CN106645539A - Method for detecting phosethyl-aluminum through ultra-high performance liquid chromatography-tandem mass spectrometry - Google Patents
Method for detecting phosethyl-aluminum through ultra-high performance liquid chromatography-tandem mass spectrometry Download PDFInfo
- Publication number
- CN106645539A CN106645539A CN201710141610.7A CN201710141610A CN106645539A CN 106645539 A CN106645539 A CN 106645539A CN 201710141610 A CN201710141610 A CN 201710141610A CN 106645539 A CN106645539 A CN 106645539A
- Authority
- CN
- China
- Prior art keywords
- ion
- phosethyl
- ratio
- acetonitrile
- acid
- 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
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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
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)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to the field of analytic chemistry and relates to a method for detecting phosethyl-aluminum through ultra-high performance liquid chromatography-tandem mass spectrometry. The method includes: adding acetonitrile into a sampled product for pretreatment, adding sodium chloride, strongly oscillating, centrifuging, and taking upper-layer acetonitrile solution; adding anhydrous magnesium sulfate and PSA adsorbent into the acetonitrile solution, strongly oscillating, centrifuging, and taking supernate as extracted liquid for detection; using ultra-high performance liquid chromatography-tandem mass spectrometry to measure content of ethyl phosphate ions and phosphite ions in the extracted liquid, and utilizing a formula to calculate content of phosethyl-aluminum in the extracted liquid. According to proportion of the ethyl phosphate ions and the phosphite ions in different solutions, the ultra-high performance liquid chromatography-tandem mass spectrometry is adopted to detect the content of the ethyl phosphate and phosphite ions, and the content of phosethyl-aluminum in a to-be-detected object is obtained through calculation and conversion; the method meets regulations of national standards on food safety and is suitable for accurate and quick analysis on residual amount of phosethyl-alumium.
Description
Technical field
The invention belongs to analytical chemistry field, is related to a kind of quantitative analysis method of organic pollution, it is one specifically
The content for determining ethyl phosphonic acid and phosphorous acid ion simultaneously using Ultra Performance Liquid Chromatography-tandem mass spectrum is planted, by calculating its ratio
Example simultaneously converts the quantitative approach for becoming phosethyl-Al content.
Background technology
Phosethyl-Al (fosetyl-aluminium) be a kind of organic phosphates efficiently, wide spectrum, absorbability low toxicity it is sterilized
Agent.It in plant body can upper and lower Bidirectional Conduction, have good to the disease that single shaft mould category, Peronospora, Phytophthora cause
Prevention effect, is the current both at home and abroad more medicament of preventing and treating rice blast, fruit tree, vegetable downy mildew, epidemic disease application.
Phosethyl-Al is made up of ethyl phosphonic acid ion and aluminium ion in the form of chemical bond, and it generally dissociates in matrix
Afterwards in the form of chemical ion ethyl phosphonic acid and phosphorous acid ion.Traditional analysis method determines triethylphosphine with complexometry
Sour aluminium content [Chemical Engineering Technology and exploitation, 2007,36 (1):39-41,35], but the method complex operation, doing trace analysis
When, error is larger.In recent years, with the popularization of chromatographic technique, all kinds of analytical technologies based on after chromatographic isolation are also applied to
In the middle of triethylphosphine acid Al-single crystal.Conventional method performed the derivatization at a constant temperature using trimethyl silicane diazomethane [agricultural chemicals,
2009,48(10):747-748,759] ethanol [color, or by phosethyl-Al is generated after complete alkaline hydrolysis in closed reaction bulb
Spectrum, 1993,11 (5):285-287], determine the product after derivatization or alkaline hydrolysis by gas chromatography is carried out to phosethyl-Al
Quantitatively, but these method pre-treatments are more complicated, the more difficult control of experiment condition.Deposited in the form of ion in view of phosethyl-Al
, have document report use ion chromatography sample ions content [Microchemical Journal, 1995,52 (1):
68-76], and the content using ethylphosphonic acid ion carries out quantitatively, but the method is easily disturbed by complex matrices, is affected
Measurement result.Additionally, liquid chromatography technology is also applied in the middle of the quantitative analysis of phosethyl-Al, have document report use from
Son RPLC-evaporative light-scattering detector is determined phosethyl-Al content [chromatogram, 2009,27 (6):
849-851], but the detection limit of the method is higher, it is impossible to meet the demand of phosethyl-Al retention analysis.
