CN112697915A - Method for measuring residual amount of phosphorous acid in plant-derived food - Google Patents
Method for measuring residual amount of phosphorous acid in plant-derived food Download PDFInfo
- Publication number
- CN112697915A CN112697915A CN202011494478.6A CN202011494478A CN112697915A CN 112697915 A CN112697915 A CN 112697915A CN 202011494478 A CN202011494478 A CN 202011494478A CN 112697915 A CN112697915 A CN 112697915A
- Authority
- CN
- China
- Prior art keywords
- sample
- phosphorous acid
- standard
- solution
- residual amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- 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
- G01N30/02—Column chromatography
-
- G—PHYSICS
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- 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
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/047—Standards external
-
- G—PHYSICS
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- G—PHYSICS
- 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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention belongs to the technical field of food detection, and particularly relates to a method for measuring the residual amount of phosphorous acid in plant source food. The method replaces the purification and methylation of acidified methanol and strong acid cation exchange resin in the existing standard by pure water extraction, has simple pretreatment operation, short time consumption and high efficiency, and greatly solves various problems in the existing standard method; the method can be used for quickly detecting the residual amount of the phosphorous acid in the plant source food, has wider specific substrate, shortens the testing time, improves the laboratory flux, reduces the laboratory cost, and can reach a lower quantitative limit of 0.025 mg/kg.
Description
Technical Field
The invention belongs to the technical field of food detection, and particularly relates to a method for measuring the residual amount of phosphorous acid in a plant source.
Background
Phosphorous acid is an inorganic compound, is easily soluble in water and alcohol, has strong reducibility, is mainly used as a reducing agent and a nylon brightener, and is also used as a phosphite raw material, a pesticide intermediate and a raw material of an organophosphorus water treatment agent. The phosphite has good effect on inhibiting oomycete germs of solanum, brassica and other leafy vegetables and the like when being used as a bactericide, and has good fertilizer effect on increasing flowering, yield, fruit size, soluble substance content and the like of crops such as strawberries, potatoes and the like. The research on the action mechanism of phosphorous acid proves that phosphorous acid state phosphorus can be transported in the xylem and phloem of crops in double channels, so that the absorption and utilization of nutrients are accelerated; in the aspect of disease resistance, researchers generally believe that phosphorous acid phosphorus can induce crops to generate defense toxin and disease course related protein (PR protein), possibly rely on Salicylic Acid (SA) to open a defense mechanism, and enable the crops to generate continuous immunity against pathogenic bacteria, but no clear determination is made so far.
At present, as for the determination of the content of the phosphorous acid in the plant-derived food, no relevant standard Method exists in China, and the currently referable foreign standard is mainly Japanese JAP-088 standard and the European Union QuPPe-PO-Method. In the Japanese JAP-088 standard, oxalic acid solution extraction and strong-acid cation exchange resin purification are adopted, wherein the purification needs to be performed by injecting and collecting twice by using the strong-acid cation exchange resin, then diazomethane ethyl ether methylation is performed, isopropanol is subjected to constant volume, and a gas chromatography-flame photometric detector is used for quantification, wherein the limit of quantification is high and is 0.5 mg/kg. In addition, in the japanese JAP-088 standard, the detection steps are complicated, the time consumption is long, the device is complex, batch processing cannot be performed, an easily toxic reagent, namely ethyl ether, is used, the risk of an experiment is increased, the samples and the standard products need to be derived, the stability of the experiment process is difficult to control in actual operation, and accurate quantification cannot be performed.
The Method of QuPPe-PO-Method of European Union is that 10mL of 1% methanoic acid methanol is added into a sample, the mixture is shaken for 15min, centrifuged for 2min at 9000r/min, and the supernatant is taken and put on a machine after being filtered by a membrane (if the matrix contains more oil, 4mL of supernatant is taken, 200mgC18 powder is filtered, and then the supernatant is put on the machine by the membrane). The standard uses acidified methanol for extraction, 1% methanoic acid methanol is adopted for shake extraction, and then the sample is centrifuged and filtered, and quantified by a liquid chromatography-tandem mass spectrometer; however, since the phosphorous acid is collected in a negative ion mode, formic acid inhibits ionization, so that the response of the project is reduced, the quantitative limit is improved, and the lower quantitative limit cannot be reached in actual operation; meanwhile, the standard curve linearity can not meet the requirement, the reproducibility is poor, and the normal test requirement can not be met.
