CN105758947A - Method for simultaneously determining glufosinate-ammonium in food and metabolin residual quantity thereof - Google Patents
Method for simultaneously determining glufosinate-ammonium in food and metabolin residual quantity thereof Download PDFInfo
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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
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Abstract
The invention provides a method for simultaneously determining glufosinate-ammonium in food and metabolin residual quantity thereof, which relates to the field of pesticide residue detection. The determining method adopts a high performance liquid chromatography-mass spectrometry/mass spectrometry method to detect, and comprises the following steps of firstly, extracting glufosinate-ammonium in a sample and metabolin thereof through water; purifying with dichloromethane and a C18 solid phase extraction column; then adopting a hydrophilic interaction NH2 chromatographic column, using the liquid chromatography-mass spectrometry/mass spectrometry method, ionizing an electrospray ionization (ESI) source with a negative ion mode, detecting with a multiple reaction monitoring (MRM) mode, and using a substrate external standard method to quantitatively determine the glufosinate-ammonium and the metabolin thereof N-acetyl glufosinate-ammonium (NAG) and 3-(methyl phosphino) propionic acid (MPP). The method provided by the invention is simple, convenient and quick, high in sensitivity and strong in practicability, and has the substantive meaning in import and export food detection and domestic food safety control.
Description
Technical field
The present invention relates to the determination techniques field of persticide residue, relate more specifically to one and measure food medium-height grass ammonium simultaneously
Phosphine and the method for metabolite residue amount thereof.
Background technology
Glufosinate-ammonium (glufosinate-ammonium is called for short GLU) is Germany Hirst company (Hearst
Corporation) in the novel steriland herbicide of the exploitation eighties in last century,
Its active ingredient is phosphinothricin (being called for short PPT), and chemical name is (RS)-2-amino-(hydroxymethyl
Phosphinyl) butyric acid ammonium, molecular formula is C5H12NO4P, molecular weight 181.1.Former medicine is that white is to Light yellow crystals powder, density
1.4g/mL (20 DEG C), fusing point 215 DEG C, boiling point 99.5 DEG C, vapour pressure < 0.1mPa (25 DEG C), highly stable, 2 can be stored for 25 DEG C
Year；When 25 DEG C, its solubility in water is 1370g/L, and when 20 DEG C, the solubility in several conventional organic solvent is respectively as follows:
Acetone 0.016g/100mL, ethanol 0.065g/100mL, ethyl acetate 0.014g/100mL, n-hexane 0.02g/100mL, toluene
0.014g/100mL.Stable to light, hydrolyze at pH 5～9, DT50 < 10d in soil.
It is currently known glufosinate-ammonium major metabolite in plant and has N-acetyl group glufosinate-ammonium (being called for short NAG) and 3-(methyl
Phosphino-) propionic acid (being called for short MPP)
Glufosinate-ammonium is the second-biggest-in-the-world genetically modified crops herbicide-tolerant that current consumption is only second to glyphosate, belongs to phosphoric acid
Class herbicide, is paddy ammonia synthesis inhibitor, and after dispenser, in short time implants body, disorder, cytotoxic agent ammonium ion are sunk in ammonium metabolism
Accumulating in plant, meanwhile, photosynthesis is seriously suppressed, and reaches weeding purpose.It has inner sucting conduction type, wide spectrum
The features such as non-selective, contact killing type, the property killed.It is miscellaneous that glufosinate-ammonium is mainly used in preventing and kill off annual and perennial dicotyledonous grass family
Grass, uses weeds cauline leaf directed spraying to process, is applied to tealeaves, orchard, vineyard, citrus orchard, coffee garden, vegetables, potato
Field, bare place etc..
Glufosinate-ammonium belongs to perishability agricultural chemicals, but it uses in a large number and arbitrarily, it is possible to remain on crops, from
And people, animal are constituted a threat to.According to FAO (Food and Agriculture Organization of the United Nation)s in 1999 and World Health Organization's residues of pesticides joint specialist meeting
(JMPR) report, the major metabolite of glufosinate-ammonium has N-acetyl group glufosinate-ammonium (being called for short NAG) and 3-(methyl phosphino-) propionic acid (to be called for short
MPP), it is toxic metabolite, there is certain risk.
At present, various countries (regional) is different to the limit standard of glufosinate-ammonium in food (GLU) with associated mechanisms: international food method
The allusion quotation committee (CAC) has formulated 40 residue limits standards of glufosinate-ammonium, and limitation scope is between 0.05～8mg/kg；U.S.'s grass ammonium
Phosphine totally 33 residue limits standards, limitation scope is between 0.05～6mg/kg；European Union's glufosinate-ammonium totally 378 residue limits marks
Standard, limitation scope is between 0.1～5mg/kg；Japan's glufosinate-ammonium totally 169 residue limits standards, limitation scope 0.05～
Between 6mg/kg；Korea S's glufosinate-ammonium totally 26 residue limits standards, limitation scope is between 0.05～0.5mg/kg；Australia
Glufosinate-ammonium totally 37 residue limits standards, limitation scope is between 0.05～20mg/kg；Singapore's glufosinate-ammonium totally 30 residual limits
Amount standard, limitation scope is between 0.1～0.5mg/kg；China has formulated 5 residue limits standards of glufosinate-ammonium, tomato, oranges and tangerines,
In tealeaves, the MRL of glufosinate-ammonium is 0.5mg/kg, and in banana, pawpaw, the maximum residue limit of glufosinate-ammonium is 0.2mg/kg.