The national food safety standard of China《Pesticide MRL》Regulation three in (GB 2763-2014)
The residual of fosetyl-aluminium is defined as ethyl phosphonic acid and phosphorous acid and its salt sum, is represented with ethyl phosphonic acid.In existing document only
Determine ethyl phosphonic acid content [Journal of AOAC International, 2003,86 (4):832-838], it is impossible to meet
The demand of definition is remained in national standard with regard to phosethyl-Al.
The content of the invention
It is an object of the invention to provide the method that a kind of Ultra Performance Liquid Chromatography-tandem mass spectrum detects phosethyl-Al, adopts
With Ultra Performance Liquid Chromatography-tandem mass spectrometry detection ethyl phosphonic acid and the content of phosphorous acid ion, while by calculating its ratio
And conversion becomes phosethyl-Al content, for accurate, the quick analysis of triethylphosphine acid Aluminium residual.
The technology used in the present invention principle：
Low toxicity bactericide -- phosethyl-Al exists in the solution in two kinds of forms of ethyl phosphonic acid and phosphorous acid, to two kinds of acid
Ionization cracking is carried out, then two kinds of ions of ethyl phosphonic acid and phosphorous acid is determined using Ultra Performance Liquid Chromatography-tandem mass spectrum
Content.40 are essentially according to the presence ratio of two kinds of ions in different solutions：60 rule, by the ion concentration Jing meters for determining
Calculate, convert the content that phosethyl-Al in determinand is obtained.
The technical solution adopted in the present invention：
The method that a kind of Ultra Performance Liquid Chromatography-tandem mass spectrum detects phosethyl-Al, its step is as follows：
1st, accurately weigh addition acetonitrile after sample to be pre-processed, then press mass volume ratio for 1 by standard of acetonitrile：10
The ratio of～15 (g/mL) adds sodium chloride, acutely shakes after 1～3min, and 4～6min is centrifuged with the rotating speed of 4000r/min, takes
Upper strata acetonitrile solution；Volume mass ratio is pressed in acetonitrile solution for 1：The ratio of 0.02～0.025 (mL/g) is separately added into anhydrous
Magnesium sulfate and PSA adsorbents, acutely shake after 1～3min, and 5～7min is centrifuged with the rotating speed of 4000r/min, take supernatant conduct
Extract, it is to be measured.The sample is fruits and vegetables sample, pedotheque or water sample.The preprocessing process is：In fruits and vegetables sample
It is 1 by mass volume ratio：The ratio of 2～3 (g/mL) adds acetonitrile, then 2～5min of high-speed homogenization；Matter is pressed in pedotheque
Amount volume ratio is 1：The ratio of 2～3 (g/mL) adds acetonitrile, then vibrates 13～18min；It is by volume 1 in water sample：
The ratio of 2～3 (mL/mL) adds acetonitrile, then vibrates 13～18min.
2nd, ethyl phosphonic acid ion and phosphorous acid ion in extract are determined using Ultra Performance Liquid Chromatography-tandem mass spectrum
The parent ion and quota ion pair of content, wherein ethyl phosphonic acid is respectively 109 and 81/63, the parent ion of phosphorous acid and it is quantitative from
Son is to being respectively 81 and 79/63.
3rd, chromatogram condition of work：UPLC chromatographic columns are ACQUITYBEH HILIC (1.7 μm, 2.1mm ×
50mm), column temperature：35 DEG C, flow velocity：0.25mL/min, sample size：2μL；Mobile phase：A phases are acetonitrile, and B phases are 0.05% formic acid water
(10/90, v/v), its condition of gradient elution is：0～0.5min, mobile phase A keeps 10%；0.5～3.0min, mobile phase A from
10% is changed into 90%；3.0～3.5min, mobile phase A is changed into 10% from 90%；3.5～5.0min, mobile phase A keeps 10%；
5.0min stop.
4th, mass spectrum condition of work：Scan mode：Negative electrospray ionization (ESI-) is scanned；Detection mode：Multiple-reaction monitoring
(MRM)；Atomization gas：379.225kPa；Spray voltage：4500kV.