Domestic literature relates to detection of residual quantity of fosetyl-aluminum in spinach by high performance liquid chromatography tandem mass spectrometry, and acetonitrile is adopted: the water is homogenized and extracted by 1:1 solution, the homogenized and extracted again by filtering through funnel diatomite, and the purified water passes through a C18 solid phase extraction column, the method aims at the problem that the matrix is too single, only spinach matrix is used, and the quantitative limit is also higher to be 0.27mg/kg, so that the requirement of lower limit of customers cannot be met.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for measuring the residual amount of phosphorous acid in plant source food. The method replaces the purification and methylation of acidified methanol and strong acid cation exchange resin in the existing standard by pure water extraction, has simple pretreatment operation, short time consumption and high efficiency, and greatly solves various problems in the existing standard method. The method can be used for quickly detecting the residual amount of the phosphorous acid in the plant source food, has wider specific substrate, shortens the testing time, improves the laboratory flux, reduces the laboratory cost, and can reach a lower quantitative limit of 0.025 mg/kg.
The technical scheme of the invention is as follows:
a method for measuring the residual amount of phosphorous acid in plant-derived food comprises the following steps:
(1) preparing a sample solution:
the method comprises the following steps: direct extraction (mainly aiming at simple substrates of fresh fruits, vegetables, fruit juice and the like)
Accurately weighing a certain mass of sample, placing the sample in a centrifuge tube, adding a certain volume of primary water, shaking and extracting for 15-30 min, centrifuging for 2-3 min at 8000-9000 r/min, taking supernate, filtering with a 0.22 mu m filter membrane, and waiting for measuring on a computer;
the second method comprises the following steps: HLB purification method (mainly aiming at complex substrate of dried fruits and vegetables)
Accurately weighing a certain mass of sample, placing the sample in a centrifuge tube, adding a certain volume of primary water, performing shaking extraction for 15-30 min, centrifuging for 2-3 min at 8000-9000 r/min, taking supernatant, passing through an HLB (hydrophile-lipophile balance) solid-phase extraction column which does not need to be activated, taking filtrate, passing through a 0.22 mu m filter membrane, and waiting for determination on a computer.
(2) Preparation of standard working solution: accurately weighing a phosphorous acid standard substance to prepare a standard solution stock solution of 1000mg/L, transferring the prepared standard solution stock solution of 1000mg/L, dissolving and diluting the standard solution stock solution with primary water to prepare standard working solutions with the concentrations of 100mg/L, 10mg/L and 1.0mg/L in sequence, and storing the standard working solutions at 4 +/-4 ℃ for later use;
(3) preparing a matrix standard curve: accurately weighing a certain mass of sample, placing the sample into a centrifuge tube, respectively adding 10 mu L, 20 mu L, 50 mu L, 100 mu L and 200 mu L of the phosphorous acid standard working solution with the concentration of 1.0mg/L prepared in the step (2), respectively adding a certain volume of first-grade water, and respectively preparing matrix standard curves of 0.001mg/L, 0.002mg/L, 0.005mg/L, 0.010mg/L and 0.020mg/L by the same operation of the first method or the second method in the step (1); waiting for testing on a machine;
(4) and (4) determining the result: and (3) measuring the concentration of the phosphorous acid in the sample solution by adopting a liquid chromatography-tandem mass spectrometer, correcting the matrix standard solution obtained in the step (3), and calculating the residual amount of the phosphorous acid in the sample.
