D, MCPA, 2,4-DP, and the response rate of 2,4,5-T, MCPB and 2,4-DB is respectively
For：103.8%th, 102.2%, 110.5%, 106.7%, 107.6% and 98.5%, meet trace analysis and the response rate is wanted
Ask.
Embodiment 2
The present embodiment 2 mesostroma is blank wheat samples, and spiked levels are 0.2mg/kg：
(1) extract：Weigh the wheat flour 10g grinding to form powdery in the centrifuge tube of 50mL, add 30mL in centrifuge tube
Deionized water, with 12000r/min high-speed homogenization 1min, with the centrifugation 3min of 4500r/min；
(2) activate：Take dispersive solid-phase extraction to purify pipe, be added to 15mL deionized water, vortex 3min, with 4500r/
The centrifugation 3min of min, abandoning supernatant.
(3) adsorb：Supernatant in extraction step is all inclined to be purified in pipe to the extremely dispersive solid-phase extraction through washing,
Vortex 3min, vibrates 15min, with the centrifugation 3min of 4500r/min, discards the supernatant；
(4) De contamination：Add the metabisulfite solution 2.00mL of 1.00mol/L in centrifuge tube, vortex 3min, vibration
15min, with the centrifugation 3min of 4500r/min, gained supernatant is the De contamination containing six kinds of phenoxy carboxylic acid herbicides
Solution.
(5) analyze：Draw above-mentioned De contamination solution, cross 0.22 μm of filter membrane, efficient liquid phase chromatographic analysis.
(6) test result analysis：From figure 3, it can be seen that six kinds of phenoxy carboxylic acid herbicides all obtain baseline separation, mesh
Mark peak is not affected by impurity peaks interference, wherein 2,4-D, MCPA, 2,4-DP, and the response rate of 2,4,5-T, MCPB and 2,4-DB is respectively
For：102.8%th, 104.2%, 108.5%, 107.7%, 105.6% and 95.4%, meet trace analysis and the response rate is wanted
Ask.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore it is interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the ordinary skill in the art,
Without departing from the inventive concept of the premise, some deformation can also be made and improve, these belong to the protection model of the present invention
Enclose, the protection domain of patent therefore of the present invention should be defined by claims.
Claims (7)
1. a kind of dispersive solid-phase extraction that can be used for six kinds of phenoxy carboxylic acid herbicides detections in corn purifies pipe, including lid
(1), body (2) and filler (3), its middle tube body (2) is connected with lid (1) by screw thread, and filler (3) is placed in body (2), and it is special
Levy and be, described filler is the magnalium type toluene-4-sulfonic acid sodium pillared hydrotalcite adsorbent that quality is 0.10g, its group of molecules
One-tenth skeleton symbol is Mg6Al2(OH)16(C7H7SO3)2·4H2O.
2. a kind of dispersive solid-phase extraction that can be used in corn six kinds of phenoxy carboxylic acid herbicides detections is net as claimed in claim 1
Change pipe it is characterised in that six kinds of described phenoxy carboxylic acid herbicides are 2,4- dichlorphenoxyacetic acid, 2,4- Dichlorophenoxy third
Acid, 2,4 dichloro benzene oxy butyrate, 2-methyl-4-chlorophenoxyacetic acid, 2- methyl -4- chlorophenoxy butanoic acid, 2,4,5- trichloro-benzenes oxygen
Acetic acid.
3., according to claim 1, a kind of dispersive solid-phase extraction that can be used in corn six kinds of phenoxy carboxylic acid herbicides detections is net
The using method changing pipe comprises the following steps：
Step one, activation：Purify in pipe to dispersive solid-phase extraction and add deionized water, be vortexed, centrifugation, abandoning supernatant；
Step 2, absorption：To dispersive solid-phase extraction purify pipe in add be extracted six kinds of phenoxy carboxylic acid herbicides extraction molten
Liquid, is vortexed, vibration, and centrifugation discards the supernatant；
Step 3, De contamination：Add De contamination solvent in centrifuge tube, be vortexed, vibration, centrifugation, gained supernatant is containing six
Plant the De contamination solution of phenoxy carboxylic acid herbicides.
4. a kind of dispersive solid-phase extraction that can be used in corn six kinds of phenoxy carboxylic acid herbicides detections is net as claimed in claim 3
Change the using method of pipe it is characterised in that the amount activating deionized water in step one is 15mL.
5. a kind of dispersive solid-phase extraction that can be used in corn six kinds of phenoxy carboxylic acid herbicides detections is net as claimed in claim 3
Change the using method of pipe it is characterised in that the extraction solution in step 2 is deionized water.
6. a kind of dispersive solid-phase extraction that can be used in corn six kinds of phenoxy carboxylic acid herbicides detections is net as claimed in claim 3
Change the using method of pipe it is characterised in that the time being vortexed is 3min, the time of vibration is 15min, and centrifugal rotational speed is 4500r/
Min, centrifugation time is 3min.
7. a kind of dispersive solid-phase extraction that can be used in corn six kinds of phenoxy carboxylic acid herbicides detections is net as claimed in claim 3
Change the using method of pipe it is characterised in that De contamination agent is the metabisulfite solution of 1.00mol/L in step 3, the desorption of interpolation
Attached dose of volume is 2.00mL.
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| CN201610743012.2A CN106404938B (en) | 2016-08-28 | 2016-08-28 | It can be used for the application method of the dispersive solid-phase extraction purification pipe of six kinds of phenoxy carboxylic acid herbicides detections in cereal |
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| CN201610743012.2A CN106404938B (en) | 2016-08-28 | 2016-08-28 | It can be used for the application method of the dispersive solid-phase extraction purification pipe of six kinds of phenoxy carboxylic acid herbicides detections in cereal |
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