5th, it is 40 according to the presence ratio of ethyl phosphonic acid ion in extract and phosphorous acid ion：60, using equation below
Calculate triethylphosphine acid aluminium content in extract：
Triethylphosphine acid aluminium content=ethyl phosphonic acid ion concentration × 0.4+ phosphorous acid contents ion × 0.6.
The present invention determine object be phosethyl-Al in different samples content, specific sample can for apple, banana,
The difference fruits and vegetables and water, soil etc. such as cucumber, wild cabbage.
The present invention is essentially 40 according to the presence ratio of ethyl phosphonic acid ion in different solutions and phosphorous acid ion：60 rule
Rule, using Ultra Performance Liquid Chromatography-tandem mass spectrometry detection ethyl phosphonic acid and the content of phosphorous acid ion, is computed, converts
The content of phosethyl-Al in determinand, in 10-500 μ g/L concentration ranges, ethyl phosphonic acid and phosphorous acid ion it is linear
Coefficient correlation is all higher than 0.999, and acquired results can more embody the content of phosethyl-Al, and error is in the reasonable scope, meets
National food safety standard《Pesticide MRL》In regulation, and determine phosethyl-Al and be quantitatively limited to
0.52 μ g/kg, it is adaptable to accurate, the quick analysis of triethylphosphine acid Aluminium residual.
Description of the drawings
Fig. 1 is the ratio of ethyl phosphonic acid and phosphorous acid ion in different solutions.
Fig. 2 is the lytic pathway of ethyl phosphonic acid and phosphorous acid ion.
Specific embodiment
With reference to embodiment, the specific embodiment of the present invention is described in further detail.Following examples are used for
The present invention is illustrated, but is not limited to the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally
According to normal condition, or according to the condition proposed by manufacturer.
The present invention set up it is a kind of using Ultra Performance Liquid Chromatography-tandem mass spectrometry determine simultaneously ethyl phosphonic acid and phosphorous acid from
The content of son, by calculating its ratio and converting phosethyl-Al content is become.Phosethyl-Al is in the solution with ethyl phosphonic acid
Exist with two kinds of forms of phosphorous acid, quantitative presence of two kinds of acid presence ratio in the solution on phosethyl-Al affects.
Embodiment one
The presence ratio of ethyl phosphonic acid ion and phosphorous acid ion, prepares respectively the three of 0.5 μ g/mL in research different solutions
Fosetyl-aluminium solution, one of which is respectively 4 for the ratio of acetonitrile and water:1、2:1、1:1、1:2 and 1:4, another group is methyl alcohol
4 are respectively with the ratio of water:1、2:1、1:1、1:2 and 1:4.Using the standard liquid of two kinds of acid of ethyl phosphonic acid and phosphorous acid to three
Two kinds of acid in fosetyl-aluminium solution are carried out quantitatively, and calculate its ratio with sour total amount.Experimental result is shown in Fig. 1, it can be seen that
The ratio of two kinds of ions of ethyl phosphonic acid and phosphorous acid is each about 40% and 60%.
Embodiment two
Phosethyl-Al exists in the solution in two kinds of forms of ethyl phosphonic acid and phosphorous acid, cracking of two kinds of acid in ionization
Rule is the key of its accurate quantitative analysis.The present invention selects first negative ion mode to be excited, and the mode using direct injected is excellent
Change the condition of mass spectral analysis ethyl phosphonic acid and phosphorous acid.Ethyl phosphonic acid and phosphorous acid molecule such as Fig. 2 of the cleaved fragment in mass spectrum
Shown, in first mass spectrometric, ethyl phosphonic acid and phosphorous acid produce respectively stable [M-H]-ion, its m/ as parent ion
Z is respectively 109 and 81.It is determined that after its parent ion, under SIM patterns, being optimized to the fragmentation voltage (DP) of compound, second
The optimum DP of base phosphoric acid and phosphorous acid is -81V.Parent ion enters second order mses, the reaction such as fracture or rearrangement occurs and produces not
With fragment ion, wherein, the daughter ion of ethyl phosphonic acid is respectively phosphorous acid (quota ion, m/z=81) and metaphosphorous acid (calmly
Property ion, m/z=63), the daughter ion of phosphorous acid be respectively metaphosphoric acid (quota ion, m/z=79) and metaphosphorous acid (it is qualitative from
Son, m/z=63).
