CN103977767A - Special solid-phase extraction cartridge for glyphosate and metabolite-aminomethyl phosphonate of glyphosate, and application of solid-phase extraction cartridge - Google Patents
Special solid-phase extraction cartridge for glyphosate and metabolite-aminomethyl phosphonate of glyphosate, and application of solid-phase extraction cartridge Download PDFInfo
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- CN103977767A CN103977767A CN201410233400.7A CN201410233400A CN103977767A CN 103977767 A CN103977767 A CN 103977767A CN 201410233400 A CN201410233400 A CN 201410233400A CN 103977767 A CN103977767 A CN 103977767A
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Abstract
The invention provides a special solid-phase extraction cartridge for glyphosate and metabolite of the glyphosate, and an application of the solid-phase extraction cartridge, wherein filler comprises anion adsorption filler, acidic material adsorption filler and a filter aid; the anion adsorption filler is magnesium-aluminum binary hydrotalcite and has the molecular composition formula of MgAl3(OH)16 CO3. 4H2O; the acidic material adsorption filler is ethylenediamine-N-propyl silicane; the filter aid is kieselguhr celite 545 filler; the weight ratio of the anion adsorption filler to the acidic material adsorption filler to the filter aid is 2 to 2 to 1. The special extraction filler for the glyphosate and the metabolite-aminomethyl phosphonate of the glyphosate is high in adsorption capacity and column capacity, is capable of effectively eliminating the interference of impurities such as vegetable oil, fat and acidic materials in food, has the recovery rate reaching up to more than 90%, and is good in stability and reproducibility; the defects that aluminium oxide is not stable in activity, and an anion exchange column is low in column capacity in the traditional method can be overcome.
Description
Technical field
The present invention relates to analytical chemistry, food security field, relate to the preparation method and application that simultaneously extract glyphosate and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid (GLY-AMPA post) thereof, be mainly used in (comprising water, animal derived food, plant-derived food etc.) in food in high selectivity separation, enrichment and the purifying of glyphosate and metabolin AminomethylphosphoniAcid Acid thereof.
Background technology
Glyphosate (glyphosate; Gly); chemical name N-((phosphonomethyl)) amion acetic acid; it is the current maximum wide spectrum nonselective herbicide of most widely used, output in the world; AminomethylphosphoniAcid Acid (aminomethylphosphonic acid; AMPA) be the major metabolite of glyphosate, its chemical property is similar to its parent, and its structural formula is in table 1.Glyphosate and major metabolite aminomethyl phosphonic acid thereof have the effect toxicity similar to organic phosphorus compound, mainly cause nervous system function imbalance by suppressing the activity of CHE, the water pollution, vegetation deterioration, the livestock that cause due to glyphosate are poisoning etc., and case increases year by year.For this reason, countries in the world, comprise China and Codex Alimentary Commission (Codex Alimentarius Commission, CAC) all the maximum residue limit to Gly in agricultural product (MRL) have strict limitation regulation.
the information such as structural formula, molecular weight of table 1 glyphosate and metabolin AminomethylphosphoniAcid Acid thereof
Glyphosate and aminomethyl phosphonic acid are strong polarity amphoteric compound, traditional solid phase extraction column taking C18, silica gel, magnesium silicate, the third amino, sulfonate sodium etc. as fixing phase carries out the problems such as adsorption and enrichment purification exists the rate of recovery low, and the penetration volume of sample on filler is little to this compound.Existing examination criteria method (GB/T 23750-2009, NY/T 1096-2006, SN/T 1923-2007) all adopt cation exchange CAX post (filler AG 50W-X8 resin, H+ type) carry out enrichment purification, this ion exchange material taking AG 50W-X8 resin as adsorption stuffing not only expensive, operating process is complicated, be also easy to be subject to the impact of other cationic interference and competitive Adsorption in the aqueous solution and cause the unstable of the rate of recovery.The filler of SPE can show absorption property to a series of same nature compound, and selecting to have extraction stuffing optionally becomes the focus of nearest exploitation solid phase extraction column.Binary magnesium-aluminum hydrotalcite (Layered Double Hydroxides, LDHs) be that typical anionic type laminated material is due to its special layer structure, thereby obtaining having compared with the composite oxides of bigger serface it, roasting under certain condition can reuptake anion in water under certain condition and revert to the hydrotalcite of layer structure, " memory effect " structure of this uniqueness makes hydrotalcite can be used as high-efficiency anion absorbent and applies, at present, hydrotalcite is as the existing many reports of adsorbent of inorganic and organic anion pollutant, as utilize hydrotalcite to adsorb the dyestuff in waste water, utilize hydrotalcite as chemical type sustained release agent of glyphosate etc., but utilize hydrotalcite to there is not yet report as the sorbing material of solid phase extraction column.