Further, the determination conditions of the liquid chromatography-tandem mass spectrometer in the step (4) are as follows:
a chromatographic column: waters Acquirty
HSS T3; 1.8 μm size 2.1X 100 mm; or equivalent in performance;
column temperature: 40 ℃; sample introduction amount: 3 mu L of the solution; flow rate: 0.3 mL/min;
the flowability and gradient are shown in the following table:
mass spectrometry reference conditions are as follows:
| type of ion source | Electrospray source ESI negative ions |
| Air curtain pressure (psi) | 30 |
| Collision air pressure (psi) | 9 |
| Electric spray voltage (V) | -4500 |
| Ion Source temperature (. degree. C.) | 650 |
| Atomization gas pressure 1(psi) | 45 |
| Atomizing air pressure 2(psi) | 45 |
And (4) determining the concentration of the phosphorous acid in the sample solution by adopting a liquid chromatography-tandem mass spectrometer, and quantitatively calculating the residual amount of the phosphorous acid in the sample by adopting an external standard method according to a matrix standard curve, wherein the minimum quantitative limit concentration is 0.025 mg/kg.
The invention has the beneficial effects that:
(1) the invention provides a brand-new pretreatment method and an instrument method for measuring the residual amount of the phosphorous acid in the plant source food, which can meet the requirement of lower quantitative limit, the quantitative limit of the invention is 0.025mg/kg, the overall experimental efficiency is greatly improved, and the requirement of lower quantitative limit of more clients is met.
(2) The invention uses pure water reagent to extract the upper machine, and pure water is more friendly to a negative mode ionization mode compared with methanoic acid, and can not inhibit the ionization efficiency of a sample, so that the phosphorous acid is better and stable, the peak shape is good, the standard curve is linear, and the quantification is more accurate.
(3) The reagent is environment-friendly and safe, and only pure water is used as an extraction reagent, so that compared with ethyl ether, diazomethane and other reagents which are easy to prepare poison and have high risk, and formic acid methanol reagents and the like used in the existing standard, the pure water is more environment-friendly and safe, is friendly to environment and human, is easy to obtain, and has lower cost.
(4) The pretreatment operation is simpler, and the detection efficiency is greatly improved by only adopting a horizontal oscillation extraction mode, compared with the complex operation of a complex device which utilizes strong acid cation exchange resin for purification and simultaneously has diazomethane methylation and the like, the pretreatment operation is simpler, safer and shorter in time consumption, and can be operated in batch.
(5) The sample treatment is flexible, different pretreatment modes are provided for fresh samples and dried samples, and the sample treatment mode is more flexible.
Drawings
FIG. 1 is a standard point spectrum of an aqueous solution of phosphorous acid (0.01. mu.g/ml) prepared with pure water;
FIG. 2 is a spectrum of a phosphorous acid matrix sample provided in example 1 of the present invention;
FIG. 3 is a mass spectrum of a standard addition point of a phosphorous acid matrix solution provided in example 1 of the present invention;
FIG. 4 is a mass spectrum of a standard solution of phosphorous acid prepared with 1% formic acid (0.05. mu.g/ml).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
For a further understanding of the invention, reference will now be made to the following description taken in conjunction with the accompanying drawings and examples.
Example 1
(1) Preparing a sample solution:
when the sample is simple matrix such as fresh fruit, vegetable, fruit juice, etc., the preparation of sample solution is carried out by adopting a direct extraction method, and the steps are as follows:
weighing 1g (accurate to 0.01g) of sample, placing the sample in a 50mL centrifuge tube, adding 10mL of first-class water, and extracting for 20min by using a horizontal oscillator; centrifuging for 2min at 8000r/min, and filtering the supernatant with 0.22 μm filter membrane to obtain sample solution to be measured;
when the sample is a complex substrate of dried fruits and vegetables, preparing a sample solution by an HLB (hydrophile-lipophile balance) purification method, comprising the following steps of:
weighing 1g (accurate to 0.01g) of sample, placing the sample in a 50mL centrifuge tube, adding 10mL of first-class water, and extracting for 20min by using a horizontal oscillator; centrifuging at 8000r/min for 2min, collecting supernatant 5ml, passing through HLB solid phase extraction column without activation, and filtering the filtrate with 0.22 μm filter membrane to obtain sample solution to be measured.
(2) Preparation of standard working solution:
preparation of a stock solution of phosphorous acid standard solution (1000 mg/L): accurately weighing a phosphorous acid standard substance which is equivalent to 10mg +/-0.1 mg (accurate to 0.01mg), dissolving the phosphorous acid standard substance in a 10mL volumetric flask by using a mixed solution of methanol and water (1:1), fixing the volume to a scale, preparing a single-standard stock solution with the concentration of 1000mg/L, storing the stock solution at-18 +/-4 ℃, and keeping the stock solution for 12 months.