Embodiment three
To mass spectral analysis, there is certain interference in ionization of the compound to target compound in matrix, in order to improve sample
The quantitative precision of phosethyl-Al in product, tests by taking wild cabbage as an example, have studied the wild cabbage matrix matrix effect quantitative to object
Should.Using wild cabbage blank sample acetonitrile extract as vehicle solution, using pure acetonitrile solution as neat solvent solution, match somebody with somebody respectively
The triethylphosphine acid aluminum solutions of 0.1 μ g/mL are made, upper machine determines the response of two kinds of solution, and (matrix is imitated using relative response method
Should=bare substrate normal response value/neat solvent normal response value × 100%) calculate matrix effect of the wild cabbage to phosethyl-Al
Should.The peak area of ethyl phosphonic acid and phosphorous acid is determined with above two different solutions, 1 is the results are shown in Table, wild cabbage matrix is to ethyl phosphorus
The matrix effect of acid and phosphorous acid is respectively 80% and 103%, illustrates that matrix effect has certain impact on sample amounts.Cause
This, in order to reduce the interference that sample substrate effect is brought to object ionization, needs using correspondence matrix in sample analysis
Extract prepares standard items.
The TIANZHU XINGNAO Capsul of phosethyl-Al in the different samples of table 1
Example IV
Sample (wherein apple, banana, cucumber, wild cabbage, pedotheque take 10g, and water sample takes 10mL) is accurately weighed, is added respectively
Plus 0.01,0.10 and 0.50mg/kg triethylphosphine acid aluminum standard solution, each sample adds 20mL acetonitriles.Fruits and vegetables sample is at a high speed
Homogenate 2min, soil and water sample vibration 15min.1.5g sodium chloride is separately added into, acutely after concussion 1min, with 4000r/min's
Rotating speed is centrifuged 5min, divides and takes 5mL upper stratas acetonitrile solution, adds 100mg anhydrous magnesium sulfates and 100mg PSA adsorbents, acutely shake
After swinging 1min, 5min is centrifuged with the rotating speed of 4000r/min, takes supernatant 2mL as extract.
Containing for ethyl phosphonic acid ion and phosphorous acid ion in extract is determined using Ultra Performance Liquid Chromatography-tandem mass spectrum
Amount, the parent ion and quota ion pair of wherein ethyl phosphonic acid are respectively 109 and 81/63, the parent ion and quota ion of phosphorous acid
To being respectively 81 and 79/63.
It is 40 according to the presence ratio of ethyl phosphonic acid ion in extract and phosphorous acid ion：60, using equation below meter
Calculate triethylphosphine acid aluminium content in extract：
Triethylphosphine acid aluminium content=ethyl phosphonic acid ion concentration × 0.4+ phosphorous acid contents ion × 0.6.Use conventional analysis
Method determines the rate of recovery, the results are shown in Table 2.
The TIANZHU XINGNAO Capsul of phosethyl-Al in the different samples of table 2
The above is only the general embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, on the premise of without departing from the technology of the present invention principle, some improvements and modifications can also be made, these improvements and modifications
Also should be regarded as protection scope of the present invention.
Claims (1)
1. the method that a kind of Ultra Performance Liquid Chromatography-tandem mass spectrum detects phosethyl-Al, it is characterised in that its step is as follows：
1), accurately weigh addition acetonitrile after sample to be pre-processed, then press mass volume ratio for 1 by standard of acetonitrile：10～
15 ratio adds sodium chloride, acutely shakes after 1～3min, and 4～6min is centrifuged with the rotating speed of 4000r/min, takes upper strata acetonitrile
Solution；Volume mass ratio is pressed in acetonitrile solution for 1：0.02～0.025 ratio is separately added into anhydrous magnesium sulfate and PSA absorption
Agent, acutely shakes after 1～3min, and 5～7min is centrifuged with the rotating speed of 4000r/min, takes supernatant as extract, to be measured；Institute
It is fruits and vegetables sample, pedotheque or water sample to state sample；The preprocessing process is：It is by mass volume ratio in fruits and vegetables sample
1：2～3 ratio adds acetonitrile, then 2～5min of high-speed homogenization；Mass volume ratio is pressed in pedotheque for 1：2～3 ratio
Example adds acetonitrile, then vibrates 13～18min；It is by volume 1 in water sample：2～3 ratio adds acetonitrile, Ran Houzhen
Swing 13～18min；
2), containing for ethyl phosphonic acid ion and phosphorous acid ion in extract is determined using Ultra Performance Liquid Chromatography-tandem mass spectrum
Amount, the parent ion and quota ion pair of wherein ethyl phosphonic acid are respectively 109 and 81/63, the parent ion and quota ion of phosphorous acid
To being respectively 81 and 79/63；
3), chromatogram condition of work：UPLC chromatographic columns are ACQUITYBEH HILIC, column temperature：35 DEG C, flow velocity：
0.25mL/min, sample size：2μL；Mobile phase：A phases are acetonitrile, and B phases are 0.05% formic acid water (10/90, v/v), and its gradient is washed
De- condition is：0～0.5min, mobile phase A keeps 10%；0.5～3.0min, mobile phase A is changed into 90% from 10%；3.0～
3.5min, mobile phase A is changed into 10% from 90%；3.5～5.0min, mobile phase A keeps 10%；5.0min stop；
4), mass spectrum condition of work：Scan mode：Negative electrospray ionization is scanned；Detection mode：Multiple-reaction monitoring；Atomization gas：
379.225kPa；Spray voltage：4500kV；
5) it is, 40 according to the presence ratio of ethyl phosphonic acid ion in extract and phosphorous acid ion：60, calculated using equation below
Triethylphosphine acid aluminium content in extract：
Triethylphosphine acid aluminium content=ethyl phosphonic acid ion concentration × 0.4+ phosphorous acid contents ion × 0.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710141610.7A CN106645539B (en) | 2017-03-10 | 2017-03-10 | A kind of method of ultra performance liquid chromatography tandem mass spectrum detection phosethyl-Al |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710141610.7A CN106645539B (en) | 2017-03-10 | 2017-03-10 | A kind of method of ultra performance liquid chromatography tandem mass spectrum detection phosethyl-Al |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106645539A true CN106645539A (en) | 2017-05-10 |
| CN106645539B CN106645539B (en) | 2018-04-03 |
Family
ID=58847108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710141610.7A Active CN106645539B (en) | 2017-03-10 | 2017-03-10 | A kind of method of ultra performance liquid chromatography tandem mass spectrum detection phosethyl-Al |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106645539B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030637A (en) * | 2017-06-08 | 2018-12-18 | 烟台杰科检测服务有限公司 | The detection method of triethylphosphine acid Aluminium residual in a kind of food |
| CN110824090A (en) * | 2019-11-27 | 2020-02-21 | 日照健安检测技术服务有限公司 | Method for rapidly detecting residual quantity of fosetyl-aluminum in vegetables |
| CN112697915A (en) * | 2020-12-17 | 2021-04-23 | 青岛海关技术中心 | Method for measuring residual amount of phosphorous acid in plant-derived food |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006079566A1 (en) * | 2005-01-25 | 2006-08-03 | Bayer Cropscience Sa | Method of analyzing phosphorous acid, fosetyl-al or both simultaneously |
| CN101650344A (en) * | 2009-08-02 | 2010-02-17 | 青岛科技大学 | Detection and analysis method of content of fosetyl-aluminium |
| 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 |
-
2017
- 2017-03-10 CN CN201710141610.7A patent/CN106645539B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006079566A1 (en) * | 2005-01-25 | 2006-08-03 | Bayer Cropscience Sa | Method of analyzing phosphorous acid, fosetyl-al or both simultaneously |
| CN101650344A (en) * | 2009-08-02 | 2010-02-17 | 青岛科技大学 | Detection and analysis method of content of fosetyl-aluminium |
| 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 |
Non-Patent Citations (5)
| Title |
|---|
| HANS G. J. MOL ET AL.: "Rapid detection of pesticides not amenable to multi-residue methods by flow injection-tandem mass spectrometry", 《ANAL BIOANAL CHEM》 * |
| RENATA DOMINGOS ALVES ET AL.: "Fast determination of four polar contaminants in soy nutraceutical products by liquid chromatography coupled to tandem mass spectrometry", 《ANAL BIOANAL CHEM》 * |
| 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》 * |
| 王雪 等: "离子色谱法同时测定三(乙基膦酸)铝原药纯度及各杂质离子的含量", 《浙江大学学报（理学版）》 * |