Summary of the invention
The object of the present invention is to provide
oneplant glyphosate and the special solid phase extraction column of its metabolin of AminomethylphosphoniAcid Acid and application thereof, utilize hydrotalcite as the sorbing material of solid phase extraction column there is high adsorption capacity, column capacity is high, can effectively remove the impurity such as vegetable oil in food, fat, acidic materials and disturb.
For achieving the above object, the present invention adopts following technical scheme:
oneplant glyphosate and the special solid phase extraction column of its metabolin of AminomethylphosphoniAcid Acid (being called for short: GLY-AMPA post), comprise post shell, sieve plate and filler, described filler is Anion-adsorption filler and acidic materials adsorption stuffing and filter aid composition; Described Anion-adsorption filler is binary magnesium-aluminum hydrotalcite, and a group of molecules accepted way of doing sth is MgAl
3(OH)
16cO
34H
2o; Described acidic materials adsorption stuffing is ethylenediamine-N-propyl group monosilane (PSA); Described filter aid is diatomite celite 545 fillers; The weight ratio of described Anion-adsorption filler, acidic materials adsorption stuffing and filter aid is 2:2:1.
Described binary magnesium-aluminum hydrotalcite (LDHs) preparation method is: by coprecipitation, prepare the stratiform magaldrate (LDHs) taking carbonate as anion, and roasting at 500 DEG C 2 hours, stir and evenly mix rear mistake 120 mesh sieves.
It is crossed post process and comprises the following steps:
(1) activation: add successively 3 mL methyl alcohol in described solid phase extraction column, 3 mL 0.1wt.% formic acid water activation;
(2) extraction: liquid to be clean is added in solid phase extraction column, then use 2 mL 0.1wt.% formic acid water wash sample cells, add in the lump in solid-phase extraction column, efflux discards;
(3) drip washing: after sample solution flows out completely, with the 0.1wt.% formic acid water of 5mL, 5 mL methyl alcohol activated solution drip washing, leacheate discards, and pillar is drained;
(4) desorb: 2.0 mL 0.5 mol/L sodium carbonate liquor desorbs, collect stripping liquid.
The preparation method of glyphosate and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid thereof, comprise the following steps: take respectively in proportion Anion-adsorption filler, acidic materials adsorption stuffing and filter aid, be filled in the pillar that bottom has sieve plate, filler upper end is fixed with sieve plate again.
The application of the special solid phase extraction column of glyphosate and metabolin thereof detection of glyphosate and metabolin AminomethylphosphoniAcid Acid thereof in food.
The invention has the advantages that: choose binary magnesium-aluminum hydrotalcite (LDHs) and there is the advantages such as adsorbance is large, good stability, high specificity as the adsorbent of solid phase extraction column; Ethylenediamine-N-propyl group monosilane (PSA) is containing two amino (pka value is respectively 10.1 and 10.9), there is stronger ion-exchange capacity, can adsorb acidic organic compound, PSA can produce chelation with metal ion simultaneously, for extracting metal ion; Mix above two kinds of adsorption stuffings as the stationary phase fraction of solid phase extraction column to having stronger adsorption capacity containing acidic organic compound, can meet extraction and the enrichment of glyphosate in different food products matrix and metabolin AminomethylphosphoniAcid Acid thereof.
Glyphosate and the special extraction stuffing of metabolin AminomethylphosphoniAcid Acid thereof in the application, there is high adsorption capacity, column capacity is high, can effectively remove the impurity such as vegetable oil in food, fat, acidic materials disturbs, the rate of recovery can reach more than 90%, and stable, reproduction, has overcome the defect that in conventional method, aluminium oxide active is unstable, anion-exchange column column capacity is few; Method is simple, quick, saving solvent.
Brief description of the drawings
The special solid phase extraction column structural representation of Fig. 1 glyphosate and metabolin thereof.
detailed description of the invention
embodiment 1
A kind of glyphosate and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid thereof, be applied to separation, enrichment and the purifying of glyphosate in tealeaves and metabolin AminomethylphosphoniAcid Acid thereof.
sample extraction:
Take approximately 200 g samples, put into pulverizer homogeneous, fully mix.Take sample 1.0 g (being accurate to 0.01g) that homogeneous is good and be placed in 50 mL tool plug polyethylene centrifuge tubes, add 5.00 mL0.1% formic acid water, 1 min that fully vibrates, ultrasonic extraction 30 min, with centrifugal 5 min of 4500r/min speed, get its supernatant; Add again 5.00 mL 0.1% formic acid water extractions to get one time, merge supernatant and be settled to 10.0 mL, to be clean.
the special solid phase extraction column of glyphosate and metabolin AminomethylphosphoniAcid Acid thereof purifies
Get supernatant 2.0 mL and add successively with 3mL methyl alcohol, in the GLY-AMPA dedicated columns after 3 mL 0.1% formic acid water activation, after sample solution flows out completely, with the 0.1% formic acid water of 5mL, 5 mL methanol solution drip washing, leacheate discards, and pillar is drained.Add 2.0 mL 0.5 mol/L sodium carbonate liquor desorbs, collect stripping liquid.
derive and measure
Get upper strata 0.4 mL and treat derivative liquid, add 0.4 mL 30 g/L dobell's solutions, 0.4 mL FMOC-Cl acetone soln, vortex vibration 1min, derivative 2 h under room temperature, in the centrifugal 5min of 4500 r/min speed, supernatant is crossed to 0.45 μ m organic phase filter membrane, and filtrate is detected for LC-MS/MS.
measurement result
Prepared solid phase extraction column has single-minded selective enrichment and purifying to glyphosate in tealeaves and metabolin AminomethylphosphoniAcid Acid thereof, three of tealeaves mark-ons are added to concentration (0.1 mg/kg, 0.2 mg/kg, 1.0 mg/kg), 6 Duplicate Samples of each concentration determination, directly add FMOC-Cl derivating agent to derive after sample purification, select 1,2-C13N15 glyphosate, as Isotopic Internal Standard, carries out LC-MS/MS mensuration.Result shows, glyphosate at 0.1 mg/kg, 0.2 mg/kg, under 1.0 tri-of mg/kg interpolation levels, average recovery rate is respectively: 109.05%, 101.00%, 105.65%, relative standard deviation is respectively: 6.74%, 5.20%, 4.46%.AminomethylphosphoniAcid Acid at 0.1 mg/kg, 0.2 mg/kg, under 1.0 tri-of mg/kg interpolation levels, average recovery rate is respectively: 101.90%, 91.92%, 96.30%, relative standard deviation is respectively: 3.85%, 5.29%, 4.67%.From the selection ion collection of illustrative plates of glyphosate and metabolin AminomethylphosphoniAcid Acid derivative, can find out, GLY-AMPA dedicated columns is compared with cation exchange column CAX good purification, and impurity disturbs few.
embodiment 2
A kind of glyphosate and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid thereof, be applied to separation, enrichment and the purifying of glyphosate in rice and metabolin AminomethylphosphoniAcid Acid thereof.
sample extraction:
Take approximately 200 g samples, put into pulverizer homogeneous, fully mix.Take sample 1.0 g (being accurate to 0.01g) that homogeneous is good and be placed in 50 mL tool plug polyethylene centrifuge tubes, add 5.00 mL0.1% formic acid water, 1 min that fully vibrates, ultrasonic extraction 30 min, with centrifugal 5 min of 4500r/min speed, get its supernatant; Add again 5.00 mL 0.1% formic acid water extractions to get one time, merge supernatant and be settled to 10.0 mL, to be clean.
the special solid phase extraction column of glyphosate and metabolin AminomethylphosphoniAcid Acid thereof purifies
Get supernatant 2.0 mL and add successively with 3mL methyl alcohol, in the GLY-AMPA dedicated columns after 3 mL 0.1% formic acid water activation, after sample solution flows out completely, with the 0.1% formic acid water of 5mL, 5 mL methanol solution drip washing, leacheate discards, and pillar is drained.Add 2.0 mL 0.5 mol/L sodium carbonate liquor desorbs, collect stripping liquid.
derive and measure
Get upper strata 0.4 mL and treat derivative liquid, add 0.4 mL 30 g/L dobell's solutions, 0.4 mL FMOC-Cl acetone soln, vortex vibration 1min, derivative 2 h under room temperature, in the centrifugal 5min of 4500 r/min speed, supernatant is crossed to 0.45 μ m organic phase filter membrane, and filtrate is detected for LC-MS/MS.
measurement result
Prepared solid phase extraction column has single-minded selective enrichment and purifying to glyphosate in rice and metabolin AminomethylphosphoniAcid Acid thereof, three of rice mark-ons are added to concentration (0.1 mg/kg, 0.2 mg/kg, 1.0 mg/kg), 6 Duplicate Samples of each concentration determination, directly add FMOC-Cl derivating agent to derive after sample purification, select 1,2-C13N15 glyphosate, as Isotopic Internal Standard, carries out LC-MS/MS mensuration.Result shows, glyphosate is at 0.1 mg/kg, 0.2 mg/kg, and under 1.0 tri-of mg/kg interpolation levels, average recovery rate is respectively: 110.17%, 101.42%, 96.62%, relative standard deviation is respectively: 3.91%, 7.56%, 7.43%; AminomethylphosphoniAcid Acid is at 0.1 mg/kg, 0.2 mg/kg, and under 1.0 tri-of mg/kg interpolation levels, average recovery rate is respectively: 93.22%, 89.50%, 86.83%, relative standard deviation is respectively: 6.87%, 7.09%, 6.38%.From the selection ion collection of illustrative plates of glyphosate and metabolin AminomethylphosphoniAcid Acid derivative, can find out, GLY-AMPA dedicated columns is compared with cation exchange column CAX good purification, and impurity disturbs few.
embodiment 3
A kind of glyphosate and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid thereof, be applied to separation, enrichment and the purifying of glyphosate in soybean and metabolin AminomethylphosphoniAcid Acid thereof.
sample extraction:
Take approximately 200 g samples, put into pulverizer homogeneous, fully mix.Take sample 1.0 g (being accurate to 0.01g) that homogeneous is good and be placed in 50 mL tool plug polyethylene centrifuge tubes, add 5.00 mL0.1% formic acid water, 1 min that fully vibrates, ultrasonic extraction 30 min, with centrifugal 5 min of 4500r/min speed, get its supernatant; Add again 5.00 mL 0.1% formic acid water extractions to get one time, merge supernatant and be settled to 10.0 mL, to be clean.
the special solid phase extraction column of glyphosate and metabolin AminomethylphosphoniAcid Acid thereof purifies
Get supernatant 2.0 mL and add successively with 3mL methyl alcohol, in the GLY-AMPA dedicated columns after 3 mL 0.1% formic acid water activation, after sample solution flows out completely, with the 0.1% formic acid water of 5mL, 5 mL methanol solution drip washing, leacheate discards, and pillar is drained.Add 2.0 mL 0.5 mol/L sodium carbonate liquor desorbs, collect stripping liquid.
derive and measure
Get upper strata 0.4 mL and treat derivative liquid, add 0.4 mL 30 g/L dobell's solutions, 0.4 mL FMOC-Cl acetone soln, vortex vibration 1min, derivative 2 h under room temperature, in the centrifugal 5min of 4500 r/min speed, supernatant is crossed to 0.45 μ m organic phase filter membrane, and filtrate is detected for LC-MS/MS.
measurement result
Prepared solid phase extraction column has single-minded selective enrichment and purifying to glyphosate in soybean and metabolin AminomethylphosphoniAcid Acid thereof, in soybean, add respectively three and add concentration (0.1 mg/kg, 0.2 mg/kg, 1.0 mg/kg), 6 Duplicate Samples of each concentration determination, directly add FMOC-Cl derivating agent to derive after sample purification, select 1,2-C13N15 glyphosate, as Isotopic Internal Standard, carries out LC-MS/MS mensuration.Result shows, glyphosate is at 0.1 mg/kg, 0.2 mg/kg, and under 1.0 tri-of mg/kg interpolation levels, average recovery rate is respectively: 99.6%, 103.9%, 103.5%, relative standard deviation is respectively: 14.3%, 9.8%, 10.1%; AminomethylphosphoniAcid Acid is at 0.1 mg/kg, 0.2 mg/kg, and under 1.0 tri-of mg/kg interpolation levels, average recovery rate is respectively: 88.0%, 86.6%, 88.4%, relative standard deviation is respectively: 7.6%, 9.8%, 4.9%.And, from the selection ion collection of illustrative plates of glyphosate and metabolin AminomethylphosphoniAcid Acid derivative, can find out, GLY-AMPA dedicated columns cation exchange column CAX good purification, impurity disturbs few.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1.
oneplant glyphosate and the special solid phase extraction column of its metabolin of AminomethylphosphoniAcid Acid, it is characterized in that: comprise shell, sieve plate and filler, described filler is Anion-adsorption filler and acidic materials adsorption stuffing and filter aid composition; Described Anion-adsorption filler is binary magnesium-aluminum hydrotalcite, and a group of molecules accepted way of doing sth is MgAl
3(OH)
16cO
34H
2o; Described acidic materials adsorption stuffing is ethylenediamine-N-propyl group monosilane; Described filter aid is diatomite celite 545 fillers; The weight ratio of described Anion-adsorption filler, acidic materials adsorption stuffing and filter aid is 2:2:1.
2. according to claim 1
oneplant glyphosate and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid thereof, it is characterized in that: described binary magnesium-aluminum hydrotalcite preparation method is: by coprecipitation, prepare the stratiform magaldrate taking carbonate as anion, and roasting at 500 DEG C 2 hours, stir and evenly mix rear mistake 120 mesh sieves.
3. according to claim 1
oneplant glyphosate and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid thereof, it is characterized in that: it is crossed post process and comprises the following steps:
(1) activation: add successively 3 mL methyl alcohol in described solid phase extraction column, 2 mL 0.1wt.% formic acid water activation;
(2) extraction: liquid to be clean is added in solid phase extraction column, then use 2 mL 0.1wt.% formic acid water wash sample cells, add in the lump in solid-phase extraction column, efflux discards;
(3) drip washing: after sample solution flows out completely, with the 0.1wt.% formic acid water of 5mL, 5 mL methyl alcohol activated solution drip washing, leacheate discards, and pillar is drained;
(4) desorb: 2.0 mL 0.5 mol/L sodium carbonate liquor desorbs, collect stripping liquid.
4. the preparation method of a glyphosate as claimed in claim 1 and the special solid phase extraction column of metabolin AminomethylphosphoniAcid Acid thereof, it is characterized in that: comprise the following steps: take respectively in proportion Anion-adsorption filler, acidic materials adsorption stuffing and filter aid, be filled in the pillar that bottom has sieve plate, filler upper end is fixed with sieve plate again.
5. an application for glyphosate as claimed in claim 1 and the special solid phase extraction column of metabolin thereof, is characterized in that: the application of the detection of glyphosate and metabolin AminomethylphosphoniAcid Acid thereof in food.
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Cited By (4)
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| CN106404938A (en) * | 2016-08-28 | 2017-02-15 | 福清出入境检验检疫局综合技术服务中心 | Dispersive solid-phase extraction purification tube for detection of six phenoxy carboxylic acid herbicides in cereals and use method thereof |
| CN107576737A (en) * | 2017-09-05 | 2018-01-12 | 四川农业大学 | A kind of method based on fish scale collagen tunica fibrosa detection glyphosate |
| CN111487330A (en) * | 2019-01-29 | 2020-08-04 | 上海安谱实验科技股份有限公司 | Detection method for glyphosate and metabolites thereof in various matrixes |
| CN114910594A (en) * | 2022-05-31 | 2022-08-16 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for rapidly measuring glyphosate by synchronously extracting and deriving |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106404938A (en) * | 2016-08-28 | 2017-02-15 | 福清出入境检验检疫局综合技术服务中心 | Dispersive solid-phase extraction purification tube for detection of six phenoxy carboxylic acid herbicides in cereals and use method thereof |
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| CN107576737A (en) * | 2017-09-05 | 2018-01-12 | 四川农业大学 | A kind of method based on fish scale collagen tunica fibrosa detection glyphosate |
| CN111487330A (en) * | 2019-01-29 | 2020-08-04 | 上海安谱实验科技股份有限公司 | Detection method for glyphosate and metabolites thereof in various matrixes |
| CN114910594A (en) * | 2022-05-31 | 2022-08-16 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for rapidly measuring glyphosate by synchronously extracting and deriving |
| CN114910594B (en) * | 2022-05-31 | 2024-05-14 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for rapidly determining glyphosate by synchronously extracting and deriving |
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