Preparing a phosphorous acid standard working solution (100mg/L), namely accurately sucking 1000 mu L of the prepared 1000mg/L standard solution stock solution by using a 1000uL liquid-transferring gun, dissolving the 1000 mu L standard solution stock solution in a 10mL volumetric flask by using primary water, fixing the volume to scale, preparing an intermediate standard solution with the phosphorous acid of 100mg/L, storing the intermediate standard solution at 4 +/-4 ℃, and prolonging the effective period for 3 months.
Preparation of phosphorous acid standard working solution (10 mg/L): accurately sucking 1000 mul of 100mg/L standard working solution by a 1000uL liquid-transferring gun, dissolving by primary water in a 10mL volumetric flask, fixing the volume to a scale, preparing an intermediate standard solution with the phosphorous acid concentration of 10mg/L, storing at 4 +/-4 ℃, and keeping the validity period for 1 month.
Preparation of phosphorous acid standard working solution (1.0 mg/L): accurately sucking 1000 microliter of standard working solution of 10mg/L hydrochloric acid by a 1000 microliter pipette, dissolving with primary water in a 10mL volumetric flask, fixing the volume to scale, preparing the working solution with the concentration of phosphorous acid of 1.0mg/L, storing at 4 +/-4 ℃ for 3 days, and prolonging the shelf life.
(3) Preparing a matrix standard curve: weighing 1g (accurate to 0.01g) of sample, placing the sample in a 50mL centrifuge tube, respectively adding 10 muL, 20 muL, 50 muL, 100 muL and 200 muL of the phosphorous acid standard working solution with the concentration of 1.0mg/L prepared in the step (2), respectively adding 10mL of first-class water, and respectively preparing the subsequent treatment mode into matrix standard curves of 0.001mg/L, 0.002mg/L, 0.005mg/L, 0.010mg/L and 0.020mg/L by the same operation of the method I or the method II in the step (1) (different methods are selected according to different sample matrixes). Taking the peak area of the phosphorous acid quantitative ion as a vertical coordinate, and taking the mass concentration of the phosphorous acid matrix standard solution as a horizontal coordinate to draw a standard curve; the linear correlation coefficient for phosphorous acid is r-0.9988.
(4) And (4) determining the result: the concentration of the phosphorous acid in the sample solution is measured by adopting a liquid chromatogram-tandem mass spectrometer, and the measurement conditions of the liquid chromatogram-tandem mass spectrometer are as follows:
a chromatographic column: waters Acquirty
HSS T3；1.8μm size 2.1×100mm；
Column temperature: 40 ℃; sample introduction amount: 3 mu L of the solution; flow rate: 0.3 mL/min;
the flowability and gradient are shown in the following table:
| time (min) | Mobile phase A (pure water) | Mobile phase B (acetonitrile) |
| 0 | 96 | 4 |
| 0.3 | 96 | 4 |
| 0.31 | 30 | 70 |
| 2.4 | 10 | 90 |
| 3.0 | 10 | 90 |
| 3.1 | 96 | 4 |
| 3.5 | 96 | 4 |
Mass spectrometry reference conditions are as follows:
the target mass spectral parameters are as follows:
and (3) after the concentration of the phosphorous acid in the sample solution is measured, quantifying through the substrate standard curve obtained in the step (3), calculating the residual amount of the phosphorous acid in the sample, calculating the residual amount of the target object in the sample according to the following formula, and deducting a blank value from the calculation result.
In the formula:
x represents the residual quantity of the component to be detected in the sample, mg/kg;
c, concentration of standard working solution of the component to be detected in mg/L;
v, the final constant volume of the sample solution, namely mL;
m is the sample weight, g.
Test example 1
The limit of quantitation of the invention is 0.025 mg/kg; the Chinese cabbage matrix is adopted as a sample, and the following verification experiment is carried out on the quantitative limit:
(1) to the sample, 25. mu.L, 50. mu.L, and 250. mu.L of 1.0mg/L standard working solutions were added, and the concentration was repeated 6 times according to the pretreatment method of method one, and the amount was determined by using the matrix curve. The result shows that the average recovery rate is 94.7-100.7% and the average relative standard deviation RSD is 1.3-3.2% when the adding concentration is 0.025-0.25 mg/kg.