| 郭春景 等: "利用QuEChERS-UPLC-MS/MS法测定甘蓝、草莓中7种农药残留的实验条件优化探索", 《质谱学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030637A (en) * | 2017-06-08 | 2018-12-18 | 烟台杰科检测服务有限公司 | The detection method of triethylphosphine acid Aluminium residual in a kind of food |
| CN110824090A (en) * | 2019-11-27 | 2020-02-21 | 日照健安检测技术服务有限公司 | Method for rapidly detecting residual quantity of fosetyl-aluminum in vegetables |
| CN112697915A (en) * | 2020-12-17 | 2021-04-23 | 青岛海关技术中心 | Method for measuring residual amount of phosphorous acid in plant-derived food |
| CN112697915B (en) * | 2020-12-17 | 2022-09-02 | 青岛海关技术中心 | Method for measuring residual amount of phosphorous acid in plant-derived food |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106645539B (en) | 2018-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104698114B (en) | The detection method of 205 kinds of persticide residues in a kind of rice | |
| CN106324123B (en) | The measuring method of persticide residue in tobacco and tobacco product | |
| CN102645498B (en) | Method for detecting residues of 202 pesticides in tobacco leaves | |
| Amais et al. | Tandem mass spectrometry (ICP-MS/MS) for overcoming molybdenum oxide interferences on Cd determination in milk | |
| CN104991019B (en) | Gelsemine and the liquid chromatography-tandem mass of koumine in biological material | |
| CN107300598B (en) | A kind of pre-treating method for Multiple Pesticides residue detection in tealeaves | |
| CN106645539B (en) | A kind of method of ultra performance liquid chromatography tandem mass spectrum detection phosethyl-Al | |
| CN107064339B (en) | Method for detecting volatile organic chloride in resin by headspace gas chromatography | |
| CN108072727A (en) | Method that is a kind of while measuring 23 kinds of organic chlorine agriculture chemicals residual quantities in Radix Notoginseng | |
| CN104458947A (en) | Method for determining 101 kinds of pesticide residues in tobaccos or tobacco products simultaneously | |
| CN106353418B (en) | A method of 28 kinds of pesticide residues in dark brownish green are measured simultaneously with the triple level four bars second order ms of gas-chromatography- | |
| Guan et al. | Modified QuEChERS method for the analysis of 11 pesticide residues in tea by liquid chromatography–tandem mass spectrometry | |
| Moghadam et al. | Simultaneous spectrophotometric determination of Fe (III) and Al (III) using orthogonal signal correction–partial least squares calibration method after solidified floating organic drop microextraction | |
| CN106153801A (en) | A kind of method of seven kinds of mycotoxins in Chinese liquor supplementary material of detection simultaneously | |
| CN109738565A (en) | The method of compound is illegally added in a kind of measurement health food | |
| CN107664670A (en) | The ultra performance liquid chromatography tandem mass spectrum detection method that kind bacterium azoles remain in corn | |
| CN106546683A (en) | A kind of method that LC MS/MS detect trifloxystrobin and metabolin oxime bacterium acid residual in rice simultaneously | |
| CN103472178B (en) | Rapid detecting method for acrylamide content in liquid state seasoning | |
| CN102331462B (en) | Method for measuring ammonia content in water base adhesive for tobaccos | |
| CN113820431A (en) | Method for measuring sulfur dioxide content in bamboo and wood products | |
| CN106404958A (en) | Method for quickly detecting contents of plant growth regulators in vegetables | |
| CN109254088A (en) | A kind of method of the chloro- 1,2- propylene glycol of 3- in measurement flavouring | |
| CN106053634A (en) | Method for detecting N-dimethyl nitrosamine in cooked meat products | |
| Shen et al. | Analysis of PAHs in air-borne particulates in Hong Kong City by heuristic evolving latent projections | |
| CN108760920A (en) | A method of cyazofamid and its metabolite residue amount are measured based on HPLC-MSMS methods |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210409 Address after: 571101 No. 201, block a, Haikou thermal science Plaza, Chinese Academy of Tropical Agricultural Sciences, Longhua District, Haikou City, Hainan Province Patentee after: Hainan TEPU Agricultural Technology Co.,Ltd. Address before: 570000, No. 4, West Xueyuan Road, Longhua District, Hainan, Haikou Patentee before: ANALYSIS & TESTING CENTER, CHINESE ACADEMY OF TROPICAL AGRICULTURAL SCIENCES |