TaiWan, China has 14 residue limits standards, and limitation scope is between 0.05～2mg/kg；There are 18 residue limits Hong-Kong
Standard, limitation scope is between 0.05～5mg/kg.Wherein in TaiWan, China, Hong-Kong, CAC, the U.S., EU criteria clearly
Regulation residue is defined as glufosinate-ammonium, N-acetyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid sum, with glufosinate-ammonium (free acid)
Represent；Korea S's regulation residue is defined as glufosinate-ammonium and 3-(methyl phosphino-) propionic acid sum, represents with glufosinate-ammonium (free acid)；In
State, Japan, Australia, Singapore the most do not indicate whether limitation comprises metabolin.
But various countries there is no concrete examination criteria at present, for reaching regulation requirement of limiting the quantity in trade, to Product checking it is
Requisite.Hence set up the method for detecting residue of glufosinate-ammonium and metabolin thereof, to China's foreign trade, food security etc.
Aspect has important meaning.
In presently disclosed prior art, there is the analysis method of multiple detection glufosinate-ammonium and metabolin thereof.
Jiang Yan, Cao Zhaoyun, Jia Ruilin, Qi Hui, Chen Mingxue, hydrophilic Interaction Chromatography one is connected the grass in mass spectrometric determination rice
Sweet phosphine and aminomethyl phosphonic acid residual quantity, " chromatogram ", 2012,30 (1) 39-44, disclose a kind of hydrophilic Interaction Chromatography-tandem mass spectrum
Method measures the glyphosate in rice and aminomethyl phosphonic acid residual quantity.Use hydrophilic Interaction Chromatography 5 tandem mass spectrum to establish to survey simultaneously
Determine rice glyphosate and the detection method of major metabolite aminomethyl phosphonic acid residual quantity thereof.Sample extracts through water, and C18 solid phase extracts
Take post and milipore filter purifies, with 1mmol/L ammonium acetate solution (adjusting pH=11.0 with ammoniacal liquor)-acetonitrile for flowing phase, hydrophilic interaction
Chromatographic column separates, and uses electric spray ion source, anion scan pattern and multiple-reaction monitoring pattern Mass Spectrometer Method, matrix matching mark
Quasi-solution quantified by external standard method.Glyphosate and aminomethyl phosphonic acid are respectively 0.001～0.250mg/L and 0.0025～0.250mg/L
In the range of mass concentration, linear relationship is good, and detection limit (signal to noise ratio is 3) is respectively 0.010mg/kg and 0.020mg/kg.Pass through
Blank rice sample is carried out the recovery test of 0.100,0.500 and 2.500mg/kg 3 mark-on levels, glyphosate and ammonia first
The average recovery rate of base phosphoric acid and relative standard deviation are respectively 96.3%～107.3% and 1.3%～9.1% (n=3).Should
When method detects glufosinate-ammonium and metabolin thereof simultaneously, the separating degree of glufosinate-ammonium and metabolin thereof is very poor.
Liu Zhengzheng, Li Li, Wang Jing, Pan Hefang, high performance liquid chromatography-pre-column derivatization measures organophosphorus herbicide in water,
" development fields of environmental monitoring in china ", 2009,25 (5) 35-38, spread out before it discloses a kind of employing chloro-carbonic acid-9-fluorenyl methyl ester (FMOC) post
After biochemistry, then measure trace glyphosate, glufosinate-ammonium and amino first in water sample by high performance liquid chromatography fluorimetric analysis method
The method of phosphoric acid.The method first adds the dobell's solution of 0.5mL 0.05M in water sample, is subsequently adding 0.5mL 1.0mg/
The FMOC solution of mL, after derivative 2h, adds 5mL ethyl acetate extraction and prepares sample, then with Waters performance liquid chromatographic column
(Atlantis C18 post 5 μm, 4.6 × 250), flowing is that the mixed liquor 80:20 of 0.02M phosphoric acid solution-acetonitrile (presses body mutually
Long-pending ratio), under conditions of column temperature 40 DEG C and flow velocity 1.0mL/min, detect sample with fluorescence detector.It is the most right that the method needs
Sample performs the derivatization, complex operation, and sensitivity is relatively low.
Naoki Yoshioka,Migiwa Asano,Azumi Kuse,Takao Mitsuhashi,Yasushi
Nagasaki,Yasuhiro Ueno,Rapid determination of glyphosate,glufosinate,
bialaphos,and their major metabolites in serum by liquid chromatography–
tandem mass spectrometry using hydrophilic interaction chromatography,Journal
Of Chromatography A, 2011 (1218) 3,675 3680. disclose one hydrophilic Interaction Chromatography (HILIC chromatogram
Post) liquid phase tandem mass spectrometry direct method quickly determines the glyphosate in serum, glufosinate-ammonium, bialaphos and metabolin ammonia first
Base phosphonic acids, the method for 3-(methyl phosphino-) propionic acid.Described method sample is not through derivatization and SPE, and glufosinate-ammonium detects
Limit is 0.03 μ g/mL.But, HILIC hydrophilic chromatographic post is a kind of can reservation and the chromatogram of separating polar-ionic compound
Post, can only solve the reservation of polarity-ionic compound, the pole such as glufosinate-ammonium, glyphosate under the precondition that organic phase is relatively low
Property material retain the most weak, appearance time early (< 1min), peak type is poor, and peak conditions of streaking is obvious.Therefore use HILIC to measure simultaneously
Glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium (being called for short NAG) and 3-(methyl phosphino-) propionic acid (being called for short MPP) thereof exist certain tired
Difficult.
Summary of the invention
Summary of the invention
The present invention provides a kind of simple and efficient relative to prior art, highly sensitive, it is possible to simultaneously in Accurate Determining food
Glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof (being called for short NAG) and the method for 3-(methyl phosphino-) propionic acid (abbreviation MPP).
Method of the present invention is first to extract the glufosinate-ammonium in sample and metabolin water thereof, through dichloromethane and
C18 solid phase extraction column purifies, and then uses hydrophilic interaction NH2Chromatographic column, by liquid chromatography-mass spectrography/mass spectrography, electron spray from
Component (ESI) negative ion mode ionize, multiple-reaction monitoring (MRM) mode detection, matrix quantified by external standard method measure glufosinate-ammonium and
Metabolite N-acetyl base glufosinate-ammonium (being called for short NAG) and 3-(methyl phosphino-) propionic acid (being called for short MPP).The method disclosure satisfy that both at home and abroad
The testing requirement of limitation, practical, it is possible to accurately to measure glufosinate-ammonium and major metabolite N-thereof of residual in import and export food
Acetyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid, the quality control to food security has essential meaning.
Term defines
" external standard method " of the present invention refers to second annex V D efficient liquid-phase chromatography method of 2010 editions Chinese Pharmacopoeias
The external standard method of indication in (annex page 31).
" negative sample " of the present invention refers to that not containing components Sample to be measured (does not such as contain glufosinate-ammonium and metabolin thereof
The food samples such as N-acetyl group glufosinate-ammonium and 3-(methyl phosphino-) Tea Industry of propionic acid, paddy).
" % " of the present invention unless otherwise indicated refers both to mass percent.
Detailed Description Of The Invention
The present invention provides one to measure in food glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and 3-(methylphosphine simultaneously
Base) method of propionic acid, described method is with hydrophilic interaction NH2Chromatographic column is analytical column, and ammonium acetate solution-acetonitrile is pressed mutually for flowing
Gradient program wash-out testing sample solution or matrix hybrid standard calibration solution, with mass spectrum/mass detector with multiple-reaction monitoring
(MRM) mode detection, then according to external standard method calculates remains glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and 3-in food
The content of (methyl phosphino-) propionic acid,
Wherein said gradient elution program is
| Gradient timetable, min | Flowing phase %, volume ratio | Acetonitrile %, volume ratio |
| 0 | 25 | 75 |
| 2 | 25 | 75 |
| 2.01 | 80 | 20 |
| 6 | 80 | 20 |
| 6.01 | 25 | 75 |
| 10 | 25 | 75 |
Wherein said testing sample solution preparation method: the glufosinate-ammonium in sample and metabolin water thereof are extracted, then
Purify through dichloromethane and C18 solid phase extraction column and obtain；
The preparation method of wherein said matrix hybrid standard calibration solution: weigh negative sample, add glufosinate-ammonium, N-second
Acyl group glufosinate-ammonium and the mixed standard solution of 3-(methyl phosphino-) propionic acid, then extract with water, then through dichloromethane and C18 solid phase
Extract little column purification to obtain.
The one that the present invention provides measures in food glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and 3-(methyl simultaneously
Phosphino-) method of propionic acid, use matrix to add hybrid standard calibration curve and carry out accurate quantitative analysis, i.e. add in standard liquid solution
Sample substrate, described method can effectively overcome ability mass spectrum/mass spectrum to measure glufosinate-ammonium and metabolin N-thereof in food simultaneously
The problem of matrix interference when acetyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid, is entered by preparation matrix hybrid standard calibration solution
Row is quantitatively, it is possible to measure glufosinate-ammonium and metabolin thereof exactly.
Extract the determinand of sample with water after, adding dichloromethane solution, vortex oscillation, high speed centrifugation takes supernatant, energy
The problem enough improving sample blocking pillar, the beneficially maintenance of instrument and being smoothed out of detection.
In certain embodiments, the method for the invention flow rate of mobile phase can be 0.1～0.5mL/min, real at some
Executing in example can be 0.25mL/min.
In certain embodiments, the hydrophilic interaction NH of the method for the invention2Chromatographic column is NH2P-50 2D post, 150mm ×
2.0mm, 5 μm.Column temperature in described chromatographic column running can be 20 DEG C～40 DEG C, can be 35 in certain embodiments
℃。
In certain embodiments, the ammonium acetate solution of the method for the invention is to use ammonium acetate to be dissolved in water, then
Obtain by ammoniacal liquor regulation pH value.The concentration of ammonium acetate solution can be 0.5～2mmol/L, and its pH value can be 9～11.
In certain embodiments, the concentration of the ammonium acetate solution of the method for the invention is 1mmol/L, and adjusts with ammoniacal liquor
Joint pH value is to 11.
In certain embodiments, the ion gun of the mass detector of the method for the invention is electric spray ion source (ESI),
And use negative ion mode ionized sample.
In certain embodiments, the mass detector of the method for the invention uses electric spray ion source (ESI), with bear from
Subpattern scans, and uses multiple-reaction monitoring (MRM) detection, detects parameter and is: dry temperature: 300 DEG C；Dry gas stream speed:
10L/min；Atomization gas pressure: 45psi；Electron spray voltage :-4500V；Sheath gas temperature: 350 DEG C；Sheath gas flow velocity: 7L/
min；Spray nozzle voltage :-1000V.
In certain embodiments, the one that the present invention provides measures glufosinate-ammonium and metabolite N-acetyl base thereof in food simultaneously
Glufosinate-ammonium and the method for 3-(methyl phosphino-) propionic acid, use High Performance Liquid Chromatography/Mass Spectrometry/mass spectrography, treats by Gradient program wash-out
Survey sample solution or matrix hybrid standard calibration solution, with mass spectrum/mass detector with multiple-reaction monitoring (MRM) mode detection,
Then according to external standard method calculates remains glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and 3-(methyl phosphino-) propionic acid in food
Content, its chromatographic test strip part is:
Chromatographic column: NH2P-50 2D post, 150mm × 2.0mm, 5 μm；
Buffer solution: with the 1mmol/L ammonium acetate solution that ammoniacal liquor regulation pH is 11；
Organic phase: acetonitrile；
Column temperature: 35 DEG C；
Flow velocity: 0.25mL/min；
Sampling volume: 5 μ L；
Gradient program
| Gradient timetable, min | Flowing phase %, volume ratio | Acetonitrile %, volume ratio |
| 0 | 25 | 75 |
| 2 | 25 | 75 |
| 2.01 | 80 | 20 |
| 6 | 80 | 20 |
| 6.01 | 25 | 75 |
| 10 | 25 | 75 |
Mass Spectrometer Method condition is to use electric spray ion source (ESI), scans with negative ion mode, uses multiple-reaction monitoring
(MRM) detection, detection parameter is: dry temperature: 300 DEG C；Dry gas stream speed: 10L/min；Atomization gas pressure: 45psi；Electricity
Spray voltage :-4500V；Sheath gas temperature: 350 DEG C；Sheath gas flow velocity: 7L/min；Spray nozzle voltage :-1000V；
Wherein said testing sample solution preparation method: the glufosinate-ammonium in sample and metabolin water thereof are extracted, then
Purify through dichloromethane and C18 solid phase extraction column and obtain；
The preparation method of wherein said matrix hybrid standard calibration solution: weigh negative sample, add glufosinate-ammonium, N-second
Acyl group glufosinate-ammonium and the mixed standard solution of 3-(methyl phosphino-) propionic acid, then extract with water, then through dichloromethane and C18 solid phase
Extract little column purification to obtain.
In certain embodiments, the preparation method of testing sample solution: weigh the good sample tealeaves 1g of homogeneous or vegetable oil,
Cereal or fruit and vegetable 5g, be accurate to 0.01g, is placed in 50mL tool plug polypropylene centrifuge tube, adds 10mL water, 10mL dichloromethane
Alkane, abundant vortex oscillation 10min, ultrasonic extraction 10min, it is centrifuged 5min with 12000r/min speed, collects supernatant；Take extraction
In the C18 solid-phase extraction column that liquid 5mL has added the most activated, filter discards front 3mL efflux, 2mL efflux after collection, crosses 0.22
μm aqueous phase filter membrane obtains.
In certain embodiments, the preparation method of matrix hybrid standard calibration solution: weigh the negative sample tea that homogeneous is good
Leaf 1g or vegetable oil, cereal or fruit and vegetable 5g, be accurate to 0.01g, is respectively placed in 50mL tool plug polypropylene centrifuge tube, adds
Appropriate ammonium phosphine, N-acetyl group glufosinate-ammonium and the mixed standard solution of 3-(methyl phosphino-) propionic acid, make glufosinate-ammonium, N-acetyl group grass
Ammonium phosphine, the extraction standard solution of 3-(methyl phosphino-) propionic acid, be subsequently adding 10mL water, 10mL dichloromethane, abundant vortex oscillation
10min, ultrasonic extraction 10min, be centrifuged 5min with 12000r/min speed, collects supernatant；Take extract 5mL addition to have lived
In the C18 solid-phase extraction column changed, filter discards front 3mL efflux, 2mL efflux after collection, crosses 0.22 μm aqueous phase filter membrane and obtains.
Glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and 3-(methylphosphine is measured in food while of the present invention
Base) method of propionic acid, wherein in mass spectrum/Mass Spectrometer Method collection of illustrative plates, the qualitative ion pair of glufosinate-ammonium is 180/95 and/or 180/
85, quota ion is to being 180/95；The qualitative ion pair of N-acetyl group glufosinate-ammonium is 222/136 and/or 222/59, quota ion
To being 222/136；The qualitative ion pair of 3-(methyl phosphino-) propionic acid is 151/133 and/or 151/107, and quota ion is to being
151/133。
Accompanying drawing explanation
Fig. 1 shows the total ion current figure of NAG, GLU and MPP standard items of embodiment 1 Plays product solution；
Fig. 2 shows the total ion current figure of NAG, GLU and MPP standard items of embodiment 2 Plays product solution；
Fig. 3 shows the selection ion flow graph spectrum of NAG, GLU and MPP standard items of embodiment 3 Plays product solution；
Fig. 4 shows the secondary fragment ion figure of the GLU of embodiment 3 Plays product solution；
Fig. 5 shows the secondary fragment ion figure of the NAG of embodiment 3 Plays product solution；
Fig. 6 shows the secondary fragment ion figure of the MPP of embodiment 3 Plays product solution；
Fig. 7 shows that in embodiment 4, MRM is schemed by tealeaves bare substrate NAG, GLU and MPP quota ion；
Fig. 8 shows that in embodiment 4, MRM is schemed by tealeaves bare substrate mark-on 0.1mg/kg NAG, GLU and MPP quota ion；
Fig. 9 shows that in embodiment 4, MRM is schemed by paddy bare substrate NAG, GLU and MPP quota ion；
Figure 10 shows that in embodiment 4, MRM is schemed by paddy bare substrate mark-on 0.05mg/kg NAG, GLU and MPP quota ion；
Figure 11 shows that in embodiment 4, MRM is schemed by apple bare substrate NAG, GLU and MPP quota ion；
Figure 12 shows that in embodiment 4, MRM is schemed by apple bare substrate mark-on 0.05mg/kg NAG, GLU and MPP quota ion；
Figure 13 shows the working curve of the corresponding peak area of GLU concentration in embodiment 5 Plays working solution；
Figure 14 shows the working curve of the corresponding peak area of NAG concentration in embodiment 5 Plays working solution；
Figure 15 shows the working curve of the corresponding peak area of MPP concentration in embodiment 5 Plays working solution.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that technical scheme, disclose some further below non-
The present invention is described in further detail to limit embodiment.
Reagent used in the present invention all can be buied from the market or can be by method system described in the invention
Standby and obtain.Unless otherwise indicated, reagent of the present invention is all analytically pure reagent.
Acetonitrile: chromatographically pure；Anhydrous acetic acid ammonium: chromatographically pure；Ammoniacal liquor: 25%, chromatographically pure；Dichloromethane, chromatographically pure.
Glufosinate-ammonium standard substance (Glufosinate ammonium, GLU, No. CAS: 77182-82-2, molecular formula:
C5H15N2O4P): purity >=97.5%.
N-acetyl group glufosinate-ammonium standard substance (N-Acetyl-glufosinate, NAG, No. CAS: 73634-73-8, molecule
Formula: C7H14NO5P): purity >=98.5%.
3-(methyl phosphino-) propionic acid standard substance (3-methylphosphinicopropionic acid, MPP, No. CAS:
15090-23-0, molecular formula: C4H9O4P): purity >=98.0%.
Embodiment 1 comparative example
Standard solution: accurately weigh the glufosinate-ammonium of 50mg, N-acetyl group glufosinate-ammonium (NAG) and 3-(methyl phosphino-) propionic acid
(MPP) standard items, dissolve with water and are settled to 50mL, obtain the Standard Stock solutions of 1.0mg/mL, deposit in polyethylene or poly-
In Acrylic plastic bottle.Less than 5 DEG C of preservations.Take a certain amount of glufosinate-ammonium Standard Stock solutions, be diluted with water to the mark of 1.0 μ g/mL
Quasi-solution, deposits in polyethylene or Polypropylene bottle.Less than 5 DEG C of preservations.
According to prior art Jiang Yan, Cao Zhaoyun, Jia Ruilin, Qi Hui, Chen Mingxue, hydrophilic Interaction Chromatography one tandem mass spectrometry is surveyed
Determine the glyphosate in rice and aminomethyl phosphonic acid residual quantity, " chromatogram ", 2012,30 (1) 39-44, a kind of hydrophilic Interaction Chromatography-string
Glyphosate in connection mass spectrometric determination rice and the chromatographic test strip part disclosed in aminomethyl phosphonic acid residual quantity, to standard solution
Detect, record total ion current figure.
Glufosinate-ammonium, total ion current figure such as Fig. 1 institute of N-acetyl group glufosinate-ammonium (NAG) and 3-(methyl phosphino-) propionic acid (MPP)
Showing, all substances 1.5～2.3min go out peak, retain more weak on a column, and the ion being subject to when detection actual sample suppresses
Effect is very big, and the rate of recovery of sample is the lowest.
Embodiment 2
Standard solution: method preparation standard solution as described in Example 1.
According to method of the present invention, standard solution is detected, record glyphosate, AminomethylphosphoniAcid Acid, glufosinate-ammonium
And the total ion current figure of metabolin, such as Fig. 2.Analysis testing conditions is as follows:
Liquid chromatography-mass spectrography testing conditions:
Chromatographic column: NH2P-50 2D post, 150mm × 2.0mm, 5 μm；
Buffer solution: 1mmol/L ammonium acetate solution (pH=11): the anhydrous acetic acid ammonium weighing 0.07708g is dissolved in right amount
In water, regulate pH=11 with ammoniacal liquor, be settled to 1000mL with water；
Organic phase: acetonitrile；
Column temperature: 35 DEG C；
Flow velocity: 0.25mL/min；
Sampling volume: 5 μ L；
Gradient program
| Gradient timetable, min | Flowing phase %, volume ratio | Acetonitrile %, volume ratio |
| 0 | 25 | 75 |
| 2 | 25 | 75 |
| 2.01 | 80 | 20 |
| 6 | 80 | 20 |
| 6.01 | 25 | 75 |
| 10 | 25 | 75 |
Mass Spectrometer Method condition is to use electric spray ion source (ESI), scans with negative ion mode, uses multiple-reaction monitoring
(MRM) detection, detection parameter is: dry temperature: 300 DEG C；Dry gas stream speed: 10L/min；Atomization gas pressure: 45psi；Electricity
Spray voltage :-4500V；Sheath gas temperature: 350 DEG C；Sheath gas flow velocity: 7L/min；Spray nozzle voltage :-1000V.
According to the method described in the present invention standard solution is detected, glufosinate-ammonium, N-acetyl group glufosinate-ammonium and 3-(methylphosphine
Base) the peak type of propionic acid total ion current figure is sharp-pointed, and response is high so that component to be measured obtains optimal sensitivity.Glufosinate-ammonium, N-second
Acyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid went out peak at about 6 minutes, separated with the interfering material in actual sample, be subject to from
Sub-depression effect is less.
Embodiment 3 system suitability is tested
Standard solution: method preparation standard solution as described in Example 1.
By the analysis testing conditions shown in embodiment 2, standard solution is detected, divide in the way of flow injection
The other standard liquid to three kinds of materials carries out full scan and daughter ion scanning, obtains fragment ion information (such as Fig. 4～Fig. 6), really
Determining parent ion, daughter ion, every kind of material determines two feature daughter ions, wherein abundance higher for quota ion, abundance is relatively low
For qualitative ion, design parameter is shown in Table 1.NAG, GLU and MPP of record standard product solution selects ion flow graph simultaneously, such as Fig. 3
Shown in.
Table 1 glufosinate-ammonium and the qualitative ion pair of metabolin, quota ion are to fragmentation voltage, collision gas energy in, source
Embodiment 4 sensitivity experiment
At random, have chosen tealeaves, paddy, 3 negative samples of apple respectively, make matrix respectively blank, and to adding
Mark experiment, finally observes qualitative, the MRM figure of quota ion of glufosinate-ammonium, N-acetyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid.
Tealeaves matrix blank solution: weigh the negative sample tealeaves 1g that homogeneous is good, be accurate to 0.01g, be respectively placed in 50mL
In tool plug polypropylene centrifuge tube, it is subsequently adding 10mL water, 10mL dichloromethane, abundant vortex oscillation 10min, ultrasonic extraction
10min, is centrifuged 5min with 12000r/min speed, collects supernatant；Take the C18 solid phase that extract 5mL has added the most activated
In extraction column, filter discards front 3mL efflux, 2mL efflux after collection, crosses 0.22 μm aqueous phase filter membrane and obtains.
Tealeaves matrix blank mark-on solution: weigh the negative sample tealeaves 1g that homogeneous is good, be accurate to 0.01g, be respectively placed in
In 50mL tool plug polypropylene centrifuge tube, add appropriate ammonium phosphine, N-acetyl group glufosinate-ammonium and the mixing mark of 3-(methyl phosphino-) propionic acid
Quasi-solution, makes glufosinate-ammonium, N-acetyl group glufosinate-ammonium, 3-(methyl phosphino-) propionic acid content are the matrix blank of 0.1mg/kg and add
Mark solution, is subsequently adding 10mL water, 10mL dichloromethane, abundant vortex oscillation 10min, and ultrasonic extraction 10min, with 12000r/
Min speed is centrifuged 5min, collects supernatant；Taking in the C18 solid-phase extraction column that extract 5mL has added the most activated, filter discards
Front 3mL efflux, 2mL efflux after collection, cross 0.22 μm aqueous phase filter membrane and obtain.
With reference to above tealeaves blank matrices and mark-on solution manufacturing method thereof, prepare paddy respectively and (claim respectively with apple
Take 5g) prepare corresponding matrix blank solution and corresponding matrix blank mark-on solution (glufosinate-ammonium, N-acetyl group glufosinate-ammonium and 3-
(methyl phosphino-) propionic acid content is 0.05mg/kg).
Testing sample solution and matrix hybrid standard are calibrated solution carry out by the analysis testing conditions shown in embodiment 2
Detection, sample introduction High Performance Liquid Chromatography/Mass Spectrometry/mass spectrometer system, record chromatogram, as shown in fig.7-12.
It can be seen that the interference of chromatographic peak equal free from admixture, explanation in the MRM figure of qualitative ion pair, quota ion pair
The method specific preferably.The detection limit (LOD) of method is defined as producing the quality of the compound of 3 times of signal to noise ratios (S/N=3)
Concentration, measures lower bound i.e. quantitative limit (LOQ) and is defined as producing the mass concentration of the compound of 10 times of signal to noise ratios (S/N=10).Press
Calculate according to signal to noise ratio S/N >=10, through representational detection, the glufosinate-ammonium of this method and metabolite N-acetyl base glufosinate-ammonium thereof,
The mensuration lower bound Tea Samples of 3-(methyl phosphino-) propionic acid be 0.1mg/kg, fruits and vegetables and cereal be 0.05mg/kg, at other food
In sensitivity technique result, same display has the highest sensitivity.This detection method detection limit can reach various countries (regional) rule
The minimum residual limit of fixed glufosinate-ammonium, the limits that various countries (regional) specifies as described in background technology, about 0.05mg/kg
～20mg/kg.
Embodiment 5 Linear Experiment
Standard working solution: accurately weigh glufosinate-ammonium and N-acetyl group glufosinate-ammonium (NAG), the 3-(methyl phosphino-) third of 50mg
Acid (MPP) standard items, dissolve with water and be settled to 50mL, obtaining the Standard Stock solutions of 1.0mg/mL, deposit in polyethylene or
In Polypropylene bottle.Less than 5 DEG C of preservations.Take a certain amount of glufosinate-ammonium Standard Stock solutions, be diluted with water to 1.0 μ g/mL's
Standard intermediate solution, deposits in polyethylene or Polypropylene bottle.Less than 5 DEG C of preservations.Pipette 1.0 μ of different volumes respectively
The standard intermediate solution of g/mL is in 10mL volumetric flask, with secondary water constant volume, compound concentration is 10,20,50,100,200,500,
The standard working solution of 1000ng/mL.
Take series of standards working solution (10,20,50,100,200,500,1000ng/mL), shown in embodiment 2
Detection method standard working solution is detected, record the peak area of each measured portions ion pair to be measured.With peak area (Y
Axle) concentration (X-axis) of corresponding determinand to be mapped, result shows, test compounds substrate concentration presents good with corresponding peak area
Good linear relationship, as shown in Figure 13～15.