(2) To each sample, 25. mu.L of 1.0mg/L of a standard working solution was added, and each concentration was repeated 10 times according to the pretreatment method of method one. The substrate curve is used for quantification, and the result shows that the LOQ is 0.007mg/kg according to the calculation result, so that the method quantification limit of 0.025mg/kg of the method is met.
Test example 2
Fresh vegetables are selected as test samples, water, methanol and acetonitrile are respectively selected as extraction reagents, homogeneous extraction methods, ultrasonic extraction methods and oscillating extraction methods are respectively selected for verification experiments, and sample standard recovery rate results under different extraction reagents and extraction methods are obtained as shown in the following table.
By comparing the sample standard recovery rates in the table above, it can be seen that the recovery rate of the homogeneous extraction method is the lowest among the three extraction methods, and the recovery rate of the oscillatory extraction method is the highest. The ethyl phosphoric acid and the phosphorous acid have extremely high water solubility, the water content in a fresh vegetable sample is high, the three extraction solutions are mutually soluble with water, and the oscillation mode ensures that the sample and the extraction solution are fully contacted to finish extraction and obtain higher extraction effect.
Test example 3
A1% formic acid aqueous solution in a European Union QuPPe-PO-Method is adopted to prepare a phosphorous acid standard solution, when the phosphorous acid standard solution is tested on a machine, the situation of two peaks shown in figure 4 can occur on the phosphorous acid standard solution, the two peaks are both target objects, and the standard solution prepared by the 1% formic acid aqueous solution is continuously fed in, the linearity of a standard curve can not meet the requirement, the reproducibility is poor, and the normal test requirement can not be met, so that the phosphorous acid is sensitive to acid, and the type of the top machine peak is poor; and pure water is adopted to prepare a phosphorous acid standard substance for determination, and the determination result is shown in figure 1, so that the upper peak type is better, and the stability is stronger.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or modification made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A method for measuring the residual amount of phosphorous acid in plant-derived food is characterized by comprising the following steps:
(1) preparing a sample solution:
the first method, direct extraction method: accurately weighing a certain mass of sample, placing the sample in a centrifuge tube, adding a certain volume of primary water, shaking and extracting for 15-30 min, centrifuging for 2-3 min at 8000-9000 r/min, taking supernate, filtering with a 0.22 mu m filter membrane, and waiting for measuring on a computer;
method two, HLB purification method: accurately weighing a certain mass of sample, placing the sample in a centrifuge tube, adding a certain volume of primary water, performing shaking extraction for 15-30 min, centrifuging for 2-3 min at 8000-9000 r/min, taking supernatant, passing through an HLB (hydrophile-lipophile balance) solid-phase extraction column which does not need to be activated, taking filtrate, passing through a 0.22 mu m filter membrane, and waiting for measuring on a computer;
(2) preparation of standard working solution: accurately weighing a phosphorous acid standard substance to prepare a standard solution stock solution of 1000mg/L, and sequentially preparing standard working solutions with the concentrations of 100mg/L, 10mg/L and 1.0mg/L according to the standard solution stock solution;
(3) preparing a matrix standard curve: accurately weighing a certain mass of sample, placing the sample into a centrifuge tube, respectively adding 10 mu L, 20 mu L, 50 mu L, 100 mu L and 200 mu L of the phosphorous acid standard working solution with the concentration of 1.0mg/L prepared in the step (2), respectively adding a certain volume of first-grade water, and respectively preparing matrix standard curves of 0.001mg/L, 0.002mg/L, 0.005mg/L, 0.010mg/L and 0.020mg/L by the same operation of the first method or the second method in the step (1); waiting for testing on a machine;
(4) and (4) determining the result: and (3) measuring the concentration of the phosphorous acid in the sample solution by adopting a liquid chromatography-tandem mass spectrometer, correcting the matrix standard solution obtained in the step (3), and calculating the residual amount of the phosphorous acid in the sample.
2. The method for measuring the residual amount of phosphorous acid in a plant-derived food according to claim 1, wherein in the step (1), when the sample is a simple substrate, including fresh fruits, vegetables, and fruit juices, a direct extraction method is adopted; when the sample is a complex matrix, including dried plant-derived food, the method two HLB decontamination method is employed.
3. The method for measuring the residual amount of phosphorous acid in a plant-derived food according to claim 1, wherein the conditions of the liquid chromatography-tandem mass spectrometer in the step (4) are as follows:
a chromatographic column: waters Acquirty
HSS T3；1.8μm size 2.1×100mm；
Column temperature: 40 ℃; sample introduction amount: 3 mu L of the solution; flow rate: 0.3 mL/min;
the flowability and gradient are shown in the following table:
Mass spectrometry reference conditions are as follows:
4. The method according to claim 1, wherein the concentration of the phosphorous acid in the sample solution is determined by a liquid chromatography-tandem mass spectrometer in the step (4), and the residual amount of the phosphorous acid in the sample is quantitatively calculated by an external standard method according to a matrix standard curve, wherein the minimum quantitative limit concentration is 0.025 mg/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011494478.6A CN112697915B (en) | 2020-12-17 | 2020-12-17 | Method for measuring residual amount of phosphorous acid in plant-derived food |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011494478.6A CN112697915B (en) | 2020-12-17 | 2020-12-17 | Method for measuring residual amount of phosphorous acid in plant-derived food |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112697915A true CN112697915A (en) | 2021-04-23 |
| CN112697915B CN112697915B (en) | 2022-09-02 |
Family
ID=75508694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011494478.6A Active CN112697915B (en) | 2020-12-17 | 2020-12-17 | Method for measuring residual amount of phosphorous acid in plant-derived food |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112697915B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107517A (en) * | 2005-01-25 | 2008-01-16 | 拜尔农科股份有限公司 | Method of analyzing phosphorous acid, fosetyl-al or both simultaneously |
| US20080257019A1 (en) * | 2005-01-25 | 2008-10-23 | Bayer Cropscience Sa | Method of Analyzing Phosphorous Acid, Fosetyl-Al, or Both Simultaneously |
| RU2007132190A (en) * | 2005-01-25 | 2009-03-10 | Байер Кропсайенс Са (Fr) | METHOD FOR ANALYSIS OF PHOSPHORIC ACID, FOSETHYL-AL OR SIMULTANEOUSLY AND THOSE AND OTHER |
| CN102944621A (en) * | 2012-11-12 | 2013-02-27 | 深圳市谱尼测试科技有限公司 | Method for determining residual quantity of fosetyl-aluminium in environmental sample |
| CN106645539A (en) * | 2017-03-10 | 2017-05-10 | 中国热带农业科学院分析测试中心 | Method for detecting phosethyl-aluminum through ultra-high performance liquid chromatography-tandem mass spectrometry |
| CN108680667A (en) * | 2018-05-08 | 2018-10-19 | 江苏安舜技术服务有限公司 | The assay method of chlorate, perchlorate, phosphite in a kind of tealeaves |
-
2020
- 2020-12-17 CN CN202011494478.6A patent/CN112697915B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107517A (en) * | 2005-01-25 | 2008-01-16 | 拜尔农科股份有限公司 | Method of analyzing phosphorous acid, fosetyl-al or both simultaneously |
| US20080257019A1 (en) * | 2005-01-25 | 2008-10-23 | Bayer Cropscience Sa | Method of Analyzing Phosphorous Acid, Fosetyl-Al, or Both Simultaneously |
| RU2007132190A (en) * | 2005-01-25 | 2009-03-10 | Байер Кропсайенс Са (Fr) | METHOD FOR ANALYSIS OF PHOSPHORIC ACID, FOSETHYL-AL OR SIMULTANEOUSLY AND THOSE AND OTHER |
| CN102944621A (en) * | 2012-11-12 | 2013-02-27 | 深圳市谱尼测试科技有限公司 | Method for determining residual quantity of fosetyl-aluminium in environmental sample |
| CN106645539A (en) * | 2017-03-10 | 2017-05-10 | 中国热带农业科学院分析测试中心 | Method for detecting phosethyl-aluminum through ultra-high performance liquid chromatography-tandem mass spectrometry |
| CN108680667A (en) * | 2018-05-08 | 2018-10-19 | 江苏安舜技术服务有限公司 | The assay method of chlorate, perchlorate, phosphite in a kind of tealeaves |