Matrix hybrid standard calibration solution: with reference to the compound method of embodiment 4 mesostroma hybrid standard calibration solution, respectively
Blank negative sample tealeaves, paddy, oranges and tangerines, pawpaw, banana, tomato are carried out pre-treatment, obtain the matrix extract of blank,
With this extract prepare respectively glufosinate-ammonium, N-acetyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid curve (tealeaves 0,10,20,
50,100,200ng/mL, other samples 0,20,50,100,200,6 standard series of 500ng/mL), by the detection of embodiment 2
Method carries out mass spectroscopy.With the response peak area (Y-axis) of quota ion, corresponding mass concentration (X-axis, ng/mL) is mapped,
Obtain linear equation, be shown in Table 2.
Glufosinate-ammonium, N-acetyl group glufosinate-ammonium, the linear relationship of 3-(methyl phosphino-) propionic acid in the different sample substrate of table 2
Result shows, glufosinate-ammonium, N-acetyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid in the range of being joined, quota ion
Response peak area and sample concentration between have good linear relationship.
Embodiment 6 recovery test
Standard solution: accurately weigh the glufosinate-ammonium of 50mg, N-acetyl group glufosinate-ammonium (NAG) and 3-(methyl phosphino-) propionic acid
(MPP) standard items, dissolve with water and are settled to 50mL, obtain the Standard Stock solutions of 1.0mg/mL, deposit in polyethylene or poly-
In Acrylic plastic bottle.Less than 5 DEG C of preservations.Take a certain amount of glufosinate-ammonium Standard Stock solutions, be diluted with water to the mark of 1.0 μ g/mL
Quasi-solution, deposits in polyethylene or Polypropylene bottle.Less than 5 DEG C of preservations.
Matrix hybrid standard calibration solution: with reference to the compound method of embodiment 4 mesostroma hybrid standard calibration solution, respectively
To blank negative sample tealeaves, paddy, corn and soybean, oranges and tangerines, apple, peach, grape, banana, pawpaw, carrot, onion, Ma Ling
Potato, tomato, American pistachios, rapeseed oil etc. carry out pre-treatment, obtain the matrix extract of blank, the most respectively to each matrix extract
Adding standard solution, dilution is configured to Glufosinate-ammoniumpesticideng, N-acetyl group glufosinate-ammonium (NAG) and 3-(methyl phosphino-) propionic acid respectively
(MPP) all kinds of sample substrate hybrid standards calibration solution of 200ng/mL it is.
Mark-on solution: with the tealeaves remained without NAG, GLU and MPP, paddy, corn and soybean, oranges and tangerines, apple, peach, Portugal
Grape, banana, pawpaw, carrot, onion, potato, tomato, American pistachios, rapeseed oil are blank sample matrix, add three concentration
(mark-on level is shown in Table 2) horizontal arrangement mark-on solution.The collocation method of mark-on solution is with reference to embodiment 4 mesostroma hybrid standard school
Quasi-solution compound method configures.Each concentration level carries out six times repeating experiment.
With reference to the detection method in embodiment 2, mark-on solution is detected and matrix hybrid standard calibration solution, record
The peak area of each measured portions ion pair to be measured, is calculated the rate of recovery of NAG, GLU and MPP of each mark-on solution by external standard method, with
Time calculate the precision of each sample.The results are shown in Table 3.
Table 3 recovery test and precision test data
Test result indicate that, the glufosinate-ammonium remained in measuring food of method provided by the present invention and metabolin N-thereof
The average recovery rate of acetyl group glufosinate-ammonium and 3-(methyl phosphino-) propionic acid is between 68.7%～109%, and each sample is surveyed continuously
The relative standard deviation (RSD) of fixed 6 results is between 1.42%～12%.
To sum up described in embodiment, showing according to the testing result of embodiment 2-6, analysis method of the present invention is in detection
It is when residual glufosinate-ammonium in different food products and metabolite N-acetyl base glufosinate-ammonium and 3-(methyl phosphino-) propionic acid thereof, highly sensitive,
System suitability is good, precision favorable reproducibility, and the rate of recovery is high, it is possible to effectively in detection food content at 0.05mg/kg～
Glufosinate-ammonium between 1mg/kg and metabolite N-acetyl base glufosinate-ammonium thereof and the residual quantity of 3-(methyl phosphino-) propionic acid.
The method of the present invention is described by preferred embodiment, related personnel substantially can present invention,
In spirit and scope, method described herein and application it is modified or suitably changes and combine, realize and apply the present invention
Technology.Those skilled in the art can use for reference present disclosure, is suitably modified technological parameter and realizes.Special needs to be pointed out is, institute
Having similar replacement and change apparent to those skilled in the art, they are considered as being included in the present invention
In.
Claims (10)
1. one kind measures in food glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and the side of 3-(methyl phosphino-) propionic acid simultaneously
Method, described method uses hydrophilic interaction NH2Chromatographic column, it is to be measured that ammonium acetate solution-acetonitrile presses Gradient program wash-out mutually for flowing
Sample solution or matrix hybrid standard calibration solution, with mass spectrum/mass detector with multiple-reaction monitoring mode detection, then according to
External standard method calculates and remains glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and the content of 3-(methyl phosphino-) propionic acid in food,
Wherein said gradient elution program is:
Wherein said testing sample solution preparation method: the glufosinate-ammonium in sample and metabolin water thereof are extracted, then through two
Chloromethanes and C18 solid phase extraction column purify and obtain；
The preparation method of wherein said matrix hybrid standard calibration solution: weigh negative sample, add glufosinate-ammonium, N-acetyl group
Glufosinate-ammonium and the mixed standard solution of 3-(methyl phosphino-) propionic acid, then extract with water, then through dichloromethane and C18 SPE
Little column purification obtains.
Method the most according to claim 1, the quota ion of component glufosinate-ammonium the most to be measured is to being 180/95；N-acetyl group
The quota ion of glufosinate-ammonium is to being 222/136；The quota ion of 3-(methyl phosphino-) propionic acid is to being 151/133.
Method the most according to claim 1, described method flow rate of mobile phase is 0.1～0.5mL/min or 0.25mL/min.
Method the most according to claim 1, described hydrophilic interaction NH2Chromatographic column is NH2P-502D post, 150mm ×
2.0mm, 5 μm；In running, the column temperature of chromatographic column is 20 DEG C～40 DEG C or 35 DEG C.
Method the most according to claim 1, described ammonium acetate solution is to use ammonium acetate to be dissolved in water, then uses ammoniacal liquor
Regulation pH value obtains, and the concentration of ammonium acetate solution is 0.5～2mmol/L or 1mmol/L, and its pH value is 9～11 or 11.
Method the most according to claim 1, the ion gun of described mass detector is electric spray ion source, and uses negative
Ion mode ionized sample.
Method the most according to claim 1, wherein mass detector uses electric spray ion source, sweeps with negative ion mode
Retouching, use multiple-reaction monitoring detection, the MS detection parameters is: dry temperature: 300 DEG C；Dry gas stream speed: 10L/min；Atomization
Atmospheric pressure: 45psi；Electron spray voltage :-4500V；Sheath gas temperature: 350 DEG C；Sheath gas flow velocity: 7L/min；Spray nozzle voltage :-
1000V。
8. one kind measures in food glufosinate-ammonium and metabolite N-acetyl base glufosinate-ammonium thereof and the side of 3-(methyl phosphino-) propionic acid simultaneously
Method, uses High Performance Liquid Chromatography/Mass Spectrometry/mass spectrography, by Gradient program wash-out testing sample solution or the calibration of matrix hybrid standard
Solution, with mass spectrum/mass detector with multiple-reaction monitoring mode detection, then according to external standard method calculates remains glufosinate-ammonium in food
And metabolite N-acetyl base glufosinate-ammonium and the content of 3-(methyl phosphino-) propionic acid, its chromatographic test strip part is:
Chromatographic column: NH2P-502D post, 150mm × 2.0mm, 5 μm；
Buffer solution: with the 1mmol/L ammonium acetate solution that ammoniacal liquor regulation pH is 11；
Organic phase: acetonitrile；
Column temperature: 35 DEG C；
Flow velocity: 0.25mL/min；
Sampling volume: 5 μ L；
Gradient program
Mass Spectrometer Method condition is to use electric spray ion source, scans with negative ion mode, uses multiple-reaction monitoring detection, detection ginseng
Number is: dry temperature: 300 DEG C；Dry gas stream speed: 10L/min；Atomization gas pressure: 45psi；Electron spray voltage :-4500V；
Sheath gas temperature: 350 DEG C；Sheath gas flow velocity: 7L/min；Spray nozzle voltage :-1000V；
Wherein said testing sample solution preparation method: the glufosinate-ammonium in sample and metabolin water thereof are extracted, then through two
Chloromethanes and C18 solid phase extraction column purify and obtain；
The preparation method of wherein said matrix hybrid standard calibration solution: weigh negative sample, add glufosinate-ammonium, N-acetyl group
Glufosinate-ammonium and the mixed standard solution of 3-(methyl phosphino-) propionic acid, then extract with water, then through dichloromethane and C18 SPE
Little column purification obtains.
9., according to the method described in claim 1-8, wherein the preparation method of testing sample solution is to weigh the sample that homogeneous is good
1g～5g, is accurate to 0.01g, is placed in 50mL tool plug polypropylene centrifuge tube, adds 10mL water, 10mL dichloromethane, abundant whirlpool
Rotation vibration 10min, ultrasonic extraction 10min, be centrifuged 5min with 12000r/min speed, collect supernatant；Extract 5mL has added
In activated C18 solid-phase extraction column, filter discards front 3mL efflux, 2mL efflux after collection, crosses 0.22 μm aqueous phase filter membrane and obtains
?.
Method the most according to claim 9, the preparation method of its mesostroma hybrid standard calibration solution is that to weigh homogeneous good
Negative sample 1g～5g, be accurate to 0.01g, be respectively placed in 50mL tool plug polypropylene centrifuge tube in, add appropriate ammonium phosphine, N-second
Acyl group glufosinate-ammonium and the mixed standard solution of 3-(methyl phosphino-) propionic acid, make glufosinate-ammonium, N-acetyl group glufosinate-ammonium, 3-(methyl
Phosphino-) the extraction standard solution of propionic acid, it is subsequently adding 10mL water, 10mL dichloromethane, abundant vortex oscillation 10min, ultrasonic carry
Take 10min, be centrifuged 5min with 12000r/min speed, collect supernatant；Extract 5mL adds the most activated C18 solid phase extraction
Taking in post, filter discards front 3mL efflux, 2mL efflux after collection, crosses 0.22 μm aqueous phase filter membrane and obtains.
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| CN105938102A (en) * | 2016-07-15 | 2016-09-14 | 四川理工学院 | Method for rapid determination of pesticide residues in fruits and vegetables through chemical developing method |
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