Non-Patent Citations (3)
| Title |
|---|
| HERNÁNDEZ F 等: "Rapid Determination of Fosetyl-Aluminum Residues in Lettuce by Liquid Chromatography/Electrospray Tandem Mass Spectrometry", 《JOURNAL OF AOAC INTERNATIONAL》 * |
| NARONG CHAMKASEM: "Determination of Glyphosate, Maleic Hydrazide, Fosetyl Aluminum,and Ethephon in Grapes by Liquid Chromatography/Tandem Mass Spectrometry", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
| 王洪艳 等: "高效液相色谱串联质谱法检测菠菜中三乙磷酸铝残留量", 《农产品加工·学刊》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112697915B (en) | 2022-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Montagner et al. | Trace analysis of pesticides and an assessment of their occurrence in surface and drinking waters from the State of São Paulo (Brazil) | |
| CN106053703B (en) | It is a kind of at the same detect food in various plants growth regulator method | |
| CN106442747B (en) | A kind of method that chloropyuril in fruits and vegetables, 2,4-D, paclobutrazol residual quantity are measured simultaneously using gas chromatography mass spectrometry | |
| CN105758947B (en) | It is a kind of while measure the method for glufosinate-ammonium and its metabolite residue amount in food | |
| CN111855871B (en) | Method for measuring iprovalicarb and fluopyram in tobacco by combination of filtration type solid-phase extraction and supercritical fluid chromatography-mass spectrometry | |
| CN106153801A (en) | A kind of method of seven kinds of mycotoxins in Chinese liquor supplementary material of detection simultaneously | |
| CN103472155A (en) | Gas chromatographic method for detecting residue amount of nine kinds of organophosphorus pesticide in rice | |
| CN114137134B (en) | Method for separating selenium form by high performance liquid chromatography-inductively coupled plasma mass spectrometry | |
| CN113376298A (en) | Method for rapidly determining residual quantity of 4 pesticides in rice | |
| CN109781889A (en) | A kind of measuring method of 24 kinds of mycotoxins in nourishing rice flour for babies | |
| Lee et al. | Rapid quantification of cellular flavonoid levels using quercetin and a fluorescent diphenylboric acid 2-amino ethyl ester probe | |
| Choi et al. | Rapid detection of pesticides in honey by solid-phase micro-extraction coupled with electrospray ionization mass spectrometry | |
| CN111896360A (en) | Method for rapidly determining content of lithium, niobium, tin and bismuth in soil | |
| CN110470768B (en) | Method for measuring residual amounts of pyrazosulfuron-ethyl, triazophos and butachlor in water | |
| CN112858542B (en) | Liquid chromatography mass spectrometry method for measuring atrazine, imidacloprid and metabolites thereof in leaves | |
| CN112697915B (en) | Method for measuring residual amount of phosphorous acid in plant-derived food | |
| CN106404958A (en) | Method for quickly detecting contents of plant growth regulators in vegetables | |
| CN108020627B (en) | Method for determining residual quantity of three phenoxy carboxylic acid pesticides in tobacco by ultra-high performance synthetic phase chromatography-tandem mass spectrometry | |
| CN113390997A (en) | Method for simultaneously and quantitatively detecting matrine and oxymatrine in tea | |
| CN103217498A (en) | Method for detecting dicyandiamide in milk powder with LC-MS (liquid chromatography/mass spectrometry) and sample preparation method | |
| Abdelwahed et al. | Polar reversed-phase liquid chromatography coupled with triple quadrupole mass spectrometer method for simple and rapid determination of maleic hydrazide residues in some fruits and vegetables | |
| CN115389669B (en) | Chromatographic detection method for banana vascular wilt | |
| CN108132309B (en) | Analysis method for determining residual quantity of thiediazole copper in dendrobium officinale | |
| CN105929060A (en) | LC-MS-MS detection method for residual quantity of spinetoram in vegetable and fruit | |
| CN110568092A (en) | method for simultaneously detecting phosphine, ethephon, glufosinate-ammonium and glyphosate in water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |